Appendix C: Non-Destructive Evaluation (NDE) & Other Tests: Visual Examination

Appendix C C-l
Appendix C: Non-Destructive Evaluation (NDE) & Other

Tests
[Note to reader: This Appendix deals with a subject that is very extensive and in which new
and modified methods are continuously being developed. The purpose of the information
presented here is to provide a simple overview to aid the user in identifying and
understanding available testing techniques].
Non-Destructive Evaluation (NDE) is designed to provide as much infonnation on the

failure site, failure mechanism, and root cause of failure without causing any damage to
the product or obscuring or removing valuable infonnation. The latter can become very
important if the part in question is still functional.
Visual Examination (5), (21)
Visual examination is very important and can be supported using conventional and digital
photography and video equipment. Magnification systems can be used and inaccessible
locations reached using fiberscopes and borescopes. With photography multiple views
should be used to give as complete scanning as possible. Labeling and good organization
of test samples is important.
Leak Testing (27)
Leaks can arise whenever a differential pressure exists and there is access via a hole, a
crack or a seal. Very small apertures can still leak appreciable amounts when the pressure
differential is high. The simplest leak detecting, with gases, is to use the soap bubble test.
With liquids tracers can be used. More sophisticated methods include ultrasonic
techniques, colonnetric development techniques, hand-held gas detectors and radioactive
tracers.
Liquid Penetrant Inspection (LPI) (28)
Liquid penetrant inspection (LPI) can be used to inspect almost any material provided its
surface is not extremely rough or porous. Materials that are commonly inspected using
LPI include:
• Metals (aluminum, copper, steel, titanium, etc.)
• Glass
• Many ceramic materials
Copyright © 2006 by Dyadem Engineering Corporation

C-2 Appendix C
• Rubber
• Plastics
The penetrant material can be applied with a spray can or a cotton swab to inspect for
flaws known to occur in a specific area or it can be applied by dipping or spraying when
inspecting large areas. Liquid penetrant inspection is used to inspect for different types of
flaws such as:
• Fatigue cracks
• Quench cracks
• Grinding cracks
• Overload and impact fractures
• Porosity
• Laps
• Seams
• Pin holes in welds
• Lack of fusion or brazing along the edge of the bond line
Primary Advantages of LPI Primary Disadvantages of LPI
Very sensitive to small surface discontinuities Only surface breaking defects can be detected
Few material limitations Only materials with a relative nonporous

surface can be inspected
Large areas can be inspected at low cost Pre-cleaning is critical as contaminants can
mask defects
Indications are produced directly on the Metal smearing from machining, grinding and
surface of the part and constitute a visual grit or vapor blasting must be removed prior
representation of the flaw to LPI
Penetrant materials and associated equipment There is a need to have direct access to the
are relatively inexpensive and using aerosol surface being inspected
spray cans makes penetrant materials very
portable.

Appendix C C-3
Optical Microscopy (5)
Optical microscopy remains one of the cornerstones of NDE since it enables fracture
surfaces and fine detail, beyond the capability of the human eye, to be viewed. During
optical inspection, the specimen is positioned perpendicularly to the axis of the objective
lens. Light is then shone on the sample, which reflects some light back to the lens. The
image seen in the microscope depends not only on how the specimen is illuminated and
positioned, but also on the characteristics of the specimen. The viewing equipment
consists of:
• a lamp to illuminate the specimen
• a nose piece to hold 4-5 objectives used in changing the viewing magnification
• an aperture diaphragm to adjust the resolution and contrast
• a field diaphragm to adjust the field of view
• an eye piece to magnify the objective image (usually by lOX or greater)
• a support for manipulating the specimen.
There are three modes by which optical microscopy is commonly conducted:
• brightfield illumination
• darkfield illumination
• interference contrast (Nomarski).
Brightfield illumination is the normal mode when viewing using an optical microscope.
This provides the most unifonn illumination of the sample. Under this mode, a full cone
of light is focused by the objective on the sample. The image observed is the result of
the various levels of reflectivities exhibited by the compositional and topographical
differences on the surface of the sample.
With darkfield illumination, the inner circle area of the light cone is blocked, so the
sample is only illuminated by light that impinges on its surface at a glancing angle. This
scattered reflected light usually comes from feature edges, particulates, and other
irregularities on the sample surface. Hence darkfield illumination is effective in detecting
surface scratches and contamination.
Interference contrast (Nomarski method) makes use of polarized light that is divided by a
Wollaston prism into two orthogonal light packets. These slightly displaced light packets
strike the specimen at two different points and return to the prism through different paths.

C-4 Appendix C
The differences in the routes of the reflected packets will produce interference contrasts
in the image, when the packets are recombined by the prism upon their return. Surface
defects or features, such as etch pits and cracks, normally difficult to see under brightfield
illumination, stand out clearly when using the Nomarski mode.
Scanning electron microscopy (SEM) (2), (5)
Scanning electron microscopy (SEM) is a method for high-resolution imaging of

surfaces. SEM uses electrons for imaging, in the same way that a light microscope uses
visible light. The advantages of scanning electron microscopy over light microscopy
include greater magnification (up to IOO,OOOX) and a much greater depth of field. An
incident electron beam is raster-scanned across the sample's surface, and the resulting
electrons emitted from the sample are collected to fonn an image of the surface. Imaging
is typically obtained using secondary electrons for the best resolution of fine surface
topographical features. Alternatively, imaging with backscattered electrons (high-energy
electrons produced by elastic collision of an incident electron beam with the electron
cone of sample atom) gives contrast based on atomic number to resolve microscopic
composition variations, together with topographical information. Qualitative and
quantitative chemical analysis information is also obtained using an energy dispersive x-
ray spectrometer with scanning electron microscopy. Applications for SEM include:
• Microscopic feature measurement
• Fracture characterization
• Microstructure studies
• Thin coating evaluations
• Surface contamination examination
• Failure analysis
Energy Dispersive Microanalysis (EDS) (5)
Energy Dispersive Microanalysis (EDS) is the measurement of X-rays emitted during

electron bombardment in an electron microscope to determine the chemical composition
of materials on the micro- and nano- scale. By determining the energies of the X-rays
emitted from the area being excited by the electron beam, the elements present in the
sample are determined to give a qualitative analysis. In the microscope, the bombardment
by the energetic electron beam induces the emission of X-rays at energies that are
characteristic of the elements present in the sample. These X-rays are collected, sorted

Appendix C c-s
and counted and the result is presented as an EDS spectrum in which the presence of
peaks indicate the presence of the associated element. In addition, the height of the peaks
can be related to the concentration of the element, so quantitative elemental analysis is
possible. If the electron beam is rastered over an area of the sample then EDS systems
can also acquire X-ray maps showing spatial variation of elements in the sample.
X-ray microscopy (5)
X-ray microscopy is most widely used in the medical and biological fields to view the
internal components of living organisms. X-ray microscopy permits nondestructive
assessment of internal damage, defects, and degradation in microelectronic devices.
Illuminating a sample with X-ray energy provides images based on material density. This
allows characterization of solder voiding, wirebond sweep, and wirebond breakage in
electronic components. Its use in incident investigation may be limited but could prove
useful where encapsulated components need to be non-destructively evaluated.
Scanning Acoustic Microscopy (SAM) (5)
Scanning Acoustic Microscopy (SAM) is a failure analysis technique used for detecting
internal defects. A sound wave is sent through the specimen, and the interaction of the
sound wave with the specimen is interpreted. A typical scanning acoustic microscope
uses either pulse echo or through transmission inspection to scan for defects. Pulse echo
inspection interprets echoes sent back by the specimen while through transmission
inspection interprets the sound wave at the other end of the specimen, after it has passed
through the latter. Scanning acoustic microscopy (SAM) uses acoustic impedance to
produce high resolution images of a specimen's interior structure to detect "difficult-to-
find" defects. The ultrasonic wave frequency used ranges from 5 to 150 MHz.
Infrared Testing (5)
Infrared cameras/monitors are nonnally used prior to incidents in order to locate "hot
spots". However if there are intact components such as, say pumps, which can be run
following an incident, then suspected failures, such as overheating pump bearings can be
identified using infrared testing. Also, if there were to be a scan required of an area for
ignition sources involving hot surfaces, infrared testing could be useful.
Magnetic particle inspection (MPI) (29)
Magnetic particle inspection (MPI) is used for the detection of surface and near-surface
flaws in ferromagnetic materials. A magnetic field is applied to the specimen, locally or

