Metal Processing with Lap

MSE 4202
Introduction
Filimon Hadish, Ph.D.
Assistant Professor of Materials Science and Engineering
Adama Science and Technology (ASTU)
Email: filimon.hadish@astu.edu.et
hadfili2005@gmail.com
Phone: +251 900740162

1
Anterenga

Buda

• https://johangerrits.com/travel/ethiopia/north_ethiopia/143_-_A_blacksmith_in_Harar_-
_Ethiopia/
• https://www.mediastorehouse.com.au/worldinprint/africa/ethiopia-abyssinia-ethiopia-
heritage-sites-aksum/portrait-blacksmith-work-town-axoum-axum-1150420.html
• https://www.superstock.com/asset/metal-objects-blacksmith-workshop-axoum-axum-tigre-
region-ethiopia-africa/1890-44473
• https://www.mediastorehouse.co.uk/fine-art-finder/artists/luca-giordano/blacksmiths-shop-
1885-oil-canvas-28649531.html
• https://www.npr.org/2021/06/29/1011043968/united-airlines-is-buying-270-new-planes-in-
massive-bet-on-future-of-travel
• https://newsghana.com.gh/zambia-starts-impounding-dubiously-imported-heavy-
duty-vehicles
• https://www.nswrailmuseum.com.au/
• 2
https://www.usamm.com/blogs/news/u-s-navy-ship-classes-a-close-
look-at-classifications
 Luke Shaw

3
https://www.sportzcraazy.com/worst-football-injuries/
 Luke Shaw

4
https://www.sportzcraazy.com/worst-football-injuries/
https://www.drfragomen.com/knock-knees 5
https://www.drfragomen.com/knock-knees 6
A. Photograph shows two sizes of the
eight-Plate Guided Growth System:
12 and 16 mm. The eight-Plate kit
includes three sizes of cannulated
screws (16, 24, and 32 mm).
B. Photograph shows the complete
eight-Plate set (clockwise from top):
a 3.2-mm cannulated drill bit, a 21-
gauge needle, two 1.5-mm wires with
1.2-mm threaded tips, a screwdriver,
four eight-Plates, ten cannulated
screws, and a drill-guide. New
instrumentation kits include a 3.2-
mm cannulated step drill and a guide
to limit penetration to 5 mm.
C. Guide wires, 21-gauge needle,
cannulated screws, and an eight-
Plate. The cannulated screws are
inserted over the guide wires. The
21-gauge needle provides temporary
fixation.
D. Photograph shows that the screws
are able to pivot within the eight-
Plate (greater than 45 of rotation is
possible)
7
Rolf D. Burghardt et.al., J Child Orthop (2008) 2:187–197
Stainless steel small fragment screws and Orthopedic plate

https://www.dreamstime.com/orthopaedic-plate-
screw-image225183093

https://www.shutterstock.com/image- https://naileditortho.com/heres-what-med-
photo/surgical-plates-osteosynthesis-case- students-should-know-about-orthopedic-
bone-fractures-2086757179 plates-and-screws-part-1/ 8
The biocompatible materials used for bone plates are:
• 316L stainless steel
• cobalt base alloys
• Bioceramics
• titanium alloys
• pure titanium
• composite materials and
• polymers (non-resorbable and bioresorbable).

Property

Bioinert
 Wear
 corrosion and
 heat resistances

9
 Binary Alloys Galvanically Induced Intergranular
Corrosion of AA5083-H131

Mg-9Gd-4Y-2Zn-0.5Zr(wt.%) alloy aged

https://www.xometry.com/resources/materials/alloy-steel-
vs-stainless-steel/
10
 Inter-element miscibility driven stabilization of ordered pseudo-binary
alloy Z3-FePd3

Journal of Magnesium and Alloys

• Multi component phases
Matsumoto, K. et.al.; Nat. Commun v(2022). • thermodynamically-stable phases?

zinc-water
system and Corrosion behavior
magnesium- of Mg64Zn36 in
water 3.5 wt.% NaCl
system
at 25 oC
F. Cao, B. Xiao, Z. Wang et al. Journal of Magnesium and Alloys 11
(2021)
 Advanced Aluminum Armor Alloys 5083-H131

https://www.lightmetalage.com/news/industr
y-news/flat-rolled-sheet/article-advanced-
aluminum-armor-
alloys/#:~:text=Based%20on%20their%20balli
stic%20characteristics,preferred%20alloys%20
for%20armored%20vehicles.

