MME365 Glass and Ceramics Materials
Lecture 05
Characterization of Ceramic Powders
PROF DR. AHMED SHARIF
Physical Characterization
Physical characterization focuses on the physical attributes of the ceramic powder that
directly influence its processability and the microstructure of the final ceramic body.
•Particle Size Distribution (PSD): This is a fundamental property, often measured by
laser diffraction or sieving. The size and range of particle sizes significantly affect
powder flowability, packing efficiency (density), and the kinetics of the subsequent
sintering process.
•Particle Shape and Morphology: This describes the shape, structure, and surface
characteristics of individual particles (e.g., spherical, irregular, agglomerated).
Techniques like Scanning Electron Microscopy (SEM) and Transmission Electron
Microscopy (TEM) are used. Particle shape affects how well the powder packs and
flows.
Physical Characterization
Density:
•Apparent/Bulk Density: Mass per unit of volume of a freely poured powder, including all
voids between particles.
•Tapped Density: Density after compaction (tapping/vibration), indicating packing
efficiency.
•Skeletal/True Density: The solid density of the material, excluding all pores and voids.
Often measured by helium pycnometry
Physical Characterization
•Flowability: The ease with which a powder flows, critical for consistent feeding and uniform
mold filling. It is often measured using an angle of repose test or devices like the Hall or
Carney flow meters.
•Specific Surface Area (SSA) and Porosity: SSA is the total surface area per unit mass. It
influences a powder's reactivity and adsorption properties. It's typically measured using the
Brunauer Emmett Teller (BET) method via gas adsorption (e.g., nitrogen). Porosity is the
ratio of empty volume (inter- and intra-particle voids) to the bulk volume.
Laser Diffraction for Particle
Sizing
Laser Diffraction (LD) is a widely used, rapid, and non-destructive technique for determining the
Particle Size Distribution (PSD) of powders, suspensions, and emulsions.
The technique is based on the principle that particles passing through a laser beam will scatter or
diffract light at an angle that is inversely proportional to their size.
Large Particles: Scatter light at small angles relative to the main laser beam with high intensity.
Small Particles: Scatter light at large angles with lower intensity.
Laser Diffraction for Particle
Sizing
How it Works
Sample Dispersion: The ceramic powder is dispersed in a medium (either a liquid solvent or an air
stream) to ensure the particles pass through the beam individually.
Illumination: A collimated laser beam is passed through the dispersed sample.
Detection: A detector array (comprising multiple photo-sensitive elements) positioned on the other side
of the sample measures the intensity and angle of the scattered light across a wide range of angles.
Calculation: A computer algorithm applies an optical model—typically the Fraunhofer approximation
(better for larger, opaque particles) or the Mie theory (more accurate for smaller particles, requiring
knowledge of the material's refractive index)—to convert the measured angular scattering pattern into a
volume-weighted particle size distribution.
Laser Diffraction for Particle
Sizing
Advantages
LD offers a wide dynamic measurement range (from submicron to millimeter size), is very fast
(results in less than a minute), and provides high repeatability, making it a staple for quality
control and process optimization in ceramic powder characterization.
Sieving: Particle Size
Classification
Sieving is a traditional, cost-effective, and rapid
method used for determining the particle size
distribution of powders and granular materials,
especially for particles typically larger than about
20-40 μm
Sieving: Particle Size
Classification
Principle and Procedure
The technique separates a powder sample into different size fractions based on the particles'
ability to pass through a mesh screen with specific, standardized aperture sizes.
[Link] Stack: A known weight of powder is placed on the top sieve of a stacked column. The
sieves are arranged with the largest mesh opening at the top and progressively smaller
openings down to a collection pan (receiver) at the bottom.
[Link]: The sieve stack is subjected to mechanical agitation (shaking, vibration, tapping, or
air jet) using a sieve shaker for a specified period of time. This motion ensures that the particles
are repeatedly presented to the sieve openings.
[Link]: Particles smaller than the mesh opening pass through (undersize), while larger
particles are retained (oversize).
[Link]: After sieving, the material retained on each individual sieve and in the pan is
carefully collected and weighed.
[Link]: The mass retained on each sieve is calculated as a percentage of the total sample
mass to generate the particle size distribution (PSD) data.
Sieving: Particle Size
Classification
Types of Sieving
•Dry Sieving: The most common method, suitable for free-flowing materials.
•Wet Sieving: Used for very fine or cohesive powders that tend to agglomerate or
stick to the mesh. A liquid (e.g., water or a dispersion agent) is used to help break up
clumps and wash the fines through the mesh.
•Air Jet Sieving: Uses a rotating column of air to fluidize the sample and pull the
fines through a single sieve into a vacuum, often used for very fine particles to
prevent screen blinding (clogging)
Sieving: Particle Size
Classification
Application in Ceramic Powders
Sieving is essential in ceramic processing for quality control and to
ensure the homogeneity of raw materials, as particle size
distribution directly impacts powder packing density, flowability,
and the final sintered microstructure and properties of the
ceramic product.