C-6 Appendix C
overall, using either a permanent magnet, an electromagnet, flexible cables or hand-held

prods. Provided that the material is sound, most of the magnetic flux is concentrated
below the material's surface. But if a flaw is present, so it interacts with the magnetic
field, then the flux is distorted locally and "leaks" from the surface of the specimen in the
zone of the flaw. Fine magnetic particles that are applied to the surface of the specimen
are attracted to the area of magnetic flux leakage, thus indicating where the flaw exists.
The materials normally used for detection are black iron particles and red or yellow iron
oxides. In some cases, the iron particles are coated with a fluorescent material that
enables them to be seen under an ultra violet lamp in a darkened environment. Magnetic
particles are usually applied as a suspension in water or paraffin that enables them to flow
over the surface and to migrate to any flaws.
MPI is very sensitive to surface-breaking or near-surface cracks, even if the crack
opening is very narrow. However should the crack run parallel to the magnetic field,
there is little disturbance and it is unlikely that the crack will be detected. For this reason
it is recommended that the inspection surface is magnetized in two directions at 90° to
each other. In some cases, MPI can leave residual magnetic fields (which subsequently
interfere with welding repairs), but these can be removed by slowly wiping the surface
with an energized AC yoke.
MPI is used to detect surface-breaking and near-surface flaws in ferromagnetic materials.
It cannot be used to detect deeply embedded flaws, nor can it be used on non-
ferromagnetic materials, such as aluminum, copper or austenitic stainless steel. MPI is
often used to look for cracks at welded joints and in areas identified as susceptible to
environmental cracking (e.g. stress corrosion cracking or hydrogen induced cracking),
fatigue cracking or creep cracking. Wet fluorescent MPI is widely used for environmental
damage on the inside of vessels.
Eddy current testing (30)
Eddy current testing evaluates the changes in magnetic permeability and electrical
conductivity and can be used to detect surface and near-surface flaws, differences in
metal composition and heat treatment, hardness, case hardness depth and residual stress.
With heat exchangers eddy current testing is widely used as it is very effective for
detecting defects in tubes. Eddy current testing provides the ability to examine the
metallurgical integrity of a tube's wall thickness. Nonferrous metals readily accept
electromagnetic fields when induced, allowing eddy current analysis to be performed in a
variety of test modes, parameters and configurations. Properly calibrated and executed
testing can identify alloy composition, heat treatment, thickness and permeability.

Appendix C C-7
Because of eddy current testing response to these metallurgical properties, a wide variety
of failure mechanisms can be readily detected on both the tube inner and outer diameter
surfaces. Defects detection includes:
• Corrosion
• Electrolytic reaction
• Erosion
• Freeze bulges
• Galvanic action
• Mechanical wear
• Pitting
• Stress corrosion cracking
• Metallic deposition and plating
Ultrasonic Testing (UT) (31)
Ultrasonic testing uses beams of sound waves of short wavelength and high frequency,
transmitted from a probe and detected by the same or other probes. Usually, pulsed
beams of ultrasound are used. In the simplest instruments a single probe, hand held, is
placed on the specimen surface. An oscilloscope display, with a time base, shows the
time it takes for an ultrasonic pulse to travel to a reflector (a flaw, the back surface or
other free surface) in tenns of distance traveled across the oscilloscope screen. The height
of the reflected pulse is related to the flaw size as seen from the transmitter probe.
A typical UT system consists of several functional units, such as the pulser/receiver,
transducer, and display devices. A pulser/receiver produces high voltage electrical pulses.
Driven by the pulser, the transducer generates high frequency ultrasonic energy. The
sound energy is introduced and propagates through the specimen in the form of waves.
When there is a discontinuity, such as a crack in the wave path, part of the energy will be
reflected back from the flaw surface. The reflected wave signal is transfonned into an
electrical signal by the transducer and is displayed on the screen. Signal travel time is
directly related to the distance that the signal travels. From the signal, information about
the reflector location, size, orientation and other features may be obtained.
The detection of a defect involves other factors than just the relationship of wavelength
and flaw size. As an example, the amount of sound that reflects from a defect also
depends upon the acoustic impedance mismatch between the flaw and the surrounding

C-B Appendix C
materiaL A void is generally a better reflector than a metallic inclusion because the
impedance mismatch is greater between air and metal than between metal and other
metal.
UT is especially useful for detecting weld defects. The most commonly occurring defects
in welded joints are:
• Porosity and slag inclusions
• Lack of side-wall fusion
• Lack of inter-run fusion
• Lack of root penetration
• Undercutting
• Longitudinal or transverse cracks.
With the exception of single gas pores, all the defects listed are usually well detectable by
UT. Most applications are on low-alloy construction quality steels, but welds in
aluminum can also be tested.
Radiographic Testing (22)
Radiography uses differential absorption of radiation penetrating an object coupled with

recording of an image on film to detect features of the object that exhibit a difference in
thickness or physical density as compared to the surrounding material.
When a source of ionizing radiation is positioned on one side of an object and a
photographic film placed in close proximity to the other side, a full-size image showing
the internal details may be obtained. The radiation is partly absorbed during transmission
and differences in material thickness or absorption qualities are recorded on the film.
Materials that have higher density absorb more radiation. The technique, called
radiography, and the processed film images are called radiographs. Industrial radiography
requires X-rays or gamma rays to reveal hidden flaws in solid objects. The terms X-
radiography and gamma radiography indicate the source of radiation in use. X-rays are
generated electrically using a high voltage X-ray tube. Gamma rays are produced by the
natural disintegration of nuclei in a radioactive isotope. Radio isotopes such as Iridium
192 and Cobalt 60 are most commonly used. Radiography is a well-established technique
that is widely used to detect internal flaws in welds and castings. Although typically used
to verify weld quality during the fabrication of pressure vessels, pipelines, storage tanks
and other engineering structures, it can also be used following incidents to check for

Appendix C C-9
faults and defects that may be causative. It can be used on all metals, including light
metals such as aluminum to dense metals such as copper, and on non-metallic materials,
if low energy radiation sources are used.
It is particularly good at detecting volumetric flaws such as voids, gas pores and solid
inclusions and detennining the nature and dimensions (length and width) of flaws. It
cannot be used to measure the dimensions of flaws in the through-thickness direction.
Radiography is very useful for detecting flaws, termed discontinuities, in welding.
Discontinuities are interruptions in the typical structure of a material. These interruptions
may occur in the base metal, weld material or "heat affected" zones. The following
discontinuities are typical of all types of welding:
• Cold lap is a condition where the weld filler metal does not properly fuse with
the base metal or the previous weld pass material.
• Porosity is the result of gas entrapment in the solidifying metal.
• Cluster porosity is caused when flux coated electrodes are contaminated with
moisture.
• Slag inclusions are nonmetallic solid material entrapped in weld metal or
between the weld and the base metal.
• Incomplete penetration or lack of penetration occurs when the weld metal
fails to penetrate the joint.
• Incomplete fusion is a condition where the weld filler metal does not properly
fuse with the base metal.
• Internal concavity or suck back is a condition where the weld metal has
contracted as it cools and has been drawn up into the root of the weld.
• Internal or root undercut is an erosion of the base metal next to the root of the
weld.
• External or crown undercut is an erosion of the base metal next to the crown of
the weld.
• Offset and mismatch are terms associated with a condition where the two pieces
being welded together are not properly aligned.
• Inadequate weld reinforcement is an area of a weld where the thickness of
weld metal deposited is less than the thickness of the base material.

C-IO Apoendix C
• Excess weld reinforcement is an area of a weld that has weld metal added in
excess of that specified by engineering drawings and codes.
• Cracks can be detected in a radiograph only when they are propagating in a
direction that produces a change in thickness that is parallel to the X-ray beam.
The following discontinuities are peculiar to the Tungsten Inert Gas (TIG) welding
process. These discontinuities occur in most metals welded by the process including
aluminum and stainless steels:
• Tungsten inclusions. Tungsten is a brittle and inherently dense material used in
the electrode in tungsten inert gas welding.
• Oxide inclusions are usually visible on the surface of material being welded
(especially aluminum).
The following discontinuities are most commonly found in Gas Metal Arc Welds
(GMAW):
• Whiskers are short lengths of weld electrode wire, visible on the top or bottom
surface of the weld or contained within the weld.
• Burn-Through results when too much heat causes exceSSIve weld metal to
penetrate the weld zone.
Radiography is also used for detecting faults in castings, these typically include:
• Gas porosity or blow holes that are caused by accumulated gas or air which is
trapped by the metal during the casting process.
• Sand inclusions and dross are nonmetallic oxides, appearing on the radiograph
as irregular, dark blotches.
• Shrinkage is a fonn of discontinuity that appears as dark spots on the
radiograph.
• Cavity shrinkage appears as areas with distinct jagged boundaries.
• Dendritic shrinkage is a distribution of very fine lines or small elongated
cavities that may vary in density and are usually unconnected.
• Filamentary shrinkage usually occurs as a continuous structure of connected
lines or branches of variable length, width and density, or occasionally as a
network.

