MSE 440/540: Processing of Metallic Materials

Instructors: Yuntian Zhu

Office: 308 RBII
Ph: 513-0559
ytzhu@ncsu.edu

Lecture 17: Advanced Processing of

Metastable Materials

Department of Materials Science and Engineering 1 NC State University

 Non-Equilibrium Processing

A metastable structure is considered to have local minima in

free energy, and not the lowest free energy of the system

1.Metastable state
2.Transitional stable state
3.Stable state

Department of Materials Science and Engineering 2 NC State University

 Non-Equilibrium Processing

We will be concerned with metastable structures, or more

accurately configurationally frozen metastable structures.

-Diamond is metastable at room temperature and atmospheric

pressure
-Microstructures that harden steel are metastable
-Snow about to avalanche

Department of Materials Science and Engineering 3 NC State University

 Non-Equilibrium Processing

Generalized procedure to obtain metastable materials:

-Energize then Quench a material

-The Energization consists of raising the energy of a phase

at ambient temperature and pressure in various ways:
- Raise the temperature or pressure to transform the material to a
phase stable at higher temperatures (or pressure), e.g. a liquid or
high temp allotrope
- Evaporation
-Dissolution
-Irradiation
-Severe Plastic Deformation

Department of Materials Science and Engineering 4 NC State University

 Non-Equilibrium Processing

-The Quenching back to ambient conditions can be

characterized by high cooling rate

- In the Energize and Quench approach, the phase of the

Energized matter can be gas, liquid, or solid; deposition from
gas or liquid phase is most common

Department of Materials Science and Engineering 5 NC State University

 Gas Phase Deposition
Thermal Evaporation
-Atoms are evaporated from one material, and deposited on a
substrate
-The cooling occurs on pico-second time scales, with cooling rates
on the order of 1013 -1014 K/s
-The atoms are frozen on the substrate/film; the low temperature
prevents diffusion
- Most times this is used to make amorphous metastable
microstructures
- Problem: Differential evaporation different components have
different vapor pressures, so the composition of the film cannot be
easily controlled

Department of Materials Science and Engineering 6 NC State University

 Gas Phase Deposition

Thermal Evaporation
-Problem: Differential evaporation different components
have different vapor pressures, so the composition of the
film is difficult to control
- Ways to avoid Differential Evaporation
- Flash evaporation powdered material is dropped
steadily onto a heated ribbon, thereby almost
instantaneously vaporizing it
- Use of separate power sources for each element and
balance the evaporation rate to obtain desired
composition

Department of Materials Science and Engineering 7 NC State University

 Gas Phase Deposition

Sputtering
-Advantage over thermal deposition in that it is easier to
control the composition since an average composition of
the sputtering target is deposited on the substrate
- Like thermal evaporation, this is also a thin film
technique, with maximum film size ~10s of micron

Department of Materials Science and Engineering 8 NC State University

 Liquid Phase Deposition
Rapid Solidification Processing (RSP)
-Became popular in the 1960s and 1970s to create new materials
with superior properties
- The definition for rapid solidification is the cooling from the melt
from its melting temperature to a low value (~room temperature)
very rapidly usually milliseconds or less
- The range of quench rates can vary from 102 to 1010 C/s, but most
techniques are in the 104 to 106 C/s range
- Effects include
- Decreased grain size
- Increased chemical homogeneity
- Extension of solid solubilities
- Creation of metastable crystal structures
- Creation of bulk metallic glasses

Department of Materials Science and Engineering 9 NC State University

 Liquid Phase Deposition
Melt Spinning
Developed by Pond and Madden in 1969, but
used more frequently in the 1970s and 80s

Free Flight Melt Spinning

-This method consists of creating and
subsequently solidifying a stable liquid jet on
passage through a gaseous or liquid quenching
medium

- Problem: solidifying the metal into a wire

prevents droplets from being formed

- Advantage: Allows production of continuous

filaments of circular cross section
http://www.youtube.com/watch?v=2--vIYNwgCY

Department of Materials Science and Engineering 10 NC State University

 Liquid Phase Deposition
Chill Block Melt Spinning
-Like free flight melt spinning, chill block melt
spinning employs a jet of liquid metal extruded
through an orifice.