Chemical and Phase Composition
This area examines the chemical identity of the ceramic powder and its crystalline
structure.
Chemical Composition (Elemental Analysis): Determines the major elements,
stoichiometry, and content of trace impurities present in the powder. Impurities can
drastically affect sintering and the final material's properties.
◦ Techniques include Inductively Coupled Plasma (ICP) spectroscopy, X-ray Fluorescence (XRF)
spectroscopy, and Combustion Analysis (LECO) for elements like C, S, N, O, and H.
Phase Composition: Identifies the crystalline phases present in the powder, which
might include the desired ceramic phase, as well as precursor compounds or
secondary phases (impurities).
◦ The primary method is X-ray Diffraction (XRD), which analyzes the atomic structure to identify and
quantify the different crystalline phases. Knowing the phase composition ensures the starting
material is the correct crystalline form required for the final product.
Inductively Coupled Plasma
(ICP) Spectroscopy
Inductively Coupled Plasma (ICP)
Spectroscopy is a powerful analytical
technique used for the detection and
quantification of chemical elements in a
sample. It relies on using an extremely hot,
energetic plasma to break down a sample and
excite the resulting atoms and ions, which
then emit characteristic radiation that is
measured by a detector.
Inductively Coupled Plasma (ICP) Spectroscopy
How It Works
Plasma Generation: An argon gas flow is ionized within a torch by a powerful radio-
frequency (RF) electromagnetic field generated by induction coils. This creates a self-
sustaining, high-temperature plasma (6,000–10,000 K), essentially a superheated gas
of ions and electrons.
Sample Introduction: A liquid sample (often a dissolved solid, like a ceramic powder
digest) is converted into a fine mist (aerosol) using a nebulizer and introduced into the
core of the plasma.
Atomization and Excitation: The extreme heat of the plasma instantaneously desolvates
(evaporates solvent), vaporizes, and atomizes the sample, breaking all chemical bonds.
The resulting free atoms and ions are excited to higher energy levels through collisions.
Inductively Coupled Plasma (ICP)
Spectroscopy
Emission/Detection:
•ICP-OES (Optical Emission Spectroscopy): As the excited electrons return
to their ground state, they emit energy as photons of light at specific,
characteristic wavelengths unique to each element. An optical spectrometer
separates this light by wavelength, and the intensity of the light is measured
to determine the concentration of each element.
•ICP-MS (Mass Spectrometry): Ions generated in the plasma are extracted,
passed into a mass spectrometer, and separated based on their mass-to-
charge ratio . A detector measures the number of ions, allowing for the
quantification of elements and even specific isotopes at very low trace levels.
Inductively Coupled Plasma (ICP)
Spectroscopy
Key Features
Multi-elemental: Can analyze most elements in the periodic table (except
some light gases) simultaneously.
Sensitivity: Offers very low detection limits, especially ICP-MS, which is used
for trace element analysis.
High Temperature: Ensures complete decomposition and minimizes chemical
interferences
X-ray Fluorescence (XRF)
Spectroscopy
X-ray Fluorescence (XRF) spectroscopy is a
powerful, non-destructive analytical technique
used primarily to determine the elemental
composition of a wide variety of materials,
including solids, liquids, and powders (like
ceramic powders).
X-ray Fluorescence (XRF) Spectroscopy
Working Principle
The technique relies on the unique way each element emits X-rays when excited, acting as a kind of
elemental "fingerprint":
Excitation: A sample is irradiated with a high-energy primary X-ray beam (typically from an X-ray tube).
Ionization: If the primary X-ray has sufficient energy, it ejects an electron from an inner shell (like the K or L
shell) of an atom, leaving a vacancy and making the atom unstable (ionized).
Fluorescence: An electron from a higher-energy outer shell immediately drops down to fill the inner-shell
vacancy. This transition releases a precise amount of energy in the form of a secondary X-ray, known as a
fluorescent X-ray .
Detection and Analysis:
◦ The energy of the emitted fluorescent X-ray is characteristic and uniquely identifies the element (qualitative
analysis).
◦ The intensity (count rate) of the characteristic X-ray is directly proportional to the concentration of that element in
the sample (quantitative analysis).
X-ray Fluorescence (XRF)
Spectroscopy
Key Features and Applications
•Non-Destructive: Analysis is performed without damaging or altering the sample, making
it ideal for precious or unique materials.
•Minimal Sample Preparation: Often requires little to no sample preparation, especially
compared to techniques requiring sample dissolution.
•Elemental Range: Typically detects elements from Sodium (Na, atomic number 11) up
to Uranium (U, atomic number 92), with some specialized instruments detecting lighter
elements like Carbon or Oxygen.