Appendix C C-ll
• Sponge shrinkage shows itself as areas of lacy texture with diffuse outlines,
generally toward the mid-thickness of heavier casting sections.
• Cracks are thin (straight or jagged) linearly disposed discontinuities that occur
after the melt has solidified.
• Cold shuts generally appear on or near a surface of cast metal as a result of two
streams of liquid meeting and failing to unite.
• Inclusions are nonmetallic materials in a supposedly solid metallic matrix.
• Core shift shows itself as a variation in section thickness, usually on
radiographic views representing diametrically opposite portions of cylindrical
casting portions.
• Hot tears are linearly disposed indications that represent fractures formed in a
metal during solidification because of hindered contraction.
• Misruns appear on the radiograph as prominent dense areas of variable
dimensions with a definite smooth outline.
• Mottling is a radiographic indication that appears as an indistinct area of more or
less dense images.
Acoustic Emission Testing (32)
In Acoustic Emission Testing, the specimen is stressed by applying a load. External or

internal forces are used to make discontinuities emit stress waves. Acoustic energy is
carried at all frequencies from well below to well above the audible range. By listening at
frequencies between the audible and ultrasonic ranges, discontinuity growth and
structural integrity can be examined. Acoustic Emission Testing can also be used with
materials such as fiberglass and other composite materials. Acoustic emission test loads
are applied in various ways that can include:
• Hydrostatic, hydraulic or pneumatic loading. Typically pressure vessels are
tested by applying pressure internal to the vessel. Storage tanks, which are not
classed as pressure vessels, are tested.
• Mechanical loading, by applying loads to load bearing locations.
• Thermal loading where temperature gradients produce time dependent
stress/strain fields.
• Normal in service loading by filling with liquid.

C-12 Appendix C
• Structures which are monitored during nonnal service conditions.
Chemical Analyses Methods
Spectroscopy (1), (2), (8), (14), (17), (23), (25)
Spectroscopy uses the interaction of energy with a specimen as the basis for analysis.
A spectrum is obtained, that is a plot of the intensity of energy detected versus
wavelength. This provides infonnation about atomic and molecular energy levels,
molecular geometries, chemical bonds, interactions of molecules, and related processes.
Spectra can be used to identify the components of a specimen (qualitative analysis) as
well as being used to measure the amount of material in a specimen (quantitative
analysis). A number of different instruments are used to perfonn spectroscopic analyses.
Spectroscopy requires an energy source (typically a laser or an ion or radiation source)
and a means of measuring the change in the energy source after it has interacted with the
sample (typically a spectrophotometer or an interferometer). There are number of
different types of spectroscopy, such as:
Atomic Absorption Spectroscopy (1), (14), (17) (also see Flame Atomic Absorption
Spectrometry, discussed below)
Energy that is absorbed by the specimen is used for identification purposes. Typically
absorbed energy causes light to be emitted from the sample, which can be measured by a
technique such as fluorescence spectroscopy.
Attenuated Total Reflectance Spectroscopy (ATR) (17)
This is the study of substances in thin films or on surfaces. The sample is penetrated by
an energy beam one or more times and the reflected energy is analyzed. Attenuated total
reflectance spectroscopy and the related technique, called frustrated multiple internal
reflection spectroscopy, are used to analyze coatings and opaque liquids. From an
incident standpoint organic, petroleum-based, non-water soluble solvents, such as
gasoline, can be detected at very low concentrations after an intense fire by several well
developed techniques. However, water miscible solvents, such as methyl, ethyl and
isopropyl alcohol have proven to be difficult to analyze. The water used to extinguish the
fire usually washes away such flammable materials by convection and also disperses it by
dissolution. Furthennore, most techniques used for analysis require organic solvents to
dissolve the materials to be analyzed. Since the flammables to be studied are in water,
they would need to be extracted with organic solvents reducing their concentration

Appendix C C-13
Purther. Attenuated Total Reflectance Spectroscopy (ATR) is a relatively sensitive and

selective technique that can be used to perform analysis on these water miscible
flammables.
Electron Paramagnetic Spectroscopy (17)
This microwave technique is based on splitting electronic energy fields in a magnetic

field. It is used to determine structures of specimens containing unpaired electrons.
Radicals are also known as paramagnetic species. The radical species respond to a
magnetic field due to the interaction of the magnetic field generated from the spin of their
unpaired electron(s) with the applied magnetic field. The interaction leads to two or
more split energy levels for the species. The gap between the levels falls in the energy
range of the microwave radiation. Thus, when a radical is subjected to suitable magnetic
field and microwave radiation simultaneously, absorption of the radiation occurs.
Electron Spectroscopy for Chemical Analysis (17)
There are several types of electron spectroscopy, all associated with measuring changes
in electronic energy levels. X-ray Photoelectron Spectroscopy is known as XPS or ESCA
(Electron Spectroscopy for Chemical Analysis). In XPS (X-ray photoelectron
spectroscopy) the sample is exposed to an X-ray beam and the energies of
characteristically emitted photoelectrons are measured. The binding energy of the photo
emitted electrons carries the information on the elements from which they originate as
well as the chemical bonding of the elements. For example, XPS can readily distinguish
between the ionic and covalent forms of fluorine, or whether the metal is in its oxidized
or in its metallic state. Therefore another name is often used for XPS, i.e. Electron
Spectroscopy for Chemical Analysis (ESCA). Instead of X-rays, resonance radiation
obtained from noble gas discharge lamps or even high energy electrons can be used to
excite electrons from solid surfaces and these methods of electron spectroscopy are
known as Ultraviolet Photoelectron Spectroscopy (UPS) and Auger Electron
Spectroscopy (AES), respectively. Due to the short inelastic mean free paths of the photo
emitted electrons, electron spectroscopy measurements only analyze the outermost two
through ten atomic layers of the surface. This means that electron spectroscopy is an
extremely surface sensitive analysis method. However, if the analyzed region is
embedded below the surface, ion etching can be u~ed to remove the topmost atomic
layers, after which the electron spectroscopy measurement can be performed. Electron
spectroscopy is sensitive to as low as 0.1 atom percent and detects elements except Hand
He. It is non-destructive and it can be applied to all solid materials, including insulators
such as polymers and glasses.

C-14 Appendix C
Fourier Transform Spectroscopy (5), (17)

This is a family of spectroscopic techniques in which the specimen is irradiated by all
relevant wavelengths simultaneously for a short period of time. The absorption spectrum
is obtained by applying a mathematical analysis to the resulting energy pattern. Fourier
Transform Spectroscopy is a measurement technique whereby spectra are collected
based on the response from a pulse of electromagnetic radiation. It can be applied to
variety of types of spectroscopic methods including infrared spectroscopy, nuclear
magnetic resonance, and electron spin resonance spectroscopy. Fourier transform
spectroscopy is more sensitive and has a much shorter sampling time than conventional
spectroscopic techniques.
With a conventional (or "continuous wave") spectrometer, a specimen is exposed to
electromagnetic radiation and the response (usually the intensity of transmitted radiation)
is monitored. The energy of the radiation is varied over the desired range and the
response is plotted as a function of radiation energy or frequency. At certain resonant
frequencies, characteristic of the specimen, the radiation will be absorbed resulting in a
series of peaks in the spectrum, which can then be used for identification.
Instead of varying the energy of the electromagnetic radiation, Fourier Transform
spectroscopy exposes the specimen to a single pulse of radiation and measures the
response. The resulting signal, called a free induction decay, contains a rapidly decaying
composite of all possible frequencies. Due to resonance by the specimen, resonant
frequencies will be dominant in the signal and by performing a mathematical operation,
known as a Fourier transform, on the signal, the frequency response can be calculated. In
this way the Fourier transform spectrometer can produce the same kind of spectrum as a
conventional spectrometer, but in a much shorter time.
The principles of the Fourier transform approach can be compared to the behavior of a
tuning fork. If a tuning fork is exposed to sound waves of varying frequencies, it will
vibrate when the sound wave frequencies are in resonance. This is similar to conventional
spectroscopic techniques, where the radiation frequency is varied and those frequencies
where the specimen is resonant with the radiation detected. However, if the tuning fork is
struck (the equivalent of applying a pulse of radiation), the tuning fork will vibrate at its
characteristic frequencies. The resulting tone consists ofa combination of all of the
characteristic frequencies for that tuning fork. Similarly the re~ponse for a specimen
exposed to a pulse of radiation is a signal consisting primarily of the characteristic
frequencies for that specimen. The Fourier transform is a mathematical technique for
determining these characteristic frequencies from a single composite signal.

Appendix C C-15
Infrared Spectroscopy (14), (17)
The infrared absorption spectrum of a substance is sometimes called its molecular

fingerprint. Although frequently used to identify materials, infrared spectroscopy may
also be used to quantify the number of absorbing molecules. Electromagnetic radiation is
comprised of perpendicular electric and magnetic fields that are in phase. Spectroscopy
involves the interaction of matter with electromagnetic radiation. Electromagnetic
radiation is composed of photons that have characteristic energies depending upon the
frequency of the radiation. Molecules can absorb this radiation and thus become excited.
These excitations can lead to structural information about the molecules in the specimen.
Infrared spectroscopy is particularly useful for identifying the various structural groups in
chemical compounds. Three typical functional groupings are shown in the table below,
although IR can also identify molecular motions for alkenes, alkynes, ethers, aldehydes,
ketones, carboxylic acids, esters, acid chlorides, anhydrides, amines, amides, alkyl
halides, nitriles, isocyanates, isothiocyanates, imines, nitro groups, mercaptans,
sulfoxides, sulfones, sulfonates, phosphines and phosphine oxides.
Functional Group Molecular Motion Wave number (em-i)
Alkanes C-H stretch 2950-2800
CH z bend --1465
CH3 bend --1375
CH z bend (4 or more) --720
Aromatics C-H stretch 3020-3000
C=C stretch --1600 & --1475
Alcohols O-H stretch --3650 or 3400-3300
C-O stretch 1260-1000
Molecular Fluorescence Spectroscopy (40)
Molecular fluorescence depends upon the optical emission from molecules that have been
excited to higher energy levels by absorption of electromagnetic radiation. The main
advantage of fluorescence detection compared to absorption measurements is the greater

