EXPERIMENTAL REPORT

DILATOMETRY (DIL)ETERMINATION OF
SINTERING ABILITY OF COPPER POWDER

Student name: Phạm Duy

KhánhHoàng Minh Đức
Student ID:
2021700427356
Class ID: MSE33173317 -
7474637474623
Instructor: Dr. Hoàng Thị
Ngọc QuyênLê Hồng Thăng
 Introduction

In SEM, the image formation process involves scanning the

electron beam across the sample surface in a raster pattern. This
information is then used to generate
a two-dimensional image, where each pixel corresponds to a
specific location on the sample surface, and its intensity
represents the signal strength at that point. By combining the
images obtained from different detectors, it is possible to obtain a
comprehensive understanding of the sample's structure,
composition, and properties.
General about chemical vapour deposition
The chemical vapour deposition (CVD) involves the formation
of a thin solid film on a substrate material by a chemical reaction
of vapour-phase precursors
The chemical reactions of precursor species occur both in
the gas phase and on the substrate. Reactions can be promoted
or initiated by heat (thermal CVD), higher frequency radiation
such as UV (photo-assisted CVD) or a plasma (plasma-enhanced
CVD).
General Theory on Hydrothermal Technology
The term hydrothermal usually refers to any heterogeneous
reaction in the presence of aqueous solvents or mineralizers
under high pressure and temperature conditions to dissolve and
recrystallize (recover) materials that are relatively insoluble under
ordinary conditions.
 In the hydrothermal method the components are subjected
to the action of water, at temperatures generally near though
often considerably above the critical temperature of water
(~370°C) in closed bombs, and therefore, under the
corresponding high pressures developed by such solutions.”

Experimental Produce
Sample preparation
In this experiment. Hydrothermal technology and chemical
vapor deposition method (CVD) were used to prepare TiO2-base
films on Ti substrate (10×10 mm2). Sodium hydroxide NaOH was
dissolved in water corresponding to a Na+ concentration of about
5M. The prepared Ti substrates were put in the NaOH solution
with the concentration of 5M in the sample container and were
then heated up to 250oC in 12h. After the hydrothermal process,
the Ti samples were heated at 850oC in 2h for the CVD process.
After cooling in the furnace, the samples were cleaned by using
an ultrasonic machine.
Operating parameters of the SEM
Magnification
The modern definition of magnification is the ratio between
two measurements, which implies that two objects are needed for
a correct evaluation of the value. The first object is obviously the
sample. The second is a picture of it. Although the sample will not
change its size, the picture can be printed in an infinite number of
different sizes.
Resolution
 Resolution is defined as the minimum distance between
two objects that still allows the observer to distinguish them as
separate entities
Thermal stability of inorganic compounds, surface
crystallization mechanisms and other dynamic processes can be
detected in real time. By heating a sample in situ SEM, one can
directly observe the microstructure evolution during heating
and/or cooling and record dynamical processes occurring on the
surface
Electron source
The electron source — or cathode, filament or electron gun
— is one of the most important modules of a desktop SEM. Its
purpose is to provide a stable beam of electrons. There are two
groups of electron sources used in SEM, varying in the amount of
current they produce into a small beam size (spot), the stability of
the beam, and the lifetime of the source.
Voltage
The voltage is an indication of the electrons’ energy
content: this will therefore determine what kind of interaction the
beam will have with the sample. As a general guideline, a high
voltage corresponds with a higher penetration beneath the
surface of the sample — also known as bigger interaction volume.
This means that the electrons will have a larger and deeper
propagation within the sample and generate signals in different
parts of the affected volume. The chemical composition of the
sample also has an impact on the size of the interaction volume:
light elements have fewer shells, and the electrons’ energy
content is lower. This limits the interactions with the electrons
from the electron beam, which can therefore penetrate deeper
into the sample, compared to a heavier element
Current intensity
In any modern scanning electron microscope, the user has
the ability to control the size of the electron probe. This is mainly
achieved by adjusting the condenser and the objective lenses of
the system and by selecting different apertures.
Electrons are flowing through electromagnetic lenses
(which simply consist of coils of wires inside metal pole pieces)
and the user is able to control the electron’s path by tuning the
current that is applied to the lenses.
Moreover, the spot size is dependent on the acceleration
voltage (high accelerating voltages decrease the spot size), the
working distance (the larger it is, the larger the spot size
becomes), and the objective lens aperture (smaller apertures
create spots of a smaller diameter).