12
 Mg–12 wt.%Zn binary alloy

Eutectic compound Mg21Zn25 + Mg51Zn20. 13

 Thermodynamic

First law of thermodynamics

• Heat (Q);
• Internal energy (U)
• Exact and inexact differentials
• Enthalpy (H)
• Joule-Thompson expansion
• Heat Capacities (Cp)

https://www.neetprep.com/section/chapter/650?sectionId=325 14
First law of thermodynamics
• Internal energy (U)

• Heat (Q)
∆ -ve ∆ +ve

• Enthalpy (H): heat content of the system ∆ -ve

∆ +ve

 –ve, the system losses its heat content to the surrounding

 +ve, system absorbs heat from surrounding
• Exact and inexact differentials

Exact differential Inexact differential

• State functions • Not state functions
• path independent • path dependent
• Eg. U, p, V, H • Eg. W, Q

15
• Intensive and Extensive properties

https://www.mechanicalbooster.com/2016/04/difference-between-
intensive-and-extensive-properties.html#google_vignette

• Joule-Thompson expansion

It is a useful relation for relating the heat capacities at constant pressure

and volume and for the liquefaction
of gases

Where is the Joule-Thompson

Cooling by isenthalpic
coefficient and is defined as expansion is now
called the Joule- Thomson
effect.
16
 • Heat Capacities (Cp)

Heat capacities (solid and liquid)

Subsequently, the enthalpy H and the entropy S can be obtained as:

Second Law of Thermodynamics. Entropy

Non-Spontaneous
• Heat always is transferred

Spontaneous
spontaneously from a warmer to a
colder body ( )
• The revers process is possible only if
work or energy is supplied
• i.e.
https://thesis.library.caltech.edu/2237/3/chapter_2.pdf 17
 Carnot cycle
• A theoretical description of a machine that represents the process of
heat transfer into mechanical work.
• Four steps of figurative representations are
 Isothermal expansion (at )
 Adiabatic Expansion (from )
 Isothermal Compression (at )
 Adiabatic Compression (back from )

From the general relation of

The efficiency ( )of a Carnot cycle is

18
Entropy (S): measure of the disturbance of a system.
• thermodynamically defined as

A general useful relation for the validation of a process of system is

• If a process is reversible the entropy change is zero.( )
• The entropy increases in all irreversible processes.( )
Entropy of mixtures

Entropy Change at Mixing Two Liquids or Solids (molar entropy of mixing)

Entropy and probability (statistical thermodynamic expression)

Entropy Change during Solidification

19
Gibbs’ Free Energy (G)

For the change of a system at constant temperature

Taking into consideration 1st and 2nd laws of TDs, we get

Thermodynamics of Single-Component Systems

• A single-component system may consist of only one phase, f(eg. a solid, a
liquid or a gas) depending on the temperature.
• Even phase transformation occurs, only single-component systems (pure
metals only is considered).
Clausius–Clapeyron’s Law
For an arbitrary phase equilibrium condition

Clausius--Clapeyron’s law

20
 Acupuncture
 An ancient Chinese medicine-based approach (2,500 years)
 Stimulate nerve-rich areas of the skin surface in order to influence
tissues, gland, organs, and various functions of the body.
•allergies •insomnia
•anxiety and depression •menstrual cramps and PMS
•osteoarthritis •migraines
•chronic pain, often in the neck, back, knees, •morning sickness
and head •sprains
•hypertension •Strokes

21
https://www.healthline.com/health/acupuncture-how-does-it-work-scientifically#what-are-the-benefits
22
(a) AN (b) AuNPs/AN and (c)rGO/AuNPs/AN

(a) PMB/P[Bvim]Br/rGO/AuNPs/AN
(b) P[Bvim]Br/PMB/P[Bvim]Br/rGO/AuN
Ps/AN
(c) MI/PMB/P[Bvim]Br/rGO/AuNPs/AN
(c) and MI/PMB/P
[Bvim]Br/rGO/AuNPs/AN + SARS-
CoV-2-S protein

23
Metal Processing with Lap
MSE 4202
Nucleation and
Crystal Growth in Vapour

Filimon Hadish, Ph.D.