C-16 Appendix C
sensitivity, achievable because the fluorescence signal has a very low background. The
resonant excitation provides selective excitation of the analyte to avoid interferences.
Analytical applications include quantitative measurements of molecules in solution and
fluorescence detection in liquid chromatography.
A typical fluorimeter contains an excitation source, a sample cell, and a fluorescence
detector. Molecules in solution are usually excited by ultra violet light and the excitation
source is usually a deuterium or xenon lamp. Broad band excitation light from a lamp
passes through a monochromator, which passes only a selected wavelength. The
fluorescence is dispersed by another monochromator and detected by a photomultiplier
tube. Scanning the excitation monochromator gives the excitation spectrum and scanning
the fluorescence monochromator gives the fluorescence spectrum.
Flame Atomic Absorption Spectrometry (7)

Flame Atomic Absorption Spectrometry can detect certain elements, as shown in the
periodic table below:
(50 elements in bold can be detected using atomic absorption while those shown in italic
cannot be detected using atomic absorption)
-- -
H He
Li Be B C N 0 F Ne
Na Mg AI Si P S CI Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg TI Pb Bi Po At Rn
Fr Ra Ac
Flame atomic absorption can be used for detecting metals and metalloids in
environmental specimens. It is very reliable and simple to use and the above periodic
table shows which elements are commonly detected through atomic absorption. This
technique uses the fact that ground state metals absorb light at specific wavelengths.
Metal ions, in a solution, are converted using a flame. Light of the appropriate

Appendix C C-17
wavelength is supplied and the amount of light absorbed is measured against a

standardized curve.
Flame atomic absorption spectroscopy requires a liquid sample to be aspirated, made into
an aerosol, mixed with combustible gases (such as acetylene and air or acetylene and
nitrous oxide) and ignited to create a flame whose temperature ranges from 2100 to 2800
°C.
During combustion, atoms of the element of interest in the specimen are reduced to free,
unexcited ground state atoms, which absorb light at characteristic wavelengths. The
characteristic wavelengths are specific to the elements present and accurate to 0.01-
O.lnm. Methods other than flame ionization include:
• Electrothermal atomization that requires a graphite furnace where, after thermal
pre-treatment, the sample is rapidly atomized. Since the dilution and expansion
effects of flame cells are avoided, and the atoms have a longer residence time in
the optical path, a higher peak concentration of atoms is obtained.
• A carbon rod analyzer that can be used to convert a powdered sample into an
atomic vapor. A current is applied to a very thin, heated carbon rod that contains
the solid sample in order to vaporize it.
• Tantalum boat analyzer that produces an atomic vapor from a solid sample. A
tantalum boat is electrically heated in a manner similar to the carbon rod system,
within an inert atmosphere.
Spectrophotometry (1)
When reacted with an organic agent the analyte forms a colored complex. The light
absorption of the colored solution is measured at a certain wavelength in the visible or
UV spectral range versus a calibrated reference standard. The absorption is proportional
to the concentration of the analyte. Normally a sample mass between 20 mg and 200 mg
is required. The detection limit varies from 1 and 10 mg/mg. Spectrophotometry has a
wide application ranging from main and minor component analysis to trace analysis of
numerous transition metals such as Fe, Co, Ni, Ti, Nb, and other elements, like Al or P.
Chromatographic Methods (33)
Chromatography is a method of separating substances in a mixture. It relies on

differences in partitioning coefficients between a flowing mobile phase and a stationary
phase to separate the components. Typically a column holds the stationary phase while

C-1B Appendix C
the mobile phase carries the sample through it. Sample components that partition strongly
into the stationary phase are retained longer by the column and are separated from
components that stay predominantly in the mobile phase and pass through the column
more rapidly.
As the components elute from the column they may be quantified by a detector and/or
collected for further analysis. Specific chromatographic methods include:
Gas Chromatography (GC) (34)
Gas chromatography is a chromatographic technique that can be used to separate organic

compounds that are volatile. A gas chromatograph consists of a flowing mobile phase, an
injection port, a separation column containing the stationary phase, a detector, and a data
recording system. The organic compounds are separated due to differences in their
partitioning coefficients between the mobile gas phase and the stationary phase in the
column.
High-Performance Liquid Chromatography (HPLC) (35)
High-performance liquid chromatography (HPLC) is a form of liquid chromatography

that separates compounds that are dissolved in solution. It consists of a reservoir of
mobile phase, a pump, an injector, a separation column, and a detector. Compounds are
separated by injecting a plug of the sample mixture into the column. The different
components in the mixture pass through the column at different rates due to differences in
their partitioning coefficients between the mobile liquid phase and the stationary phase.
Liquid Chromatography (LC) (36)
Liquid chromatography (LC) is an analytical chromatographic technique that separates

ions or molecules that are dissolved in a solvent. If the sample solution is in contact with
a second solid or liquid phase, the different solutes will interact with the other phase to
differing degrees due to differences in adsorption, ion-exchange, partitioning or size.
These differences allow the mixture components to be separated from each other to
determine the transit time of the solutes through a column.
Size Exclusion Chromatography (SEC) (37)
Size-exclusion chromatography (SEC) is also called gel-filtration or gel-penneation

chromatography (apC) and uses porous particles to separate molecules of different sizes.
It is generally used to separate biological molecules, and to determine molecular weights
and molecular weight distributions of polymers. Molecules that are smaller than the pore
size can enter the particles and therefore have a longer path and longer transit time than
larger molecules that cannot enter the particles. Molecules larger than the pore size

Appendix C C-19
cannot enter the pores and elute together as the first peak in the chromatogram. This
condition is known as total exclusion. Molecules that can enter the pores will have an
average residence time in the particles that depends on the molecules' size and shape.
Different molecules therefore have different total transit times through the column. This
portion of a chromatogram is called the selective permeation region. Molecules that are
smaller than the pore size can enter all pores, and have the longest residence time on the
column and elute together as the last peak in the chromatogram. The last peak in the
chromatogram determines the total permeation limit.
Thin-Layer Chromatography (TLC) (38)
Thin-layer chromatography (TLC) is useful for separating organic compounds. Because

of its simplicity and rapidity, it is often used to monitor the progress of organic reactions
and to check the purity of products. Thin-layer chromatography consists of a stationary
phase immobilized on a glass or plastic plate, and an organic solvent. The sample, either
liquid or dissolved in a volatile solvent, is deposited as a spot on the stationary phase. The
components of a sample can be identified by simultaneously running known references
and comparing with the sample. The bottom edge of the plate is placed in a solvent
reservoir, and the solvent moves up the plate by capillary action. When the solvent front
reaches the other edge of the stationary phase, the plate is removed from the solvent
reservoir. The separated spots are made visible using ultraviolet light or by placing the
plate in iodine vapor. The different components in the mixture move up the plate at
different rates due to differences in their partitioning coefficients between the mobile
liquid phase and the stationary phase.
Chemical Analysis and Measurement (10), (16)
Qualitative Chemical Analysis deals with the identification of elements or grouping of

elements present in a specimen. The techniques employed in qualitative analysis vary in
complexity, depending on the nature of the specimen. In some cases it is necessary only
to verify the presence of certain elements or groups for which specific tests applicable
directly to the specimen (e.g., flame tests, spot tests) may be available. Very often the
specimen is of a complex mixture, and a systematic analysis must be made so all the
constituents may be identified. The classical procedure for the complete systematic
analysis of an inorganic specimen consists of several parts. First, a preliminary dry test
may be performed, which may consist of heating the specimen to detect the presence of
such constituents as carbon (through the appearance of smoke or char) or water (through
the appearance of moisture) or introducing the specimen into a flame and noting the color
produced (certain elements may be identified by means of their characteristic flame

C-20 Appendix C
colors). After preliminary tests have been performed, the specimen is commonly
dissolved in water for later determination of anionic constituents (i.e., negatively charged
elements or groupings of elements) and cationic constituents (i.e., positively charged
elements or groupings of elements). The procedure followed is based on the principle of
treating the solution with a succession of reagents so that each reagent separates a group
of constituents. The groups are then treated successively with reagents that divide a large
group into subgroups or separate the constituents singly. When a constituent has been
separated it is further examined to confirm its presence and to establish the amount
present (quantitative analysis). Portions of the material are dissolved separately, and
different procedures are used for each to detect the cationic and anionic constituents. The
analysis for anions is more difficult and less systematic than for cations. The organic
nature of a compound is generally indicated by its behavior on being heated in air; solids
usually melt, then bum with either a smoky or non-smoky flame, in some instances
leaving a black residue of carbon. The elements usually present in these compounds are
carbon, hydrogen, oxygen, nitrogen, sulfur, and, occasionally, phosphorus, halogens, and
some metals. Specific tests are available fJr each of the individual elements.
Qualitative analysis is normally used to analyze for inorganic components. It is used to
separate and detect cations and anions in a specimen. The semi-micro level of qualitative
analysis is used to detect 1-2 mg of an ion in 5 mL of solution. First, ions are removed in
groups from the initial aqueous solution. After each group has been separated, testing is
conducted for the individual ions in each group. A common grouping of cations is as
follows:
• Group I: Ag+, Hg22+, Pb2+ (precipitated in 1 M HCI)
• Group II: Bi3+, Cd2+, Cu2+, Hg2+, (Pb2+), Sb3+ and Sb5+, Sn2+ and Sn4+
(precipitated in 0.1 M H2S solution at pH 0.5)
• Group III: AI3+, (Cd2+), Co2+, Cr3+, Fe2+ and Fe3+, Mn2+, Ni2+, Zn2+
(precipitated in 0.1 M H2S solution at pH 9)
• Group IV: Ba2+, Ca2+, K+, Mg2+, Na+, NH4+ (Ba2+, Ca2+, and Mg2+ are
precipitated in 0.2 M (NH4)2C03 solution at pH 10 while the other ions are
soluble)
A number of reagents are used in qualitative analysis, but only a few are involved in
nearly every group procedure. The four most commonly used reagents are 6M HeI, 6M
RN0 3, 6M NaOH, and 6M NH3 and their effects are shown below:

Appendix C C-21
Reagent Used Effects of Reagent
Increases [H+]
Increases [CI-]
Decreases [OH-]
6MHCI
Dissolves insoluble carbonates, chromates, hydroxides, some sulfates
Destroys hydroxo and NH 3 complexes
Precipitates insoluble chlorides
Increases [Hl
Decreases [OH-]
Dissolves insoluble carbonates, chromates, and hydroxides
6MHN0 3
Dissolves insoluble sulfides by oxidizing sulfide ion
Destroys hydroxo and ammonia complexes
Good oxidizing agent when hot
Increases [OH-]
Decreases [H+]
6MNaOH
Forms hydroxo complexes
Precipitates insoluble hydroxides
Increases [NH 3]
Increases [OH-]
Decreases [H+]
6MNH3
Precipitates insoluble hydroxides
Forms NH 3 complexes
Forms a basic buffer with N~+
Among the most common reactions in qualitative analysis are those involving the
formation or decomposition of complex ions and precipitation reactions. These reactions
may be performed directly by adding the appropriate anion, or a reagent such as H2S or
NH 3 may dissociate in water to provide the anion. Strong acid may be used to dissolve
precipitates containing a basic anion. Ammonia or sodium hydroxide may be used to
bring a solid into solution if the cation in the precipitate forms a stable complex with NH3
or OH-. The following table shows complexes of cations with NH 3 and OH-:

C-22 Appendix C
Cation NH3 Complex OH- Complex
Ag+ Ag(NH 3)2+ -

A1 3+ - AI(OH)4-
Cd 2 + Cd(NH 3)4 2+ -
Cu 2 + Cu(NH 3)4 2 + (blue) -
Ni 2 + Ni(NH 3)6 2 + (blue) -
Pb 2 + - Pb(OH)3-
Sb 3+ - Sb(OH)4-
Sn 4+ - Sn(OH)6 2 -
Zn 2 + Zn(NH3)4 2 + Zn(OH)4 2 -
A cation is usually present as a single principal species, which may be a complex ion, a
free ion, or precipitate. If the reaction goes to completion the principal species is a
complex ion. The precipitate is the principal species if most of the precipitate remains
undissolved. If a cation forms a stable complex addition of a complexing agent, at 1 M or
greater generally, will convert the free ion to a complex ion.
The dissociation constant Kt can be used to determine the extent to which a cation is
converted to a complex ion. The solubility product constant K sp can be used to determine
the fraction of cation remaining in a solution after precipitation. Kt and Ksp are both
required to calculate the equilibrium constant for dissolving a precipitate in a complexing
agent.
Quantitative Chemical Analysis is a branch of chemistry that deals with the determination
of the amount or percentage of one or more constituents of a sample. A variety of
methods is employed for quantitative analyses, which for convenience, are broadly
classified as chemical or physical analyses, depending upon the properties utilized.
Chemical methods depend upon such reactions as precipitation, neutralization, oxidation,
or, in general, the formation of a new compound. The major types of strictly chemical
methods are known as gravimetric analysis and volumetric, or titrimetric, analysis.
Physical methods involve the measurement of some physical property such as density,
refractive index, absorption or polarization of light, electromotive force, magnetic

Appendix C C-23
susceptibility, and numerous others. An analysis will often require a combination of

methods: qualitative for separating desired constituents from a sample and quantitative
for measuring the amounts present. The basic tool in all quantitative analyses is the
analytical balance, used for the accurate weighing of samples and precipitates. For usual
analytical work the balance should be able to determine differences in mass of 0.1
milligram (about 0.000004 ounce). In microanalyses the balance must be about 1,000
times more sensitive, and, for special work, balances of even higher sensitivity have been
constructed.
Electron Spin Resonance (4)
The phenomenon of electron spin resonance (ESR) is based on the principle that an
electron is a charged particle which spins around its axis: this causes it to act like a tiny
bar magnet so it has a magnetic moment, the value of which is called the Bohr magneton.
If an external magnetic field is present, the electron will align itself with the direction of
this field and process around this axis. Increasing the applied magnetic field induces the
electron to process faster and acquire more kinetic energy. In practice, the magnetic field
will divide the electrons into two groups. In one group the magnetic moments of the
electrons are aligned with the magnetic field, while in the other group the magnetic
moments are aligned opposite or anti-parallel to this external field.
If a second weaker alternating magnetic field oscillating at a microwave frequency is now
applied at right angles to the main field, then the electron can be "tipped" over when the
microwave frequency is equal to the precession frequency. Another way to describe the
phenomenon of ESR is to say that the quanta of the incident microwaves induce
transitions between the two states of the unpaired electron. When the energy of these
quanta coincides with the energy level separation between the two states then resonance
absorption of energy takes place. The incoming radiation absorbed by the electrons in the
lower energy level will induce these electrons to jump into the higher energy state. The
incoming radiation is also absorbed by the electrons in the higher energy level, causing
them to jump down to the lower level, a phenomenon called stimulated emission.
Since the coefficients of absorption and stimulated emission are equal, no net value
would be observed if the spin population was equally distributed between these two
levels. However the population of the ground state exceeds the population of the excited
state, and a net absorption of microwave radiation takes place. The population ratio of
these two states at the temperature can, in most cases, be described by the Boltzmann
distribution. A material containing atomic magnetic moments satisfying this Boltzmann
distribution is called paramagnetic

c- 24 Appendix C
In most substances chemical bonding results in the pairing of the electrons which are
transferred from one atom to another atom to form an ionic bond; or are shared between
atoms to form a covalent bond, so these materials are not magnetic. However, in a
paramagnetic substance, Le. one which contains unpaired electrons, resonance occurs at
defmite values of the applied magnetic field and incident microwave radiation.
An observed spectrum sometimes contains several lines referred to as hyperfine structure
arising from the electrons interacting with nuclear spins. The electronic spin of a
transition metal ion usually interacts with its own nuclear spin, and in aromatic free
radicals, the unpaired electron circulates among several atoms; and the resultant
hyperfine structure is the result of the interaction of this electronic spin with several
atoms, such as hydrogen, with nuclear spins. Electron spin resonance is used for a
number of different analyses, including:
• Identification of elements of the various transition series in solids and solids
• Identification of valence states
• Identification of various magnetic states, such as ferromagnetic and anti-
ferromagnetic
• Study of catalyst surfaces and their free radical reactions
Inductively-Coupled Plasma - Atomic Emission Spectroscopy (ICP-AES) (1),

(9), (12)
Atomic emission spectroscopy (AES) measures the optical emission from excited atoms
to determine the sample concentration. Atoms from the sample in solution are aspirated
into the excitation region where they are desolvated, vaporized, and atomized by a flame,
discharge, or plasma. High-temperature atomization sources are used to promote the
atoms into high energy levels. This causes them to decay back to lower levels by emitting
light. Inductively-coupled plasma (ICP) is a very high temperature (7,OOO-8,OOOK)
excitation source that efficiently desolvates, vaporizes, excites, and ionizes atoms.
The standard ICP-AES instrument is a radial configuration. Newer models have an axial
configuration, and give lower detection limits. Each configuration has pro's and con's;
radial configurations have a proven track record and higher detection limits, while axial
configurations have lower detection limits but may not able to reproduce results as
consistently. The following is a periodic table showing elements that may be detected
using ICP-AES, together with the limits of detection, in parts per billion.