Results and Discussion

Discussion of the operating parameters of the SEM
influences the images
Paramet Primary Effects on Key
er Image Considerations
Accelerating Resolution, surface detail, Match voltage to
Voltage charging, penetration depth sample type and imaging
depth required.
Beam Signal intensity, damage Adjust for signal
Current risk strength versus sample
sensitivity.
Spot Size Resolution, brightness Use small spots for
detail; larger spots for
noise reduction.
Working Depth of field, resolution Balance resolution
Distance and depth for the sample
geometry.
Scan Speed Signal-to-noise ratio, Use slow scans for
 imaging time clarity; fast scans for
speed.
Detector Surface vs. composition Select detector
Type imaging based on analytical goals.
Vacuum Resolution, non- Use low vacuum for
Level conductive sample compatibility sensitive samples, high
vacuum for detail
Introduction

Thermodilatometry is a thermal analysis technique that measures how

materials change in size when they're exposed to different temperatures.
Think about how a metal spoon expands slightly when you put it in hot water
- thermodilatometry measures this kind of dimensional change with extreme
precision.
The core principle relies on the fact that nearly all materials expand when
heated and contract when cooled. This happens because as temperature
increases, atoms vibrate more vigorously, increasing their average spacing.
Imagine a crowd of people - when they stand still (low temperature), they
take up less space than when they're dancing energetically (high
temperature).
The LVDT has three main components:
+ A primary coil in the center that receives an AC input
+ Two secondary coils arranged symmetrically on either side
+ A movable magnetic core that slides inside these coils
When we connect the LVDT to our sample in a thermodilatometer, any
expansion or contraction of the material moves this magnetic core. As the
core moves, it changes how much magnetic coupling exists between the
primary and secondary coils. This creates a difference in voltage between
the secondary coils that's directly proportional to the core's position.
The beauty of this system is that it can measure incredibly small changes -
often down to micrometers or even nanometers. To put this in perspective,
that's like being able to measure a change in length smaller than a
bacterium!

connection between atomic interactions and

thermal expansion in solids
This relationship is fundamental to understanding why materials behave the
way they do at different temperatures.
Imagine two atoms in a solid. The potential energy between them typically
follows what we call an asymmetric curve, often modeled by the Lennard-
Jones potential or similar functions. This curve has two important features: a
deep well representing the equilibrium position where atoms prefer to sit,
and an asymmetric shape where the repulsive force (when atoms get too
close) rises more steeply than the attractive force (when atoms move apart).
Picture this potential as a ball rolling in a curved bowl. The bottom of the
bowl represents the equilibrium position where the atoms would sit at
absolute zero temperature. But here's where it gets interesting: atoms aren't
static - they're constantly vibrating due to thermal energy. These vibrations
are like the ball oscillating back and forth in the bowl.
To make this more concrete, let's consider what happens as we increase
temperature:
+ At very low temperatures, atoms vibrate with small amplitudes around
their equilibrium positions, staying near the bottom of the potential well.
+ As temperature increases, atoms gain more thermal energy, leading to
larger vibrations. Due to the asymmetric potential, these larger vibrations
result in a greater average separation between atoms.
+ This increased average separation between atom pairs, when multiplied
across the entire crystal lattice, manifests as macroscopic thermal
expansion.
The mathematical relationship can be expressed through the Grüneisen
parameter, which relates the anharmonicity of these atomic vibrations to the
thermal expansion coefficient. The stronger the asymmetry in the potential
(greater anharmonicity), the larger the thermal expansion tends to be.

how glasses undergo softening at their glass

transition temperature (Tg)
To understand glass softening, let's first consider what makes glasses
special. Unlike crystalline solids, glasses lack long-range atomic order - their
structure is more like a frozen liquid, where atoms are arranged randomly
but held relatively fixed in position. This atomic arrangement profoundly
influences how glasses respond to temperature changes.
As we heat a glass from room temperature toward its Tg, several important
changes occur. Initially, the glass behaves like a rigid solid, with atoms
vibrating around fixed positions. The material's response to stress is
primarily elastic - it deforms under force but returns to its original shape
when the force is removed. The viscosity at this stage is extremely high,
typically above 10¹² Pascal-seconds.

