METALLIC GLASSES :- A NEW ENGINEERING

MATERIAL
FINAL PROJECT REPORT

Submitted By:
ADITYA RANJAN & ASHWAJIT SINGH
(2K20/A3/74) (2K18/EP/018)

Under the supervision of

Dr. MS NIRANJAN

DEPARTMENT OF MECHANICAL ENGINEERING

DELHI TECHNOLOGICAL UNIVERSITY

BAWANA ROAD, NEW DELHI-110042

 CERTIFICATE

I hereby certify that the project Dissertation titled” METALLIC

GLASSES- A NEW ENGINEERING MATERIAL” which is
submitted by ADITYA RANJAN [B. Tech 1st Year] & ASHWAJIT
SINGH [B. Tech 3rd year], Delhi Technological University, Delhi
in complete fulfilment of the requirement for the award of
the degree of the record of the project work carried out by
the students under my supervision. To the best of my
knowledge this work has not been submitted in part or full
for any Degree or Diploma to this University or elsewhere.
 ABSTRACT

The development of new metallic alloys which form bulk

glasses at low cooling rates has led to significant advances in
the study of undercooled liquid metals and the glass
transition in metallic systems. For the first time it has become
possible to carry out measurements of thermophysical
properties such as specific heat, viscosity, atomic diffusion,
and crystal nucleation rates for liquid alloys over the full
temperature range of the undercooled melt. These new
materials exhibit a rich variety of phenomena, such as liquid
crystal phase separation and nanocrystalline phase
formation, and have interesting potential as engineering
materials.
 ACKNOWLEDGEMENT

The completion of this project could not have been

accomplished without the advice, support and direction from
those around me. I would like to thank Prof. MS NIRANJAN
for his help throughout the duration of the project. He gave
us valuable advice and ideas while letting me able to work
autonomously. Finally, I would like to convey my sincere
gratitude for the continuous support from my fellow
colleagues, as well as all my family and friends, over the
course of this project.
In addition, we would like to thank Department of
Mechanical engineering Delhi Technological University for
giving us the opportunity to work on this topic.
 CONTENTS
TITLE PAGE
CERTIFICATE
ABSTRACT
ACKNOWLEGMENT
CONTENTS
1. INTRODUCTION
2. HISTORY
3. TYPES
4. STRUCTURE
5. PROPERTIES
6. APPLICATIONS
7. CONCLUSION
 INTRODUCTION
An Metallic glasses (also known as amorphous metal or glassy metal) is a solid
metallic material, usually an alloy, with disordered atomic-scale structure.
Most metals are crystalline in their solid state, which means they have a highly
ordered arrangement of atoms. Amorphous metals are non-crystalline, and
have a glass-like structure. But unlike common glasses, such as window glass,
which are typically electrical insulators, amorphous metals have good electrical
conductivity and they also display superconductivity at low temperatures.

There are several ways in which metallic glasses can be produced, including
extremely rapid cooling, physical vapour deposition, solid-state reaction, ion
irradiation, and mechanical alloying. Previously, small batches of amorphous
metals had been produced through a variety of quick-cooling methods, such as
amorphous metal ribbons which had been produced by sputtering molten
metal onto a spinning metal disk (melt spinning). The rapid cooling (in the
order of millions of degrees Celsius a second) is too fast for crystals to form
and the material is "locked" in a glassy state. Currently, a number of alloys with
critical cooling rates low enough to allow formation of amorphous structure in
thick layers (over 1 millimeter) have been produced; these are known as bulk
metallic glasses (BMG). More recently, batches of amorphous steel with three
times the strength of conventional steel alloys have been produced.

Metallic glasses are preferred over metals, ceramics, magnetic and some other
types of existing materials due to their enhanced properties. Some of the
important reasons for which we consider these glasses for specific applications
are discussed in the followings.

As discussed earlier metallic glasses have no long-range of ordering like

crystalline materials. It develops more homogeneity inside the material
because defects like point defects, dislocations and stacking faults are absent.

These materials possess very high strength in the elastic region. It can be
declared as a good yielding strength of the material which is higher than steel.
Because of the good homogeneity of atoms in metallic glasses, very good
corrosion resistance is achieved along with good wear resistance.

These materials have good luster and mirror effects but they are opaque.

The metallic glasses are very hard materials and their fracture resistance is
much better compared to ceramics.