Appendix C C-25
Periodic Table showing elements detectable, shown in bold, using Inductively-Coupled

Plasma - Atomic Emission Spectroscopy (ICP-AES) and displaying limits of detection, in
parts per billion:
r----- r----
H He
Li Be B C N 0 F Ne
0.3 .08 0.8 75
3 .07 3 3 30 30
20 .02 .2 .4 .5 2 .4 2 1 5 .4 1 4 20 50 50
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
30 .03 .3 .7 10 3 6 5 3 .9 1 9 60 10 10
.09 1 4 10 8 5 6 5 10 8 1 30 10 30
Fr Ra Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lw
15
Rare Earths
Ce Pr Nd Pm 8m Eu Gd Tb Dy Ho Er Tm Yb Lu
5 2 2 2 .2 .9 2 2 .4 1 .6 .3 .2
Inert Gas Fusion (15)
Inert Gas Fusion is used to determine nitrogen and oxygen content in ferrous and non-
ferrous metals in one analysis on the same instrument by inert gas fusion. Samples are
carefully weighed and placed in a graphite crucible - usually with a fluxing agent such as
Ni - and then the crucible is inserted into a DC electrode furnace. After purging with He,
a high current is applied to the crucible and the sample fuses, releasing nitrogen and
oxygen. The helium gas purging the crucible carries the nitrogen and oxygen through a

C-26 Apoendix C
series of traps and catalysts designed to convert the gases so they can be detected. The
gas stream then goes to an infrared or thennal conductivity detector for measurement.
Instrument calibrations are performed using known reference standards. Hydrogen is also
determined by inert gas fusion. The main difference is that the detector system is tuned
for hydrogen instead of nitrogen or oxygen.
The specimens are usually around 2 g or less, so that they may need to be cut to size.
Contamination with nitrides, oxides or hydrides should be avoided. Materials with stable
nitrides or oxides require addition of fluxes.
Neutron Activation Analysis (NAA) (19)
Neutron activation analysis (NAA) is a sensitive analytical technique used for both
qualitative and quantitative multi-element analysis of major, minor, and trace elements in
samples. For many elements and applications, it offers sensitivities that are superior to
those attainable by other methods, of the order of parts per billion or better. In addition,
because of accuracy and reliability, NAA is sometimes known as the "referee method"
when new procedures are being developed or when other methods yield results that do
not agree. To carry out an analysis of samples by NAA a source of neutrons,
instrumentation suitable for detecting gamma rays, and a detailed knowledge of the
reactions that occur when neutrons interact with target nuclei, are required.
The most common type of nuclear reaction used for NAA is the neutron capture or (n,
gamma) reaction. When a neutron interacts with the target nucleus, via a non-elastic
collision, a compound nucleus forms, in an excited state. The excitation energy of the
compound nucleus is due to the binding energy of the neutron with the nucleus. The
compound nucleus almost instantaneously de-excites into a more stable configuration
through emission of one or more characteristic prompt gamma rays. In many cases, this
new configuration yields a radioactive nucleus. This de-excites (or decays) by emission
of one or more characteristic delayed gamma rays, but at a much slower rate according to
the unique half-life of the radioactive nucleus. Depending upon the particular radioactive
species, half-lives can range from fractions of a second to several years.
As regards to time measurement, NAA falls into two categories: (1) prompt gamma-ray
neutron activation analysis, where measurements take place during irradiation, or (2)
delayed gamma-ray neutron activation analysis, where the measurements follow
radioactive decay. The second operational mode is more common and thus it is generally
assumed that measurement of the delayed gamma rays is intended. About 70% of
elements have properties suitable for measurement by NAA.

Appendix C C-27
The sensitivities for NAA depend upon the irradiation parameters, such as neutron flux,
irradiation and decay times, measurement conditions such as measurement time and
detector efficiency, nuclear parameters of the elements being measured such as isotope
abundance, neutron cross-section, half-life, and gamma-ray abundance. The accuracy of
an individual NAA detennination usually ranges between 1 to 10 percent of the reported
value. The following periodic table lists approximate sensitivities for determination of
elements, assuming interference free spectra.
Periodic table, showing estimated detection limits of sensitivity in nanograms, for INAA
using decay gamma rays for elements (in bold) detectable by INAA. Assuming
irradiation in a reactor neutron flux of 1E 11 neutrons per square centimeter per second.

...---- ....----
H He
Li Be B C N 0 F Ne
1E4 1E4
to to
1E5 1E5
100 1E3 100 1E3 1E3 1E6 10 10

to to to to to to to
1E3 1E4 1E3 1E4 1E4 100 100
1E3 1E3 10 1E3 10 100 .1 1E4 10 100 10 100 10 100 10 10 10 100

to to to to to to to 1 to to to to to to to to to to to
1E4 1E4 100 1E4 100 1E3 1E5 100 1E3 100 1E3 100 1E3 100 100 100 1E3
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
100 100 1E3 100 1E4 100 100 100 100 10 100 .1 to 1E3 10 100 10 1E3
to to to to to to to to to to to 1 to to to to to
1E3 1E3 1E4 1E3 1E5 1E3 1E3 1E3 1E3 100 1E3 1E4 100 1E3 100 1E4

Cs Ba La Hf Ta W Re as Ir Pt Au Hg TI Pb Bi Po At Rn
10 100 10 10 10 1 to 1 to 100 1 to 1E3 1 to 100 1E3 1E6 1E3

to to to to to 10 10 to 10 to 10 to to to
100 1E3 100 100 100 1E3 1E4 1E3 1E4 1E4
10 10
to to
100 100
Rare Earths
Ce Pr Nd Pm 8m Eu Gd Tb Oy Ho Er Tm Vb Lu
100 100 1 to .1 100 10 .1 1 to 10 10 10 .1 to

to to 10 to to 10 to to to 1
1E3 1E3 1E3 100 100 100 100

C-30 Appendix C
Nuclear Magnetic Resonance (NMR) Spectroscopy (11), (14), (20), (24)
Nuclear magnetic resonance spectroscopy, commonly referred to as NMR, has become

very important for detennining the structure of organic compounds. It can provide a
complete analysis and interpretation of the entire spectrum. Although larger amounts of
sample are needed than for mass spectroscopy, NMR is non-destructive, and with modem
instruments good results may be obtained from samples weighing less than a milligram.
NMR is the same as the medical technique known as, MRI or Magnetic Resonance
Imaging. NMR is a characterization technique where a sample is immersed in a magnetic
field and bombarded with radio waves. These radio waves encourage the nuclei of the
molecule to resonate. The decoder used is called the Fourier Transfonn algorithm.
Nuclei possessing angular moment (also called spin) have an associated magnetic
moment. A few examples of magnetic isotopes are 13C, IH, 19F,14N , 170, 31p, and 33S
although not every isotope is magnetic. In particular, 12C is not magnetic. If a nucleus is
not magnetic, it cannot be studied by NMR. Generally speaking, these special nuclei
should be thought of as tiny, atomic, bar magnets. NMR is based on the fact that when a
population of magnetic nuclei is placed in an external magnetic field, the nuclei become
aligned in a predictable and finite number of orientations. For IH there are two
orientations. In one orientation the protons are aligned with the external magnetic field
(north pole of the nucleus aligned with the south pole of the magnet and south pole of the
nucleus with the north pole of the magnet) and in the other where the nuclei are aligned
against the field (north with north, south with south). The alignment with the field is also
called the "alpha" orientation and the alignment against the field is called the "beta"
orientation.
NMR spectroscopy involves using energy in the fonn of electromagnetic radiation to
pump the excess alpha oriented nuclei into the beta state. When the energy is removed,
the energized nuclei relax back to the alpha state. The fluctuation of the magnetic field
associated with this relaxation process is called resonance and this resonance can be
detected and converted into the peaks we see in an NMR spectrum.
The presence of electrons around a nucleus shields the nucleus from the applied magnetic
field. Therefore the magnetic field that is actually experienced by the nucleus will depend
on the local chemical structure. Because the nuclei experience different effective applied
magnetic fields, their Larmor frequencies vary too. Thus they experience a shift in
Lannor frequency due to their chemical structure. Chemical shift is measured in Hz or
parts per million (ppm). The preferred unit is ppm, because it is independent of magnetic

Appendix C C-31
field strength, but there are specific occasions In which it is useful to measure the
chemical shift in Hz.
Chemical concentrations are measured by comparison with a standard of a known
chemical concentration. Each atom of a particular chemical compound produces a peak at
a specific chemical shift (ppm). The area underneath this peak is an indication of the
numbers of that particular atom present in the sample. Additional consideration must be
made for relaxation time differences between the chemicals. By comparing areas
between the peaks corresponding to the atom of interest with that of an atom from a
chemical compound of known concentration, one can determine the chemical
concentration of the atom of interest.
Raman Spectroscopy (14), (18)
Raman spectroscopy is based upon the Raman effect which is the scattering of light from
a gas, liquid or solid with a shift in wavelength from that of the usually monochromatic
incident radiation. Discovered by the Indian physicist, C. V. Raman in 1928, it has also
been called the Smekal-Raman effect. The vibrational Raman effect is especially useful
in studying the structure of polyatomic molecules.
Like infrared spectrometry, Raman spectrometry is used to detennine modes of molecular
motion, especially the vibrations: their use in analysis is based on the specificity of these
vibrations. The methods are mainly applicable to the qualitative and quantitative analysis
of covalently bonded molecules rather than to ionic structures. However, they can give
information about the lattice structure of ionic molecules in the crystalline state and about
the internal covalent structure of complex ions and the ligand structure of coordination
compounds both in the solid state and in solution.
Both the Raman and the infrared spectrum yield a partial description of the internal
vibrational motion of the molecule in terms of the normal vibrations of the constituent
atoms. Neither the Raman nor the infrared alone gives a complete description of the
pattern of molecular vibration, although, by analysis, the difference between the two
spectra can yield additional information about the molecular structure. Physical chemists
have made extremely effective use of such comparisons to obtain finer structural details
of small symmetrical molecules, such as methane and benzene. The mathematical
techniques of vibrational analysis are not yet sufficiently developed to permit the
extension of these differential studies to the Raman and infrared spectra of the more
complex molecules that constitute the main body of both organic and inorganic
chemistry. The analytical chemist can use Raman and infrared spectra in two ways. At
the purely empirical level they provide " fingerprints " of the molecular structure to