 The long arrows in FIG symbolize the transfer of temperature energy by

external impulses of gas molecules or radiation coming from all
directions in irregular intervals, stimulating the molecules of the liquid
matter to vibrate inharmoniously.
 The vibration frequencies and amplitudes are distributed around a
mean value. The short arrows demonstrate that the molecular centers
and the axes may tend to move in different directions (the drawn
vectors are not arranged correctly). The drawn molecules demonstrate
the field limitations.
When we approach the glass transition temperature, something remarkable
happens. Thermal energy becomes sufficient to allow for local
rearrangements of atoms or molecules. These rearrangements, often called
relaxations, begin to occur over observable timescales. Think of it like a very
slow-motion version of ice melting - but instead of a sharp transition, the
process occurs gradually over a temperature range.
physical changes during this softening process include:
First, the viscosity begins to decrease dramatically. As the temperature rises
through the glass transition region, the viscosity typically drops by several
orders of magnitude. This change isn't sudden like melting ice - instead, it
occurs over a temperature range of about 10-20°C around Tg.
Second, the material's mechanical properties undergo significant changes.
The elastic modulus decreases substantially, and the glass begins to exhibit
viscoelastic behavior. This means it responds to stress partly like a solid and
partly like a liquid. If you were to apply a constant force, the glass would
initially deform elastically, but then continue to slowly flow over time.
Third, there's a marked increase in the material's heat capacity. This reflects
the fact that additional thermal energy can now go into rearranging atomic
positions rather than just increasing atomic vibrations. This shows up as a
step in the heat capacity versus temperature curve, which is one way we can
experimentally determine Tg.

Experimental Procedure
Dilatometry is an important method for measuring the change in length or
volume of materials as it varies with temperature or other external
influences. It is the method of choice for studying changes in length for
ceramics, glasses, metals, composites and polymers as well as other
structural materials. It allows for information to be obtained on thermal
behavior, process parameters, and Sintering is a production process for
forming a mechanically strong body out of a ceramic or metallic powder.
sintering (as well as crosslinking) kinetics.
Discussion of temperature influences the samples

1. Switch on the DIL control unit; allow the controller to warm-up for at least
15 minutes before stating the experiment.
2. Use a vernier caliper or a micrometer to measure the length of each
sample assigned to you and record the value in you notebook.
3. Hold the slider knob and slide the furnace on the right slowly. Place the
sample in the sample carrier using tweezers. Blend the sample thermal
couple close to the sample (note: dose not touches the sample). Carefully
slide the furnace at the initial position.
4. Adjust the fine vernier control using the adjusting screw for a low LVDT
output (close to zero). If the sample requires a protective gas setting a
required amount of gas purge to the furnace.
5. Start the DIL 402 PC measurement program; define the temperature
program (max: 5000C) and measurement file name.
6. At regular intervals, approximately every 5 minutes, record the sample
temperature and the LVDT output in a table and plot the data to make sure
everything is working correctly.
7. When the set point temperature is reached, the computer stops
automatically recording the data.
8. Allow the furnace to cool down to 1000C and switch off the power to the
furnace.

DATA analysis
solids expand when heated. Amorphous solids, polycrystalline materials, and
cubic single crystals expand isotopically and therefore the expansion can be
characterized by a single parameter, the coefficient of linear expansion.

L0 is the length at temperature T1

L is the length at T2
α is a function of temperature. Often, α is approximately constant in the
temperature interval T1 to T2

the equation above can simplifies to

The graph shows relative length change (dL/Lo × 10^-3) versus temperature
(°C). The curve appears to be non-linear, which is typical for thermal
expansion over large temperature ranges. Temperature control of
samples in SEM is used for different applications, among them
water condensation and evaporation, particles thermal migration,
phase transformation, in situ synthesis, low temperature
spectroscopy and more. The sample’s temperature in the SEM can
be controlled by special stages for heating or cooling.

 At 30.7-60°C: α = 0.1988E-06 /K
 At 60-90°C: α = 7.3168E-06 /K
 At 90-120°C: α = 15.2316E-06 /K
 At 150-180°C: α = 22.0647E-06 /K
 At 210-240°C: α = 15.9457E-06 /K
 At 240-270°C: α = 15.1650E-06 /K

This material show:

 Very low expansion at low temperatures
  A significant increase in expansion rate as temperature rises
 A peak in the expansion coefficient around 150-180°C
 Stabilization at higher temperatures
 The extremely low thermal expansion coefficient at room
temperature (near zero)
 The characteristic increase in α as temperature rises
Conclusion: Based on characteristics, this behavior appear to be
a Nikel-Iron alloy might the Invar alloy (A steel manufactured to
have a very low thermal expansion), which makes it valuable for
precision instruments and applications requiring dimensional
stability. The increase in its expansion coefficient at higher
temperatures is a well-documented behavior of this alloy.

High temperature experiments in situ SEM can be of great

importance for materials characterization. Thermal stability of
inorganic compounds, surface crystallization mechanisms and
other dynamic processes can be detected in real time. By heating
a sample in situ SEM, one can directly observe the microstructure
evolution during heating and/or cooling and record dynamical
processes occurring on the surface.
Temperature control is also required to cool down samples when
working in wet mode. In that case the condensation/evaporation
of water can be controlled by a Peltier cooling stage (-20°C-60°C).
High temperature experiments are mostly performed on inorganic
materials as moderate low temperature experiments can be
performed on organic and inorganic materials.

SEM image