Effects of temperature, stress state, and

strain rate on flow and fracture of Mg

metallic glass and viscous fluids

Lisa A. Deibler

Submitted in partial fulfillment of the

requirements for a Masters Degree

Advisor:
Prof. John Lewandowski

Department of Materials Science and

Engineering
CASE WESTERN RESERVE UNIVERSITY
May, 2009
Print out two copies of this form on 25% Cotton Bond paper, as it will accompany your thesis or dissertation.
(This notice will not show up on printouts).

CASE WESTERN RESERVE UNIVERSITY

SCHOOL OF GRADUATE STUDIES

We hereby approve the thesis/dissertation of

Lisa A Deibler
______________________________________________________

Master's
candidate for the ________________________________degree *.

John Lewandowski
(signed)_______________________________________________
(chair of the committee)

Gary Michal
________________________________________________

Dave Schwam
________________________________________________

________________________________________________

________________________________________________

________________________________________________

4-1-09
(date) _______________________

*We also certify that written approval has been obtained for any
proprietary material contained therein.
 Dedication
To my parents, to prove to them that 18+ years of teaching me everything from
how to read to how to do calculus was not in vain.

1
Contents

List of Tables 4

List of Figures 5

1 Introduction 9

2 Background 11
2.1 Development of metallic glasses . . . . . . . . . . . . . . . . . . . . . 11
2.2 Structural properties of metallic glasses . . . . . . . . . . . . . . . . . 12
2.3 Flow and fracture behavior of metallic glasses . . . . . . . . . . . . . 12
2.4 Developments in model viscous material experiments . . . . . . . . . 15

3 Experimental procedures 17
3.1 Effects of test conditions on viscous fracture . . . . . . . . . . . . . . 17
3.1.1 Materials preparation and characterization . . . . . . . . . . . 17
3.1.2 Substrate design . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.1.3 Mechanical tests . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.1.4 Data analysis/characterization . . . . . . . . . . . . . . . . . . 21
3.2 Metallic glass ribbon characterization . . . . . . . . . . . . . . . . . . 22
3.2.1 Materials preparation . . . . . . . . . . . . . . . . . . . . . . . 22
3.2.2 DSC and XRD . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.2.3 Tensile tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.2.4 Viscosity approximation . . . . . . . . . . . . . . . . . . . . . 23
3.2.5 Hardness tests . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.2.6 Bending around a mandrel . . . . . . . . . . . . . . . . . . . . 24
3.2.7 Fracture surface and true strain characterization . . . . . . . . 25

4 Experimental results 26
4.1 Characterization of model viscous fracture surfaces . . . . . . . . . . 26
4.1.1 Geometry effects on viscous fracture . . . . . . . . . . . . . . 27
4.1.2 Rheology of grease . . . . . . . . . . . . . . . . . . . . . . . . 30
4.1.3 Temperature effects on viscous fracture . . . . . . . . . . . . . 30
4.1.4 Viscosity calculation from tensile data . . . . . . . . . . . . . 31
4.2 Characterization of Mg based metallic glass ribbon . . . . . . . . . . 32
4.2.1 Structure of materials . . . . . . . . . . . . . . . . . . . . . . 33

2
 4.2.2 Vickers microhardness . . . . . . . . . . . . . . . . . . . . . . 35
4.2.3 Tensile tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
4.2.4 Fracture surfaces . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.2.5 Bending over mandrel test . . . . . . . . . . . . . . . . . . . . 42
4.2.6 Viscosity determination . . . . . . . . . . . . . . . . . . . . . 45

5 Discussion 48
5.1 Comparison of viscous model results to model by Spaepen [1] . . . . . 48
5.2 Mechanical behavior of Mg-based metallic glass . . . . . . . . . . . . 49
5.2.1 Unique stress-strain curve appearance . . . . . . . . . . . . . . 50
5.2.2 Agreement between mechanical tests . . . . . . . . . . . . . . 51
5.2.3 Temperature effects on structure, fracture surfaces, and me-
chanical properties . . . . . . . . . . . . . . . . . . . . . . . . 52
5.2.4 Comparison of data to deformation map . . . . . . . . . . . . 54
5.2.5 Comparison of viscosity obtained to literature values . . . . . 56
5.2.6 Comparison of data with other Mg metallic glasses . . . . . . 57
5.3 Comparison of viscous material model experiments to metallic glasses 58