C-32 Appendix C
permit the qualitative analysis of individual compounds, either by direct comparison of

the spectra of the known and unknown materials run consecutively, or by comparison of
the spectrum of the unknown compound with catalogs of reference spectra.
By comparisons among the spectra of large numbers of compounds of known structure, it
has been possible to recognize, at specific positions in the spectrum, bands which can be
identified as "characteristic group frequencies" associated with the presence of localized
units of molecular structure in the molecule, such as methyl, carbonyl, or hydroxyl
groups. Many of these group frequencies differ in the Raman and infrared spectra. In
inorganic materials, the information is linked to specific bonds, which helps to identify
the material as carbonate, oxide etc.
Laser-Induced Breakdown Spectroscopy (LIBS) (39)
Laser-Induced Breakdown Spectroscopy (LIBS) is a type of atomic emISSIon

spectroscopy, a pulsed laser being used as the excitation source. The output from a pulsed
laser is focused onto the surface of the material that is being analyzed. The laser pulse
could typically last for around 10 nanoseconds at an intensity of 1 Gigawatt per square
centimeter using a compact laser device and simple focusing lenses. At such high
localized power densities, a fraction of a microgram of material is ejected from the
material surface by laser ablation. This is short-lived and involves a highly luminous
plasma with instantaneous temperatures that can reach 10,OOO°C at the surface. The
ejected material dissociates into excited ionic and atomic species. Following the laser
pulse the plasma rapidly cools as it expands outwards at supersonic speeds. Under these
conditions the excited ions and atoms emit radiation in the optical spectra as they revert
to their lower energy states. This radiation spectra characterizes the material being
analyzed. Detection and spectral analysis can yield information about the material's
elemental composition.
Periodic Table showing elements detectable, shown in bold, using Laser-Induced
Breakdown Spectroscopy (LIBS) and displaying limits of detection, in parts per million
and Q = Qualitative detection only:

,....-- -
H He
Li Be B C N 0 F Ne
1-10 < 1 1-10 1- Q
ppm ppm ppm 100

ppm
1-10 < 1 1- 1- 100- 1-

ppm ppm 100 100 500 100
ppm ppm ppm ppm
1- 1-10 Q 1-10 100- < 1 1-10 < 1 1- 1-10 1-10 1-10 1- 100- 100-
100 ppm ppm 500 ppm ppm ppm 100 ppm ppm ppm 100 500 500
ppm ppm ppm ppm ppm ppm
Rb Sr y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
1- 1-10 >500 1- 1- 100- 1- Q 1- < 1 1- >500 1- >500 >500

100 ppm ppm 100 100 500 1 100 ppm 100- ppm 100 ppm ppm
ppm ppm ppm ppm 0 ppm ppm ppm

0

p
p
m
1- 1-10 >500 >500 1- 100- < 1 1- 1-10 100-

100 ppm ppm ppm 100 500 ppm 100 ppm 500
ppm ppm ppm ppm ppm
1-10 Q Q Q
ppm
Rare Earths I
Ce Pr Nd Pm 8m Eu Gd Tb Dy Ho Er Tm Yb Lu
1- Q Q
100
ppm

Appendix C C-35
X-Ray Diffraction (2), (26)
X-rays are electromagnetic radiation of wavelength about 1 A (10- 10 m). They are found
in that portion of the electromagnetic spectrum between gamma and ultraviolet rays. As a
result of the discovery of X-rays, in 1895, scientists were able to probe crystalline
structure at the atomic level. X-ray diffraction has been used for both the fingerprint
characterization of crystalline materials and the determination of their structure. Each
crystalline solid has a unique characteristic X-ray powder pattern that may be used for
identification purposes. Once the material has been identified, X-ray crystallography may
then be used to determine the structure. The structure relates how the atoms pack together
in the crystalline state and what the inter-atomic distance and angles are. X-ray
diffraction is used in solid state chemistry and can determine the size and shape of the
unit cell for any compound using the diffraction of X-rays. Diffraction patterns are
governed by the Bragg equation.
Gravimetric and electrogravimetric analysis (1)
By using gravimetric analysis, the mass of a product can be used to calculate the quantity
of the original analyte. An insoluble, easily filterable and very pure precipitate of a
defined chemical compound should be formed by a chemical reaction of a reagent with
the analyte solution. In electrogravimetry, a metal, except for alkali and earth alkali
elements, is electrochemically deposited on a platinum gauze cathode. Sample
requirements are about 100-500 mg as solid sample are needed. The detection limit is
about 5 mg. The main applications are for main component analysis of some metallic or
non-metallic elements such as eu, Ni, Pd, or Si.
Titration (1)
In a titration, increments of a reagent solution, known as the titrant, are added to the
analyte until the reaction is fully completed. From the quantity of titrant required, the
quantity of analyte present can be calculated. The main requirements for a titration
reaction are to have a large equilibrium constant and to proceed rapidly. Each increment
of titrant should be completely and quickly consumed by the analyte until the analyte is
fully converted. The most common types of titrations are acid-base, oxidation-reduction,
complex formation, or precipitation reactions titrations. Equivalence occurs when the
quantity of added titrant comes up to the exact amount necessary for stoichiometric
reaction with the analyte. The end point is usually marked by a sudden change of a
physical property, such as electrochemical potential, conductivity, pH, or the color of an
indicator. Normally a sample mass between 20 mg and 500 mg is required, the detection

C-36 Appendix C
limit being around 0.1 mg. Titration is used for the main component analysis of metals
(except earth alkali metals), precise determination of stoichiometric and oxidation
numbers and for determining the concentrations of acids and bases.
Mechanical Testing (3), (6)
Samples of materials from an incident scenario may need to be tested for a number of
mechanical properties that may typically include:
• Adhesion (bonding)
• Bending tests
• Compression testing
• Crack detection
• Creep and stress relaxation
• Drop (shock) testing
• Ductility testing
• Elasticity testing
• Fatigue testing
• Hardness testing
• Impact toughness
• Shear force testing
• Tensile force testing
• Thermal expansion
• Vibration testing
Specific mechanical tests are listed above. ASTM defines adhesion as the state in which
interfacial forces, which may consist of valence forces, interlocking action, or both,
holding two surfaces together. Adhesion is considered to be one of the most important
properties of thin film systems. Compressive properties can be very different from
tensile properties. Tests that characterize material performance under which there is
constant strain or stress conditions fall into the category of creep and stress relaxation
tests. Such tests can provide valuable information as to material or component properties
under long term conditions. Drop mechanical testing is also called shock testing.

Appendix C C-37
Information obtained during shock testing can confirm the survivability when in service.
Ductility is also called flex or bend testing: it is the ability to undergo plastic deformation
in tension or bending before fracturing. Fatigue testers are also called dynamic testers:
they measure the fatigue resistance, or resistance to failure, of materials under controlled
conditions of cyclic deformation. The two most commonly used methods of impact
testing are Charpy and Izod tests: impact tests measure the energy absorbed by the
specimen before it breaks, a quantity composed of several energy contributions, including
energy absorbed by the impact machine through vibrations after initial contact with the
specimen and loss in pendulum energy (in pendulum impact tests) when the hammer
strikes the specimen as well as the total energy consumed by specimen deformation and
fracture. The shear strength is the maximum stress that a material can withstand before
failure in shear and the calculation of shear strength is dependent upon the test method.
Tensile mechanical testing is one of the most common type of testing. Vibration tests are
often most relevant on assemblies where it is suspected that a resonant harmonic effect
may exist that could lead to destruction by over-displacement.