•Applications: Widely used across many industries for Quality Control (QC) and
elemental analysis:
•Ceramics/Cement: Analyzing major and minor oxides.
•Metallurgy: Alloy identification and grade confirmation.
•Mining/Geology: Ore and soil analysis.
•Environmental: Screening for heavy metals (e.g., Lead) in products and soil.
Combustion Analysis (LECO)
Combustion Analysis (LECO),
often performed using instruments
manufactured by LECO Corporation,
is a fast and accurate elemental
analysis technique used primarily to
determine the content of Carbon
(C) and Sulfur (S), and in some
variations, Oxygen (O), Nitrogen
(N), and Hydrogen (H) in a wide
range of materials, including ceramic
powders.
Combustion Analysis (LECO)
Key Principles
[Link]/Fusion: A precisely weighed sample is placed in a
crucible (often ceramic) and introduced into a high-temperature
furnace (up to 1350°C or even over 2000°C, typically under a pure
oxygen atmosphere. For O, N, and H analysis, the sample is often
fused in an inert gas (like helium or argon).
[Link]: The high temperature causes the elements of interest
to rapidly oxidize and be converted into stable, measurable gases:
Combustion Analysis (LECO)
•Detection: The resulting combustion gases are swept through the system,
often passing through traps to remove moisture and interfering species. The
concentrations of the specific gas molecules are then measured using
Infrared (IR) absorption for CO2 and SO2, and often thermal conductivity
for N2 and H2.
•Quantification: The instrument integrates the detector signal over time. By
knowing the sample mass and having a calibration curve established with
known standards, the instrument calculates and reports the final elemental
content as a percentage or in parts per million (ppm).
Combustion Analysis (LECO)
Relevance to Ceramics
In ceramic powder characterization, LECO combustion analysis is
crucial for:
•Carbon Content: Measuring the amount of residual carbon left
from organic binders or processing aids used during powder
synthesis and forming. High carbon content can be detrimental to
the final properties or appearance (e.g., blackening) of the
sintered ceramic.
•Impurity Control: Detecting trace levels of other light elements
like S or N that can act as contaminants and inhibit proper
sintering or negatively affect the final material's performance.
X-ray Diffraction (XRD)
X-ray Diffraction (XRD) is a
powerful, non-destructive
analytical technique used to reveal
the atomic and molecular
structure of crystalline materials,
primarily for determining the
phase composition of ceramic
powders.
X-ray Diffraction (XRD)
How It Works
[Link] (Bragg's Law): The technique is based on the interaction of X-rays
with the periodic structure of a crystal. When an X-ray beam hits a crystalline
sample, it is diffracted by the atoms. When the path difference between X-rays
reflected from successive planes of a crystal lattice is equal to a whole number of
wavelengths, constructive interference occurs, and a strong diffracted beam is
produced. This relationship is defined by Bragg's Law: nλ = 2dsinϴ.
•n: integer (order of reflection)
•λ : wavelength of the X-rays
•d: spacing between the crystal lattice planes
•ϴ : angle of incidence (Bragg angle)
[Link]: The ceramic powder is irradiated with monochromatic X-rays
while a detector measures the intensity of the diffracted X-rays as a function of the
angle (2ϴ).
X-ray Diffraction (XRD)
What the Results Show
The output is a diffraction pattern (a plot of intensity vs. 2ϴ ), which acts as a
"fingerprint" for the material.
•Peak Positions (2ϴ) The specific angles where peaks occur are directly related
to the lattice parameters and crystal structure of the phases present (via
Bragg's Law).
•Peak Intensities: The height and area of the peaks are proportional to the
amount of the crystalline phase present, allowing for quantitative analysis of
different phases in a mixture.
•Peak Shape (Width): Broadening of the peaks can be used to estimate the
crystallite size (the size of the individual coherent domains) within the powder
particles.
X-ray Diffraction (XRD)
In ceramic characterization, XRD is crucial for:
•Phase Identification: Determining which crystalline compounds
(phases) make up the powder (e.g., identifying Al2O3 vs. SiO2
phases).
•Purity Assessment: Detecting and quantifying undesirable
crystalline impurity phases.
•Amorphous Content: Identifying the presence of non-crystalline
(glassy) material, although quantification is more challenging.
Scanning Electron Microscope (SEM)
A Scanning Electron Microscope
(SEM) is a type of electron microscope
that produces high-resolution images
of a sample's surface topography and
composition. It achieves a much
greater magnification and resolution
(often down to the nanometer scale)
than traditional optical microscopes
by using electrons instead of light.
SEM
Working Principle
Electron Beam Generation: An electron gun generates a focused beam of high-energy electrons (the primary
beam) at the top of an evacuated column.