Assistant Professor of Materials Science and Engineering
Adama Science and Technology (ASTU)
Email: filimon.hadish@astu.edu.et
hadfili2005@gmail.com
Phone: +251 900740162

24
 Nucleation
The formation of crystals (influenced by the number of crystals growing in the
melt).
Homogeneous nucleation (HN):
very high supersaturation is needed before any crystals form

Pure Metals Supersaturation intermediate phases

• Clusters Theory of Homogeneous Nucleation of Solid

• Nucleation rate Crystals from Liquids
• Nuclei (Critical size)
• Embryos (Sub-critical size)

• Nucleation Rate
• HN as a Function of Undercooling. Nucleation Temperature
• HN as a Function of Concentration in Binary Alloys
• Influence of Variable Surface Energy on HN
• HN of Non-Spherical Embryos. Nucleation of Faceted Crystals
25
Schematics of nucleation mechanisms 26
Secondary Nucleation:
• The presence of the crystal
seed of parent solution acts
as catalysts for the formation
of nuclei.
• Reduced

27
Secondary Nucleation:
• The presence of the crystal seed of parent solution acts as catalysts for the
formation of nuclei.
• Reduced the required energy for nucleation less super-saturation will be
necessary.
• Van der Waals force of the seed crystals in a supersaturated solution
attracts the
solute clusters or embryos.
• By increasing these embryos in the near crystals rapid coagulation occurs, so
the creation of nuclei bigger than critical size happens.
• The crystal seed of parent solution operates as the origin of nuclei, either by
micro-attrition because of the fluid shear or needle breeding.
• Since the impact force brings a bigger disturbance to the adsorbed layer and
transfers a greater number of nuclei to the bulk.
• contact is more effective in the creation of secondary nucleation relative to
bulk fluid shear. 28
 Cluster and Nuclei
• if r< the system can lower its free
energy by dissolution of the solid
• Unstable solid particles with r<r* are
known as clusters or embryos
• if r> the free energy of the system
decreases if the solid grows
• Stable solid particles with r> are
referred to as nuclei
• Since ∆G = 0 when r = r* the critical
nuclei is effectively in (unstable)
equilibrium with the surrounding liquid

29
30
31
Experiment on seed solution of AgNPs and adding further Ag precursor
and reducing electrons to check how the seed particles affected.

• At optimal concentrations: surface reduction of Ag ions occurs on the

surface of formed AgNPs owing to the reduction potential of the citrate
adsorbed onto the surface.
• At low concentrations, coalescence of smaller silver NP clusters occurs.
32
33
 Crystal Morphologies

• Many different crystal morphologies (shape and structure) can be observed

during crystal growth from a vapour phase.
• Experiments show that the morphology is strongly related to the growth
conditions, i.e. the supersaturation of thewater vapour as well as the growth
temperature. This is a general observation, valid for all sorts of crystals.
• Eg. Thin film Crystals growth models

Volmer

Frank Vander

Stansky Chrstanove
34
https://www.sciencedirect.com/topics/chemic Prachi Sharma et.al. Journal of Materials Science: Materials
al-engineering/vacuum-deposition in Electronics volume 28, pages3891–3896 (2017)

35
 Chemical Vapor deposition
CVD is a chemical process to produce high quality solid materials. The precursor
gases are delivered into the reaction chamber at approximately ambient
temperature. As they pass over or come into contact with heated substrate,
they react and decompose to form a solid phase which are deposited onto
substrate.
1. Chemical transport methods

2. Vapor decomposition methods

3. Vapor synthesis methods

36
Chemical vapor deposition (CVD)
Lindberg Blue M Mini-Mite-Roll to roll (R2R) CVD

Polsen et.al. (2015) 37

Sample holder CVD Instrumentation
Oven

Flow meter
controller
Concentric Tube/Quartz tube

Oven

Pump
Gas out

Gases cylinder

Ethylene,
Methane,
Hydrogen, and
Ar
www.kejiafurnace.com
Zhengzhou Kejiafurnace Co., LTD
38
 Substrates: metals, alloys, and
pure elements:
Eg; Cu and Ni

https://www.mks.com/n/cvd-physics

39
https://is.muni.cz/el/sci/podzim2007/C7780/um/L24_CVD.pdf
Typical precursors for CVD processes include:

• Oxygen
• Halides: H2SiCl2, HSiCl3, TiCl4, WF6, etc.
• Hydrides: SiH4, GeH4, AlH3(NMe3)2, NH3, etc.
• Organometallics: AlMe3, Ti(CH2tBu)4, etc.
• Metal Alkoxides: TEOS, Tetrakis Dimethylamino Titanium (TDMAT),
Ti(OiPr)4, etc.
• Metal Dialkylamides: Ti(NMe2)4, etc.
• Metal Diketonates: Cu(acac)2
• Metal Carbonyls: Ni(CO)4

40
https://www.mks.com/n/cvd-physics
 CVD categories and variants

• Horizontal chemical vapour deposition (CVD) and vertical CVD

• Low-pressure CVD and atmospheric pressure CVD

• Hot-wall CVD and cold-wall CVD

• Plasma-enhanced CVD, photo-assisted CVD and laser-assisted CVD

• Metal–organic CVD (MOCVD)

• Hot filament/wire CVD

• Initiated CVD

• Oxidative CVD

• Atomic layer deposition and molecular layer deposition

https://www.nature.com/articles/s43586-020-00005-y 41
42
 Diamond
Natural diamond Artificial Diamond
• Diamond stability field
• P & T are just right for
 CVD
diamonds to form  2 weeks
 Hydrocarbon gases

https://sciencequery.com/structure-of-diamond/

120 - 200 km

https://www.jewellerybusiness.com/features/synthetic-
https://gemscience.net/geological-origin-of-natural-diamonds/ gemstones-where-knowledge-is-power/

43
Metal Processing with Lap
MSE 4202

Faceted and Dendrite

Filimon Hadish, Ph.D.

Assistant Professor of Materials Science and Engineering
Adama Science and Technology (ASTU)
Email: filimon.hadish@astu.edu.et
hadfili2005@gmail.com
Phone: +251 900740162

44
 Gallium antimonide (GaSb):
• high thermal conductivity and low latent heat and vapor pressure
• zinc-blende single-crystal structure used
 mid-infrared-emitting diodes and
 thermophotovoltaic cells

Crystal–melt interfaces during the directional solidification of molten GaSb

• stoichiometric composition, and
• the formation of dendrite structures 45
• Because GaSb
o has the high thermal conductivity
o low latent heat
o vapor pressure
• The growth of crystals with a low dislocation density is not very difficult.
• During the single-crystal growth of GaSb is the formation of twin
boundaries is important.
• The formation of twin boundaries gives rise to
 Polycrystallization
 Dendrite growth.

Crystal–melt interfaces formed during the directional solidification of GaSb

were observed using system consisting
• A furnace (suited with a thermocouples) and
• A digital microscope with a zoom lens having a long working distance
46
 GaSb crystal–melt interface
• Dendrite growth was initiated as the planar crystal–melt interface became
unstable with increases in growth velocity
• Dendrites having {111} facets were found to grow in either the 110 or 112
directions
• A pair of twin boundaries was identified at the center of a dendrite.
• Thus, the growth of dendrites in GaSb is associated with nucleation at twin-
related reentrant corners.

47
Electron backscatter diffraction (EBSD) used to determine GaSb dendrites
crystallographic orientations

48
Color coded inverse pole figures (IPFs) for a plane cut perpendicular to the
112 growth direction
• Here, A1 and A2 are the axes parallel to the growth direction and the
normal direction of the top surface of the dendrite, respectively.
• Two {111} twin planes parallel to the top surface of the dendrite and
• The existence of two twin boundaries in the dendrite provides evidence
• The dendrite growth in GaSb is associated with reentrant corners.
49
Metals and alloys also have crystalline structures (Scanning electron microscope)
Molar Gibbs’ Free Energy of a Pure Metal

Two crystal structures

Faceted crystals and faceted growth Dendrite crystals and dendritic

growth
• The shape is determined by the
• Most metals solidify by a primary
growth of the surfaces
precipitation of dendrites.
• The driving force of a faceted
crystal Geometric structures
o the surface tension • Grooves (reentrant corners)
o the growth rate (the kinetics) • Ridges
o the mass transport
time
steel 50
ingots
Dendrite propagation in silicon based on reentrant corners at twin boundaries

• The equilibrium form bounded by {111} facet planes contains two twin boundaries
(Figure (a)).
• Two morphologies can be present at a crystal–melt interface associated with a twin
boundary:
o A reentrant corner with an external angle of 141° and
o A ridge structure with an external angle of 219°.