Because of the metallic atoms, these glasses possess significant magnetic

effects. It helps to easily magnetize or demagnetize these materials. Metallic
glasses with soft magnetism have very small hysteresis loop. Due to the narrow
hysteresis, in these glasses hysteresis loss is minimized.
 HISTORY
The first reported metallic glass was an alloy (Au75Si25) produced at Caltech
by W. Klement (Jr.), Willens and Duwez in 1960. This and other early glass-
forming alloys had to be cooled extremely rapidly (on the order of one
megakelvin per second, 106 K/s) to avoid crystallization. An important
consequence of this was that metallic glasses could only be produced in a
limited number of forms (typically ribbons, foils, or wires) in which one
dimension was small so that heat could be extracted quickly enough to achieve
the necessary cooling rate. As a result, metallic glass specimens (with a few
exceptions) were limited to thicknesses of less than one hundred micrometers.

In 1969, an alloy of 77.5% palladium, 6% copper, and 16.5% silicon was found
to have critical cooling rate between 100 and 1000 K/s.

In 1976, H. Liebermann and C. Graham developed a new method of

manufacturing thin ribbons of amorphous metal on a supercooled fast-
spinning wheel.[4] This was an alloy of iron, nickel, and boron. The material,
known as Metglas, was commercialized in the early 1980s and is used for low-
loss power distribution transformers (amorphous metal transformer). Metglas-
2605 is composed of 80% iron and 20% boron, has Curie temperature of 373 °C
and a room temperature saturation magnetization of 1.56 teslas.

In 1982, a study on amorphous metal structural relaxation indicated a

relationship between the specific heat and temperature of (Fe0.5Ni0.5)83P17.
As the material was heated up, the properties developed a negative
relationship starting at 375 K, which was due to the change in relaxed
amorphous states. When the material was annealed for periods from 1 to 48
hours , the properties developed a positive relationship starting at 475 K for all
annealing periods, since the annealing induced structure disappears at that
temperature.[6] In this study, amorphous alloys demonstrated glass transition
and a super cooled liquid region. Between 1988 and 1992, more studies found
more glass-type alloys with glass transition and a super cooled liquid region.
From those studies, bulk glass alloys were made of La, Mg, and Zr, and these
alloys demonstrated plasticity even when their ribbon thickness was increased
from 20 μm to 50 μm. The plasticity was a stark difference to past amorphous
metals that became brittle at those thicknesses.
In 1988, alloys of lanthanum, aluminium, and copper ore were found to be
highly glass-forming. Al-based metallic glasses containing Scandium exhibited a
record-type tensile mechanical strength of about 1500 MPa.

In the 1990s new alloys were developed that form glasses at cooling rates as
low as one kelvin per second. These cooling rates can be achieved by simple
casting into metallic molds. These "bulk" amorphous alloys can be cast into
parts of up to several centimeters in thickness (the maximum thickness
depending on the alloy) while retaining an amorphous structure. The best
glass-forming alloys are based on zirconium and palladium, but alloys based on
iron, titanium, copper, magnesium, and other metals are also known. Many
amorphous alloys are formed by exploiting a phenomenon called the
"confusion" effect. Such alloys contain so many different elements (often four
or more) that upon cooling at sufficiently fast rates, the constituent atoms
simply cannot coordinate themselves into the equilibrium crystalline state
before their mobility is stopped. In this way, the random disordered state of
the atoms is "locked in".

In 1992, the commercial amorphous alloy, Vitreloy 1 (41.2% Zr, 13.8% Ti, 12.5%
Cu, 10% Ni, and 22.5% Be), was developed at Caltech, as a part of Department
of Energy and NASA research of new aerospace materials.

In 2004, bulk amorphous steel was successfully produced by two groups: one
at Oak Ridge National Laboratory, who refers to their product as "glassy steel",
and the other at the University of Virginia, calling theirs "DARVA-Glass
101".The product is non-magnetic at room temperature and significantly
stronger than conventional steel, though a long research and development
process remains before the introduction of the material into public or military
use.

In 2018 a team at SLAC National Accelerator Laboratory, the National Institute

of Standards and Technology (NIST) and Northwestern University reported the
use of artificial intelligence to predict and evaluate samples of 20,000 different
likely metallic glass alloys in a year. Their methods promise to speed up
research and time to market for new amorphous metals alloys.
 TYPES
There are two types of Metallic glasses

• Metal - metal metallic glasses.