6 Conclusions 60

7 Future research 63

Bibliography 64

3
List of Tables

4.1 Yield stresses and fracture strains of samples at various temperatures 40

4.2 Mandrel bend test results . . . . . . . . . . . . . . . . . . . . . . . . 46
4.3 Calculated viscosities of Mg metallic glass under various conditions . 47

5.1 Comparison of Spaepen’s model prediction to measured grease features 50

5.2 Comparison of strengths and strains for mechanical tests performed at
room temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
5.3 Flow stress and failure strain data for points in figure 5.2 . . . . . . . 55
5.4 Summary of compressive mechanical properties from [2]. . . . . . . . 58

4
List of Figures

2.1 Deformation map of a metallic glass [1] . . . . . . . . . . . . . . . . . 13

2.2 Deformation map of a metallic glass with strain-temperature axes [3] 14
2.3 Schematic of veins developing via the Taylor model in a viscous mate-
rial [4] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

3.1 Parallel plate rheometer setup . . . . . . . . . . . . . . . . . . . . . . 18

3.2 Procedure for rheology of all greases . . . . . . . . . . . . . . . . . . 19
3.3 Cylindrical substrates: a) 0◦ ; b) 30◦ . . . . . . . . . . . . . . . . . . . 19
3.4 Rectangular substrates: a)10:1, 2:1, and 1:1 substrates; b) 1:1 substrate
clamped at 30◦ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.5 Schematic of substrate design showing variables changed. a) cylindrical
substrates, α varied from 0 to 75◦ b) rectangular substrates, L varied
from 0.75” to 7.5” . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.6 Setup for viscous tests in Instron testing rig . . . . . . . . . . . . . . 21
3.7 Schematic of intercept counting method for feature size determination 22
3.8 Schematic of metallic glass tensile sample . . . . . . . . . . . . . . . . 22
3.9 Metallic glass ribbon in tensile fixture . . . . . . . . . . . . . . . . . . 23

4.1 Effect of thickness of viscous layer on feature size in AP-1 grease . . . 27

4.2 Effect of substrate shape on feature size and character produced by on 28
4.3 Effect of test angle on feature size in model feature experiments . . . 29
4.4 Effect of test angle on feature size in AP-1 grease on square substrate:
a) 0◦ , b) 30◦ , c) 45◦ , d) 60◦ . . . . . . . . . . . . . . . . . . . . . . . . 29
4.5 Viscosity of three greases as a function of temperature . . . . . . . . 30
4.6 Feature size of three greases as a function of viscosity . . . . . . . . . 31
4.7 Viscosity plotted as a function of temperature, comparing viscosity
measured with rheometer to viscosity calculated from tensile tests. . . 33
4.8 Ratio of measured viscosity to calculated viscosity versus temperature. 34
4.9 DSC trace of Mg metallic glass ribbon heated at 3◦ C/min . . . . . . 34
4.10 X-ray diffraction patterns from as-received metallic glass . . . . . . . 35
4.11 X-ray diffraction patterns of samples heated to temperatures shown . 36
4.12 Vickers microhardness of sample with heating to glass transition tem-
perature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
4.13 Vickers microhardness of samples previously tested in tensile tests . . 38

5
4.14 Vickers microhardness of samples annealed for use in XRD experiments
(figure 4.11) *Samples exhibited large cracks around the indents, so
actual hardnesses are higher. . . . . . . . . . . . . . . . . . . . . . . . 39
4.15 Effect of changes in strain rate on tensile properties of Mg-based glass
tested at room temperature . . . . . . . . . . . . . . . . . . . . . . . 40
4.16 Effect of changes in strain rate on tensile properties of Mg-based glass
tested at the glass transition temperature (100◦ C) . . . . . . . . . . . 41
4.17 Effects of changes in test temperature and strain rate on tensile prop-
erties of Mg-based glass . . . . . . . . . . . . . . . . . . . . . . . . . 42
4.18 Effect of change in test temperature on reduction in area in Mg-based
metallic glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
4.19 Sample tested at strain rate 10−3 1/s and room temperature . . . . . 43
4.20 Sample tested at strain rate 10−3 1/s and 80◦ C showing a region of the
sample containing ductile rupture . . . . . . . . . . . . . . . . . . . . 44
4.21 Sample tested at strain rate 10−3 1/s and 80◦ C showing a region of the
sample viscous-like fracture . . . . . . . . . . . . . . . . . . . . . . . 44
4.22 Sample tested at strain rate 10−3 1/s and 100◦ C showing a region of the
sample displaying viscous-like fracture transitioning to ductile rupture 45
4.23 Sample tested at strain rate 10−3 1/s and 100◦ C showing a region of
the sample displaying ductile rupture . . . . . . . . . . . . . . . . . . 45
4.24 Sample tested at strain rate 10−3 1/s and 140◦ C showing a region of
the sample displaying brittle fracture . . . . . . . . . . . . . . . . . . 46
4.25 Arrows indicate shear bands present on the surface of Mg-based metal-
lic glass bent around a mandrel of diameter 1.87 mm . . . . . . . . . 47