K. Shiga et al. / Scripta Materialia 168 (2019) 56–60 51

• (a) Typical microstructure of high
aspect ratio dendritic domains,
• (b) Transition from faceted to high
aspect ratio dendritic morphology (right
to left)

52
Thomas A. Griffiths, Journal of Petrology, 2023, Vol. 64, No. 1
• IPF color-coded EBSD maps of the orientation of branching Cpx indicates for
each pixel the crystal direction that is parallel to a fixed reference direction
in sample coordinates,
• According to the IPF color key the reference direction for
• (a) is the sample Z direction and for (b) the sample Y direction

Thomas A. Griffiths, Journal of Petrology, 2023, Vol. 64, No. 1 53

Dynamics at crystal/melt interface
during solidification of multi-
crystalline silicon
Kozo Fujiwara*, Lu-Chung Chuang, and Kensaku Maeda
Institute for Materials Research, Tohoku University,
Sendai, 980-8577, Japan,
High Temperature Materials and Processes 2022; 41: 31–47
54
Directional solidification processes in various methods for producing mc-Si
ingots for solar cells:

(a) conventional directional solidification method,

(b) dendritic casting method, where dendrite growth is promoted along the
bottom wall of the crucible to create a grain structure with large grains,
(c) mono casting method, where a single crystal is preset on the bottom wall of
the crucible to grow a single crystal ingot in the crucible, and
(d) HP mc-Si growth, where tiny beads are preset on the bottom wall of the
crucible to enhance nucleation to obtain a grain structure with small grains.
55
Kozo Fujiwara et al. https://doi.org/10.1515/htmp-2022-0020
Transformation of microscopic interface shape for atomically rough and
smooth planes

(a) the case of a rough plane. The flat interface is transformed to a zigzag
interface with increasing growth rate due to the interface instability and
(b) the case of a smooth plane (facet plane). The flat interface is maintained
even at a higher growth rate. 56
Kozo Fujiwara et al. https://doi.org/10.1515/htmp-2022-0020
 Process of interface instability:

actual images of the interface at the point of interface instability for a Si

single crystal.

57
Kozo Fujiwara et al. https://doi.org/10.1515/htmp-2022-0020
Metal Processing with Lap
MSE 4202

Eutectic and Peritectic Solidification

Filimon Hadish, Ph.D.

Assistant Professor of Materials Science and Engineering
Adama Science and Technology (ASTU)
Email: filimon.hadish@astu.edu.et
hadfili2005@gmail.com
Phone: +251 900740162

58
 Eutectic solidification (ES)
ES of a liquid: a simultaneous precipitation of two or more phases via a
eutectic reaction
Liquid
Liquid

Solidification process before Solid

Solubility Limit (Single Phase Alloy)

• = pure liquid of phase (brick red)

• = between liquid and solid of phase
(light blue)
• = composition below solid of phase
(yellow line) all down to
solidification process
https://www.southampton.ac.uk/~pasr1/eutectic.htm
d eT
m1 o d e m o d e m o d e m o

d e m o d e m o d e m o d e m o
Cooling Curve
d e m o Td2 e m o d e m o d e m o

Temp (oC) d e m o d e m o d e m o d e m o

d e m o d e m o d e mTo d e m o
3

d e m o d e m o d e m o d e m o

d e m o d e m o d e m o d e m o

d e m o d e m o d e m o d e m o

d e m o d e m o d e m o d e m o

Time (sec) 59
 Eutectic solidification (ES)
ES of a liquid: a simultaneous precipitation of two or more phases via a
eutectic reaction
Liquid
Liquid
Solidification Beyond Solid
Solubility Limit (Joule Phase Alloy)