• Metal - metalloid metallic glasses.

1. Metal - metal metallic glasses.

They are formed by combination of metals.

Example:

1. Ni - Nb (Nickel & Niobium).

2. Mg - Zn (Magnesium & zinc).

3. Cu - Zr (Copper & Zirconium).

4. Hf - V (Hafnium & Vanadium).

2. Metal - metalloid metallic glasses.

They are formed by combination of metals and metalloid.

Example:

Metals like Fe, Co, Ni and metalloid such as B, Si, C, P.

 STRUCTURE
Structure of material defines its property. BMGs do not exhibit a long-range
order structure, as they solidify from liquid without reaching the crystalline
ground state. However, short to medium-range structural order does develop
to a considerable extent under the given kinetic constraints. This happens
because the atoms strive to find comfortable configurations to lower their
energy. The structure of the bulk metallic liquids was first observed by Bernal
and it was described as dense random packing. Structural features of metallic
glasses are discussed by Michael et al. where the concept of efficient filling of
space is supported. The rationalization of the good glass forming compositions
can be possible by the analysis of dense packing. An example of simple binary
metallic glass is shown in Figure 2. These structural motifs arise from the
strong tendency to form as many bonds as possible between unlike species
because of the large negative heat of mixing which is usual in good glass
formers. The size of the cluster and its type depend on the relative size of the
solvent and the solute. The replacement of Pt solute in Figure 2 by much
smaller Be reduce the number of Zr neighbours which can be accommodated
around the solute, and the solute concentration in the alloy would be
correspondingly much higher. The medium-range order and dense packing in
three-dimensional space can be possible by the overlapping of the cluster via
various solvent-atom sharing schemes.

Figure –Model of Structure of metallic glass

 PROPERTIES
Amorphous metal is usually an alloy rather than a pure metal. The alloys
contain atoms of significantly different sizes, leading to low free volume (and
therefore up to orders of magnitude higher viscosity than other metals and
alloys) in molten state. The viscosity prevents the atoms moving enough to
form an ordered lattice. The material structure also results in low shrinkage
during cooling and resistance to plastic deformation. The absence of grain
boundaries, the weak spots of crystalline materials, leads to better resistance
to wear and corrosion. Amorphous metals, while technically glasses, are also
much tougher and less brittle than oxide glasses and ceramics. Amorphous
metals can be grouped in two categories, as either non-ferromagnetic, if they
are composed of Ln, Mg, Zr, Ti, Pd, Ca, Cu, Pt and Au, or ferromagnetic alloys, if
they are composed of Fe, Co, and Ni.

Thermal conductivity of amorphous materials is lower than that of crystalline

metal. As formation of amorphous structure relies on fast cooling, this limits
the maximum achievable thickness of amorphous structures. To achieve
formation of amorphous structure even during slower cooling, the alloy has to
be made of three or more components, leading to complex crystal units with
higher potential energy and lower chance of formation. The atomic radius of
the components has to be significantly different (over 12%), to achieve high
packing density and low free volume. The combination of components should
have negative heat of mixing, inhibiting crystal nucleation and prolonging the
time the molten metal stays in supercooled state.

The alloys of boron, silicon, phosphorus, and other glass formers with magnetic
metals (iron, cobalt, nickel) have high magnetic susceptibility, with low
coercivity and high electrical resistance. Usually the electrical conductivity of a
metallic glass is of the same low order of magnitude as of a molten metal just
above the melting point. The high resistance leads to low losses by eddy
currents when subjected to alternating magnetic fields, a property useful for
e.g. transformer magnetic cores. Their low coercivity also contributes to low
loss.
The superconductivity of amorphous metal thin films was discovered
experimentally in the early 1950s by Buckel and Hilsch. For certain metallic
elements the superconducting critical temperature Tc can be higher in the
amorphous state (e.g. upon alloying) than in the crystalline state, and in
several cases Tc increases upon increasing the structural disorder. This
behavior can be understood and rationalized by considering the effect of
structural disorder on the electron-phonon coupling.