-In chill block melt spinning, however,

solidification is achieved when the molten jet
impinges on the surface of a rotating solid
substrate (rotating water cooled metal disks

- Filaments several mm wide and 25

micrometers thick are produced

https://www.youtube.com/watch?v=L00HbH8Vla8

Department of Materials Science and Engineering 11 NC State University

 Metastable Materials

-Metastable crystalline alloys made by rapid solidification

Among the differences which may result from rapid
solidification are:
- Microstructural refinement
- Solid solubility extension
- Formation of unique metastable phases
- Greater chemical homogeneity
- Changes in crystal morphology

Department of Materials Science and Engineering 12 NC State University

 Metastable Materials
Most alloy development via Rapid Solidification has been with Al
alloys, tool steel and superalloys involving precipitation
hardening or solution hardening mechanisms

The greater homogeneity and extended solid solubility which

may result from rapid solidification alloy greater freedom in alloy
design

Alumimum alloys: Al alloys for higher strength, higher elastic

modulus for aerospace applications include
- Al-Li-X alloys which involve precipitation of Al3Li from a
supersaturated solid solution.
- Al-Mn-X and Al-Fe-N-Co alloys have also been developed

Department of Materials Science and Engineering 13 NC State University

 Metastable Materials
Irons and Steels: High speed tool steels have rapidly solidified
gas-atomized powders which are consolidated by HIPing. These
have finer, more uniform microstructures (distribution of carbides)
than the same alloys made by ingot metallurgy

Superalloys and Titanium: Rapidly solidified Ni-based

superalloys (Ni-Al-Mo) powder has been consolidated by HIPing,
hot pressing or extrusion for use in gas turbine blades to increase
their operating temperatures.

Ti alloys (Ti-6Al-4V) have been rapidly solidified by the melt

extraction method and by powder atomization methods. Finer,
more uniform microstructures and chemical homogeneity give
better mechanical properties

Department of Materials Science and Engineering 14 NC State University

 Laser or Electron Beam Methods (3D Printing)
Additive Manufacturing
Laser or Electron Beam Surface
Melting
-Involve local melting of the alloy;
also called self quenching,
laser annealing:, laser glazing.
-High power densities are
concentrated on a small spot (0.1
to 1.0 mm) for short times (~10-5 s)
-Cooling rate of 106 108 K/s are
reported, but for very thin layers
(0.01 to 0.1 micrometers), can be
1010-1013 K/s (highest cooling
rates for RSP)
http://www.youtube.com/watch?v=BxxIVLnAbLw

https://www.youtube.com/watch?v=cRE-PzI6uZA

Department of Materials Science and Engineering 15 NC State University

 Solid State Methods
Severe Plastic Deformation
- Mechanical Alloying or Mechanical Milling
Ball milling of either dissimilar powders (MA) or single
composition powders (elements or compounds (MM) ) has been
found to induce metastable structures in many materials. These
metastable phases include:
-Amorphous
-Metastable crystalline compounds
-Supersaturated solid solutions
-Quasicrystalline phases (2011 Nobel Prize in Chemistry
Schectman)
-Nanocrystalline microstructures

Department of Materials Science and Engineering 16 NC State University

 Solid State Methods
Severe Plastic Deformation
- Mechanical Alloying or Mechanical Milling

MM/MA has been carried out in a variety of high

energy shaker, vibratory, or planetary mills, as well
as larger attritor and ball mills.

Conventional low energy mills are used, but long

times (weeks to months) are required to obtain the
same microstructures a high energy mill can get in
a day or less

Usually carried out in inert atmosphere to prevent

oxidation

Department of Materials Science and Engineering 17 NC State University

 Solid State Methods
Severe Plastic Deformation
- Mechanical Alloying or Mechanical Milling

The central event in mechanical milling or alloying is the ball-

powder-ball collision, where powder particles are trapped between
the colliding balls during milling and undergo deformation and/or
fracture processes which define the ultimate structure of the powder

Department of Materials Science and Engineering 18 NC State University

 Severe Plastic Deformation
Severe Plastic Deformation of Bulk Samples
- Plastic deformation of bulk samples gets around the
problem of consolidation of powder
- In recent years, there has been high interest in methods
which give submicron and nanocrystalline materials
- The two most common methods are:
-High Pressure Torsion (HPT)
-Equal Channel Angular Extrusion (ECAE)

Department of Materials Science and Engineering 19 NC State University

 Severe Plastic Deformation
High Pressure Torsion (HPT)
involves superimposing high
hydrostatic pressure on a sample
being sheared in torsion.
- Very high strains can be achieved
by this technique
- Grain sizes obtained are typically
100-200 nm but in some cases, <100
nm

Department of Materials Science and Engineering 20 NC State University

 Severe Plastic Deformation
Equal Channel Angular Extrusion (ECAE),
also called Equal Channel Angular Pressing
(ECAP) involves bending and rebending a
rod through a special die, which is typically
90 degrees
- The advantage is that larger samples can
be processed than with HPT Army testing
15 x 15 x 3.4 billets of Al-alloys

-The disadvantage is that only materials

with ductility can be processed, and grain
sizes are typically 200 500 nm

Department of Materials Science and Engineering 21 NC State University

 Surface Mechanical Attrition

Department of Materials Science and Engineering 22 NC State University