C-38 Appendix C
Ref. References and Suggested Reading

No. (Note: Internet URLs current at date of publication)
1 "Analytical Methods & Applications" Dr. Volker Hoffmann, IFW Dresden
http://www.ifw-
dresden.de/ifs/33/Methoden/Mk_e.htm#Wet % 20ChemicaIOjo20Element % 20analys
is
2 "Chemical Analysis Techniques", Materials Co. UK
http://www.materials.co.uk/chem.htm
3 "Izod Impact Test", About Inc.
http://metals.about.com/library/bldef-Izod-Impact-Test.htm
4 "Overview of Electron Spin Resonance and its Applications", H. A. Farach et aI.,

Dept. of Physics and Astronomy, University of South Carolina
http://www.uottawa.ca/publications/interscientia/inter.2/spin.html
5 "Non-Destructive Evaluation and Failure Analysis", CALeE and the University of

Maryland
http://www.calce.umd.edu/general/Facilities/eds.htm
6 "Mechanical Testing Equipment Companies", Globalspec
http://test-
eq uipment. g 10 ba Ispec. co m/Lea rn M0 refLa bware_Test_Measu rement/Prod uct_M ate
rial_Testing/Mechanical_Testing_Equipment
7 "Flame Atomic Absorption Spectrometry", G. Ma et al.
http://ewr.cee.vt.edu/environmentaljteach/smprimer/aa/aa.html
8 "Frequently Asked Questions About Magnetic Resonance Spectroscopy (MRS)",

B.M. Damon, Vanderbilt University, T. B. Price, Yale University
http://vuiis.vanderbilt.edu/rvnins/M RS_FAQ.htm#_What_is_MRS

Appendix C C-39
9 "Sample Analysis Tools for Metals"
http://www .frtr.gov/site/7_1_2. html
10 "Physical and Chemical Analysis and Measurement", Chemical Products
http://www.c-f-c.com/gaslink/docs/chemproidx/chemintro.htm #q ua ntitative
11 "Nuclear Magnetic Resonance Spectroscopy (NMR)"
http://www.chem.arizona .ed u/facil ities/n mr/ nm ri ntro. pdf
12 "Inductively Coupled Plasma -Atomic Emission Spectrometry", T. J. Manning et ale

Dept. Of Chemistry, Valdosta State University
http://www.mrl.ucsb.edu/mrl/centralfacilities/chemistry/icp.pdf
13 "Chemical Analysis", Castle View
http://www.castleviewuk.com/Frameless/Analysis/chemical_analysis.htm
14 "ISP Knowledge Portal - Spectroscopy Resources", International School of

Photonics at Cochin University of Science and Technology
http://www.photonics.cusat.edu/links_spectroscopy.html
15 "Interstitial Gas Analysis", Shiva Technologies Inc.
http://www.shivatec.com/new/igs. php4
16 "Introduction to Qualitative Analysis - Identifying Anions and Cations", 2005

About Inc.
http://chemistry.about.com/library/weekly/aa09100 la. htm
17 "Introduction to Spectroscopy", About Inc.
http://chemistry.about.com/library/weekly/aa021302a. htm
18 "What is Raman Spectroscopy", McPherson Inc.
http://www.mcphersoninc.com/whatisraman.htm
19 "Neutron Activation Analysis", Worcester Polytechnic Institute
http://www.me.wpi.edu/Nuclear/Reactor/Labs/R-naa.html

C-40 Appendix C
20 "Nuclear Magnetic Resonance Spectroscopy", William Reusch
http://www.cem.msu.edu/ rv reusch/VirtuaIText/Spectrpy/nmr/nmr1.htm
21 "The Basics of Visual Testing", F.A. Iddings, American Society for Non-Destructive
Testing
http://www .asnt.org/publ ications/materia IsevaI/basics/may04basics/may04basics

.htm
22 "Radiograph Interpretation - Castings", NDT Resource Center
http://www.ndt-
ed.org/EducationResources/CommunityCollege/RadiographyjTechCalibrationsjRad
iographInterp_Castings. htm
23 Spectroscopy links:
http://www.solutions.iq.unesp.br/spectroscopy3.htm
24 "The Basics Nuclear Magnetic Resonance Spectroscopy", M.Nerz-Stormes, Bryn

Mawr Organic Chemistry Laboratory
http://www.brynmawr.edu/Acads/Chem/mnerzstojThe_Basics_Nuclear_Magnetic
_Resonance%20_Spectroscopy_2.htm
25 "Visible and Ultraviolet Spectroscopy", William Reusch
http://www.cem.msu.edu/rvreusch/VirtuaIText/Spectrpy/UV-Vis/spectrum.htm
26 "X-Ray Analysis of a Solid", M. S.Whittingham
http://materials.binghamton.edu/labs/xray/xra y.htmI
27 "About Thin Film Leak Testing", Amgas
http://www.amgas.com/ltpage.htm
28 "Common Uses of Liquid Penetrant Inspection", NDT Resource Center
http://www.ndt-
ed.org/EducationResources/CommunityCollege/PenetrantTest/Principles/common
uses.htm

Appendix C C-41
29 "Introduction to Magnetic Particle Inspection", NDT Resource Center
http://www.ndt-
ed.org/EducationResources/CommunityCollege/MagParticie/Introduction/introduct
ion.htm
30 "Introduction to Eddy Current Testing", NDT Resource Center
http://www. ndt-
ed.org/EducationResources/CommunityCollege/EddyCurrents/cc_ec_index.htm
31 "Basic Principles of Ultrasonic Testing", NDT Resource Center
http://www. ndt-
ed.org/EducationResources/CommunityCollege/Ultrasonics/Introduction/descriptio
n.htm
32 "Acoustic Emission Testing", Applied Inspection Systems Inc.
http://www.appliedinspection.com/ae.htm
33 "Chromatography"
http://www.rpi.edu/dept/chem-eng/Biotech-Environ/CHROMO/chromintro.html
34 "Gas Chromatography"
http://www.shu.ac.uk/schools/scijchem/tutorials/chrom/gaschrm.htm
35 "High Performance Liquid Chromatography ( HPLC ) Primer", Waters
http://www. waters. com/watersd ivision/ContentD. asp?watersit=J DRS- 5LTGBH
36 "Liquid Chromatography", Univ. of Adelaide
http://www.chemistry.adelaide.edu.au/external/soc-rel/content/lc.htm
37 "Size Exclusion Chromatography (SEC)"
http://www.proteinchemist.com/tutorial/sec.html
38 "Principles & Practice of Chromatography", R.W. Stott
http://www. ch romatog ra phy-on Ii ne. org/Principles/TLC/Cha mbers/rs62. htm I

C-42 Appendix C
39 "What is laser-induced breakdown spectroscopy (LIBS)?" Army Research

Laboratory
http://www.arl.army.mil/main/main/default.cfm?Action=247&Page=247
40 "UV-Vis Luminescence Spectroscopy",
http://www.shu.ac.uk/schools/scilchem/tutorials/molspec/luminl.htm

Appendix C: Non-Destructive Evaluation (NDE) & Other Tests: Visual Examination

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Appendix C C-l

Appendix C: Non-Destructive Evaluation (NDE) & Other

Non-Destructive Evaluation (NDE) is designed to provide as much infonnation on the

Visual Examination (5), (21)

Leak Testing (27)

Liquid Penetrant Inspection (LPI) (28)

Copyright © 2006 by Dyadem Engineering Corporation

Primary Advantages of LPI Primary Disadvantages of LPI

Few material limitations Only materials with a relative nonporous

Copyright © 2006 by Dyadem Engineering Corporation

Copyright © 2006 by Dyadem Engineering Corporation

Scanning electron microscopy (SEM) (2), (5)

Scanning electron microscopy (SEM) is a method for high-resolution imaging of

Energy Dispersive Microanalysis (EDS) (5)

Energy Dispersive Microanalysis (EDS) is the measurement of X-rays emitted during

Copyright © 2006 by Dyadem Engineering Corporation

X-ray microscopy (5)

Scanning Acoustic Microscopy (SAM) (5)

Infrared Testing (5)

Magnetic particle inspection (MPI) (29)

Copyright © 2006 by Dyadem Engineering Corporation

overall, using either a permanent magnet, an electromagnet, flexible cables or hand-held

Eddy current testing (30)

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Copyright © 2006 by Dyadem Engineering Corporation

Radiographic Testing (22)

Radiography uses differential absorption of radiation penetrating an object coupled with

Copyright © 2006 by Dyadem Engineering Corporation

Copyright © 2006 by Dyadem Engineering Corporation

Copyright © 2006 by Dyadem Engineering Corporation

Acoustic Emission Testing (32)

In Acoustic Emission Testing, the specimen is stressed by applying a load. External or

Copyright © 2006 by Dyadem Engineering Corporation

• Structures which are monitored during nonnal service conditions.

Chemical Analyses Methods

Spectroscopy (1), (2), (8), (14), (17), (23), (25)

Attenuated Total Reflectance Spectroscopy (ATR) (17)

Copyright © 2006 by Dyadem Engineering Corporation

Purther. Attenuated Total Reflectance Spectroscopy (ATR) is a relatively sensitive and

Electron Paramagnetic Spectroscopy (17)

This microwave technique is based on splitting electronic energy fields in a magnetic

Electron Spectroscopy for Chemical Analysis (17)

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Fourier Transform Spectroscopy (5), (17)

Copyright © 2006 by Dyadem Engineering Corporation

The infrared absorption spectrum of a substance is sometimes called its molecular

Functional Group Molecular Motion Wave number (em-i)

Alkanes C-H stretch 2950-2800

CH3 bend --1375

CH z bend (4 or more) --720

Aromatics C-H stretch 3020-3000

C=C stretch --1600 & --1475

Alcohols O-H stretch --3650 or 3400-3300

C-O stretch 1260-1000

Molecular Fluorescence Spectroscopy (40)

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Flame Atomic Absorption Spectrometry (7)

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wavelength is supplied and the amount of light absorbed is measured against a

Chromatographic Methods (33)

Chromatography is a method of separating substances in a mixture. It relies on

Copyright © 2006 by Dyadem Engineering Corporation

Gas chromatography is a chromatographic technique that can be used to separate organic