5.1 Cross section of Mg-based metallic glass ribbon, illustrating the non-
uniform cross section of the samples. . . . . . . . . . . . . . . . . . . 52
5.2 Deformation map from Schuh [3] with Mg-based metallic glass data.
Dots mark data points. The flow stress and failure strains for each dot
are in table 5.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
5.3 Shear bands near the fracture surface of a sample tested at room tem-
perature, 10−3 s−1 . The fracture surface is at the bottom of the image. 56
5.4 Viscosity of a Zr-based metallic glass as a function of temperature from
Nouri [5] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
5.5 Calculated viscosities of various metallic glasses plotted against frac-
ture surface feature size . . . . . . . . . . . . . . . . . . . . . . . . . 59

6
 Acknowledgments

I would like to thank Professor John Lewandowski for his guidance and support on
this project. I’d also like all the members of the MMC group and Chris Tuma for
their technical support. Mohit Gupta and Zheng Li from the CWRU Macromolecular
Science project provided very kind assistance with DSC and rheological measurements
for which I am very grateful. I’d like to thank my parents for their support and Ken
Craymer for his friendship and all the great food while I was busy.
Thanks to the University of Virginia for providing the Mg-based metallic glass
ribbons.
Thanks for financial support go to Boeing, DARPA SAM II program, and the
NDSEG Fellowship.

7
 Effects of Temperature, Stress State, and Strain
Rate on Flow and Fracture of Mg Metallic Glass
and Viscous Fluids
Abstract
by
Lisa A. Deibler

The purpose of this study is to examine how changes in viscosity affect the fracture
surface observations on a model test system, and to apply the knowledge gained to
the tensile properties of amorphous Mg85 Cu5 Ca10 ribbons. Experiments were first
conducted on tensile samples of varying geometries constructed to contain liquids of
different viscosity that were tested at three temperatures. The observed fracture sur-
faces of these viscous materials were quantitatively examined to provide a comparison
with metallic glass fracture surfaces. Metallic glass ribbons were subsequently tested
in tension at various temperatures up to and beyond the glass transition temperature
and examined via scanning electron microscopy. The different viscosities produced via
changes in test temperature and or initial liquid viscosity affected both flow behavior
and fracture appearance. The results will be discussed in the light of the various
models for flow and fracture in such systems.

8
Chapter 1

Introduction

Interest in metallic glasses, or amorphous alloys, has been growing over the years. The
technology which was developed in the 1990s to fabricate metallic glasses in relatively
large diameters caused interest to be renewed. With these advances, research into
many different compositions was conducted in an attempt to find a glass with good
mechanical properties which was easily manufactured. Many metallic glasses have
higher strengths than their crystalline counterparts, and can be manufactured to
net shape with greater ease. An emphasis on strong, lightweight materials brought
researchers to the light metals, such as magnesium in their search for useful metallic
glasses.
The most important material properties for any metallic glasses designed to be
used as a structural material are the mechanical ones. For this reason, much work
has been conducted on characterizing the failure of metallic glasses in an attempt to
provide a unifying theory of deformation mechanisms for these materials. The fracture
surfaces of metallic glasses often are said to have a vein-like appearance such as what
is seen when grease is smeared between two plates and pulled apart. With this in
mind, it is instructive to study various experimental parameters that might influence
the formation of vein-like features in a set of model experiments on various greases

9
tested under different stress states, temperatures, and strain rates. The knowledge
gained from this study may provide further insight into the failure mechanisms that
occur in metallic glasses.
This research project is composed of two sections. First, in a set of model ex-
periments three different greases were placed between substrates of various shapes
and under various conditions in order to determine the effects of changes in viscosity
and stress state on fracture surface features. The results of the model experiments
were compared to results from both the Mg-based metallic glass from this research,
and other literature works. In the second section the mechanical properties of a
new metallic glass, Mg85 Cu5 Ca10 in ribbon form were investigated. Three types of
mechanical tests were performed at various temperatures and under various testing
conditions: Vickers hardness, tensile tests, and bending around a mandrel. In ad-
dition, the structural characteristics of the alloy were investigated via differential
scanning calorimetry (DSC) and X-ray diffraction (XRD).