Amorphous metals have higher tensile yield strengths and higher elastic strain
limits than polycrystalline metal alloys, but their ductilities and fatigue
strengths are lower. Amorphous alloys have a variety of potentially useful
properties. In particular, they tend to be stronger than crystalline alloys of
similar chemical composition, and they can sustain larger reversible ("elastic")
deformations than crystalline alloys. Amorphous metals derive their strength
directly from their non-crystalline structure, which does not have any of the
defects (such as dislocations) that limit the strength of crystalline alloys. One
modern amorphous metal, known as Vitreloy, has a tensile strength that is
almost twice that of high-grade titanium. However, metallic glasses at room
temperature are not ductile and tend to fail suddenly when loaded in tension,
which limits the material applicability in reliability-critical applications, as the
impending failure is not evident. Therefore, there is considerable interest in
producing metal matrix composites consisting of a metallic glass matrix
containing dendritic particles or fibers of a ductile crystalline metal.

Perhaps the most useful property of bulk amorphous alloys is that they are
true glasses, which means that they soften and flow upon heating. This allows
for easy processing, such as by injection molding, in much the same way as
polymers. As a result, amorphous alloys have been commercialized for use in
sports equipment, medical devices, and as cases for electronic equipment.

Thin films of amorphous metals can be deposited via high velocity oxygen fuel
technique as protective coatings.
 APPLICATIONS
Commercial
Currently the most important application is due to the special magnetic
properties of some ferromagnetic metallic glasses. The low magnetization loss
is used in high efficiency transformers (amorphous metal transformer) at line
frequency and some higher frequency transformers. Amorphous steel is a very
brittle material which makes it difficult to punch into motor laminations. Also
electronic article surveillance (such as theft control passive ID tags,) often uses
metallic glasses because of these magnetic properties.

A commercial amorphous alloy, Vitreloy 1 (41.2% Zr, 13.8% Ti, 12.5% Cu, 10%
Ni, and 22.5% Be), was developed at Caltech, as a part of Department of
Energy and NASA research of new aerospace materials.

Ti-based metallic glass, when made into thin pipes, have a high tensile strength
of 2100 MPA, elastic elongation of 2% and high corrosion resistance.[30] Using
these properties, a Ti–Zr–Cu–Ni–Sn metallic glass was used to improve the
sensitivity of a Coriolis flow meter. This flow meter is about 28-53 times more
sensitive than conventional meters,[31] which can be applied in fossil-fuel,
chemical, environmental, semiconductor and medical science industry.

Zr-Al-Ni-Cu based metallic glass can be shaped into 2.2–5 mm by 4 mm

pressure sensors for automobile and other industries, and these sensors are
smaller, more sensitive, and possess greater pressure endurance compared to
conventional stainless steel made from cold working. Additionally, this alloy
was used to make the world's smallest geared motor with diameter 1.5mm
and 9.9mm to be produced and sold at the time.

Potential
Metallic glass exhibit unique softening behaviour above their glass transition
and this softening has been increasingly explored for thermoplastic forming of
metallic glasses. Such low softening temperature allows for developing simple
methods for making composites of nanoparticles (e.g. carbon nanotubes) and
BMGs. It has been shown that metallic glasses can be patterned on extremely
small length scales ranging from 10 nm to several millimetres. This may solve
the problems of nanoimprint lithography where expensive nano-molds made
of silicon break easily. Nano-molds made from metallic glasses are easy to
fabricate and more durable than silicon molds. The superior electronic,
thermal and mechanical properties of BMGs compared to polymers make
them a good option for developing nano-composites for electronic application
such as field electron emission devices.

Ti40Cu36Pd14Zr10 is believed to be non-carcinogenic, is about three times

stronger than titanium, and its elastic modulus nearly matches bones. It has a
high wear resistance and does not produce abrasion powder. The alloy does
not undergo shrinkage on solidification. A surface structure can be generated
that is biologically attachable by surface modification using laser pulses,
allowing better joining with bone.

Mg60Zn35Ca5, rapidly cooled to achieve amorphous structure, is being

investigated, at Lehigh University, as a biomaterial for implantation into bones
as screws, pins, or plates, to fix fractures. Unlike traditional steel or titanium,
this material dissolves in organisms at a rate of roughly 1 millimeter per month
and is replaced with bone tissue. This speed can be adjusted by varying the
content of zinc.
 CONCLUSION

It has been shown that metallic glasses have outstanding physical,

chemical and magnetic properties. In addition, metallic glasses are
produced directly from the liquid state into the net shape in a single
step and thus the process is much cheaper than the conventional
methods and so economically viable. These factors are responsible
for the intensive activity throughout the world to see that metallic
glasses replace the existing crystalline materials at least in some
spheres.