Focusing and Scanning: Electromagnetic lenses focus this beam to a very fine spot on the sample surface,
which is mounted inside a high-vacuum chamber. Scanning coils systematically deflect the beam, causing it
to scan the sample's surface in a rectangular pattern (a raster).
Electron-Sample Interaction: When the primary electron beam strikes the sample, it interacts with the
atoms, causing the emission of various signals, primarily:
◦ Secondary Electrons (SE): Low-energy electrons emitted from the very surface of the sample, providing excellent
information about the surface topography (shape and texture), giving the image a three-dimensional appearance.
◦ Backscattered Electrons (BSE): Higher-energy electrons from the primary beam that are scattered back out of the
sample. Their yield is sensitive to the atomic number (heavier elements produce more BSE), providing compositional
contrast.
Image Formation: Detectors collect these emitted electrons (or other signals, like X-rays for elemental
analysis). The signal intensity is synchronized with the position of the scanning beam to create a point-by-
point, grayscale image displayed on a monitor.
Scanning Electron Microscope
(SEM)
Key Applications
The SEM is widely used in materials science, biology, and quality
control to analyze:
Surface morphology and topography (e.g., surface roughness,
particle shape).
Chemical composition (often coupled with Energy Dispersive X-ray
Spectroscopy or EDS).
Microstructure (e.g., grain size, defects).
X-ray Photoelectron Spectroscopy
(XPS)
X-ray Photoelectron Spectroscopy
(XPS), also known as Electron
Spectroscopy for Chemical
Analysis (ESCA), is a powerful, non-
destructive, surface-sensitive
analytical technique used to study
the chemical composition and
electronic state of materials.
X-ray Photoelectron Spectroscopy (XPS)
Working Principle
1. Irradiation: The sample, placed in an ultra-high vacuum (UHV)
environment, is bombarded with a beam of monochromatic X-rays
2. Photoelectric Effect: The X-ray photons interact with atoms in the
sample, causing inner-shell (core-level) electrons to be ejected. This is
known as the photoelectric effect.
3. Kinetic Energy Measurement: The kinetic energy of these
emitted electrons (photoelectrons) is precisely measured by an
electron energy analyzer.
4. Binding Energy Calculation: The binding energy of the electron
is then calculated.
X-ray Photoelectron Spectroscopy (XPS)
Information Provided
•Elemental Composition: Each element produces a unique set of peaks, allowing
for the identification and quantification of all elements present in the sampling
volume (except Hydrogen and Helium).
•Chemical State/Oxidation State: The exact BE of a core-level electron is slightly
affected by the atom's chemical environment (i.e., its oxidation state and what
other atoms it is bonded to). This slight shift in BE, known as the chemical shift,
provides crucial information about the chemical bonding and compound structure
(e.g., distinguishing between a metal and its oxide).
•Surface Sensitivity: Because the emitted photoelectrons have low kinetic energy
and can only escape from the top 1-10 nm of the surface without losing energy
through inelastic scattering, XPS is highly sensitive only to the surface and near-
surface layers of the material.
•Depth Profiling: By combining XPS analysis with controlled argon ion sputtering
(etching away the surface layer by layer), a depth profile of the elemental and
chemical composition can be obtained.
Auger Electron Spectroscopy
(AES)
Auger Electron Spectroscopy (AES) is a surface-sensitive analytical
technique used to determine the elemental composition and
chemical state of a solid material's near-surface region, typically
probing the top 1 to 10 nanometers (a few atomic layers).
Auger Electron Spectroscopy (AES)
Principle: The Auger Effect
Ionization: A high-energy electron beam (typically 3–25 keV) bombards
the sample, ejecting an inner-shell electron from an atom. This creates a
vacancy or "hole."
Relaxation: An electron from a higher-energy outer shell drops into the
inner-shell vacancy, releasing a specific amount of energy.
Auger Electron Emission: This released energy is simultaneously
transferred to another electron, which is then ejected from the atom. This
ejected electron is called the Auger electron.
Auger Electron Spectroscopy (AES)
Analysis
The kinetic energy of the emitted Auger electron is characteristic of the element
from which it originated, making it a "fingerprint" for elemental identification
(qualitative analysis).
The intensity of the Auger peaks is proportional to the concentration of the
element present (semi-quantitative analysis).
Because the Auger electrons have relatively low energies, they can only escape
the solid without losing energy if they originate very close to the surface, which is
why AES is highly surface-sensitive
Auger Electron Spectroscopy (AES)
Applications
AES is a powerful tool due to its high lateral spatial resolution (as low as 10
nm). When combined with an ion sputtering technique (ion milling), it can
perform depth profiling, revealing the composition as a function of depth. It is
widely used for:
Analysis of thin films and coatings.
Identifying surface contaminants and defects (e.g., in semiconductors).
Studying corrosion and oxidation processes.
Elemental mapping to show the distribution of elements across a surface.