𝜶 𝜷

https://www.southampton.ac.uk/~pasr1/eutectic.htm
phase precipitates d eT
m1 o d e m o d e m o d e m o

d e m o d e m o d e m o d e m o
Cooling Curve
d e m o Td2 e m o d e m o d e m o

Temp (oC) d e m o d e m o d e m o d e m o

d e m o d e m o d e mTo d e m o
3

d e m o d e m o d e m o d e m o

d e m o d e m o d e m o d e m o

d e m o d e m o d e m o d e m o

d e m o d e m o d e m o d e m o

Time (sec) 60
 Eutectic solidification (ES)
ES of a liquid: a simultaneous precipitation of two or more phases via a
eutectic reaction
Liquid
Liquid
Solidification at Eutectic point
(Eutectic point alloys)

𝜶 𝜷

• There is a solidification at a single https://www.southampton.ac.uk/~pasr1/eutectic.htm

temperature (Thermal arrest)
• Formation of lamellar plates d e m o d e m o d e m o de m o

d e m o d e m o d e m o de m o
Cooling Curve
d e m o d e m o d e m o de m o
Temp (oC)
d e m o d e m o d e m o de m o

d e m o d e m o d e m o de m o
Thermal Arrest
d e m o d e m o d e m o de m o

d e m o d e m o d e m o de m o

d e m o d e m o d e m o de m o

d e m o d e m o d e m o de m o
61
Time (sec)
 Eutectic solidification (ES)
ES of a liquid: a simultaneous precipitation of two or more phases via a
eutectic reaction
Liquid
Liquid
Solidification at Near Eutectic
point (Near Eutectic alloys)

liquid 𝑬

𝜶 𝜷

Primary https://www.southampton.ac.uk/~pasr1/eutectic.htm
dem o dem o dem o dem o

dem o dem o dem o dem o

Cooling Curve
dem o dem o dem o dem o

Temp(OC)
dem o dem o dem o dem o

dem o dem o dem o dem o

, ; ,
dem o dem oThermal
dem o dem o

dem o d e mArrest
o dem o dem o

dem o dem o dem o dem o

, dem o dem o dem o dem o

62
Time(sec)
 Classification of Eutectic Structures

Rod-like and plate-like Irregular plate-like eutectic Spiral eutectic structure in

eutectic structures in Cu-Ag structure in Al-Si ZnMg-Zn2

Irregular plate-like eutectic Irregular eutectic structure in Rod-like eutectic structure

structure in Cd-Bi Co-TaC in FeFe2B 63
Alloys with Eutectic Alloys with out Eutectic

Lamellar Homogenous grain

• High strength • Low strength

• Low ductility • High ductility

• High brittleness • High corrosion resistance

• Low corrosion resistance • Low brittleness

https://www.youtube.com/watch?v=K9pZZ3DjvCU 64
 65
P. Lü & H. P. Wang | 6:22641 | DOI: 10.1038/srep22641 www.nature.com/scientificreports
 Peritectic reaction
• Peritectic reaction, in which the primary phase reacts with a liquid phase at
a triple junction on cooling to produce the peritectic phase.

• Observed in many binary alloys systems, such as Ti-Al, Fe-Co, Fe-Ni, etc.
• Terminates once the primary phase is enwrapped by the peritectic phase.
• Then, the primary phase transforms to the peritectic phase by peritectic
transformation.
at 1573K
• Peritectic phase grows equiaxially at a cooling rate of 0.167K/s
• . . alloy is a typical peritectic composition in Ni-Zr binary alloy
system.
• The primary phase and peritectic
phase are both intermetallic
compounds.
• Phase selections between primary
phase and peritectic phase have great
influence on the final solidified
microstructures, which directly relate
to the materials characteristics. 66
P. Lü & H. P. Wang | 6:22641 | DOI: 10.1038/srep22641 www.nature.com/scientificreports
Average cooling rate andundercooling Average volume fractions of peritectic
versus droplet diameter. phase Ni5Zr versus droplet diameter

P. Lü & H. P. Wang | 6:22641 | DOI: 10.1038/srep22641 www.nature.com/scientificreports

liquid

liquid

67
Solidified microstuctures of 𝑵𝒊𝟖𝟑.𝟐𝟓 𝒁𝒓𝟏𝟔.𝟕𝟓 peritectic droplets with different diameters

2.8× 103 K/s

0.167 K/s Cooling rate
Cooling rate in the drop
at DSC tube

68
P. Lü & H. P. Wang | 6:22641 | DOI: 10.1038/srep22641 www.nature.com/scientificreports