10
Chapter 2

Background

The first metallic glasses were discovered by Duwez and coworkers in 1960 with the
synthesis of an amorphous gold-silicon alloy [6]. A glassy state in a metallic glass is
defined as “when a cooled liquid solidifies without crystallization” [7]. The past 15
years have been particularly fruitful in terms of metallic glass research. This chapter
contains background on the history of development of metallic glasses (section 2.1),
a discussion of the typical structural behavior with changing temperature in section
2.2 and flow and fracture behavior in section 2.3. Finally, background on models for
fracture of metallic glasses using viscous materials is described in section 2.4.

2.1 Development of metallic glasses

Since the 1960s work at California Institute of Technology, many advances have been
made in the field of metallic glasses. Until the 1990s, metallic glasses (apart from
expensive Pd-based systems) could only be formed in thin foils or ribbons by splat-
quenching or rolling. In the 1990s, interest in the subject was renewed with experi-
ments with larger numbers of elements which make the glass forming ability higher
and therefore allow larger diameters of glasses to be cast, making bulk metallic glasses
a possibility [8]. One of the first systems studied was Zr-based glass, which came to be

11
known as Vit 1 [9]. Other common and well developed alloys are Fe [10] and Pd [11]
based glasses. As the number of viable bulk metallic glasses increased, researchers
began designing glasses with specific engineered characteristics based on their compo-
sition instead of simply producing a material which would have a high glass forming
ability. In the interest of designing lightweight, strong materials researchers have
turned to the light metals such as Ca [12], Al [13], and Mg [14] for metallic glasses.

2.2 Structural properties of metallic glasses

Metallic glasses are characterized by a glass transition temperature (Tg ) such as

what would commonly be encountered in polymers or silica-based glasses, where the
relaxation of bonds allows the material to flow more. The range between Tg and
the crystallization temperature (Tx ) is very important because of the high degree
of formability, even superplasticity in some cases, which exists in this temperature
range. This range is known as the supercooled liquid regime. When the material is
exposed to temperatures above Tx it crystallizes, typically producing a reduction in
mechanical properties.

2.3 Flow and fracture behavior of metallic glasses

Plastic flow in metallic glasses is characterized by two types of flow; inhomogeneous

flow with deformation in localized areas like shear bands, and homogeneous flow
where the whole volume of the specimen is strained. A deformation mechanism map
as described by Spaepen [1] provides one of the easiest ways of visualizing under what
conditions each type of flow will occur. As pictured in figure 2.1, at low temperatures
and high stresses the flow is inhomogeneous while at lower stresses and higher tem-
peratures the flow is homogeneous. In the homogeneous flow deformation mode the
flow is Newtonian viscous. A Newtonian fluid is one in which the shear stress which

12
evolves is linearly proportional to the shear strain rate. In the homogeneous flow part
of the deformation map, Spaepen describes three regimes. At and above the liquidus
temperature, the flow is fluid with a viscosity of 10−3 Nm−2 sec. For temperatures
near Tg , the material is viscous and has a viscosity between 1015 Nm−2 sec and 1010
Nm−2 sec. For temperatures less than Tg , the material has a viscosity higher than 1015
Nm−2 sec and is termed a solid. This model has been the basis of metallic glass flow
work since 1977, and was further improved upon in Schuh et al. [3] with an extension
of the similar concept to a deformation map with strain rate on one axis (figure 2.2).
The stress values shown develop in the metallic glass Zr41.2 Ti13.8 Cu12.5 Ni10 Be22.5 .

Figure 2.1: Deformation map of a metallic glass [1]

The homogeneous flow regime is the one which incites the most interest in novel
manufacturing and forming applications. It is proposed that flow under this con-
dition is governed by the creation and annihilation of free volume [1]. Two ideas
exist concerning the mechanism behind the inhomogeneous flow regime, where the

13
 Figure 2.2: Deformation map of a metallic glass with strain-temperature axes [3]

deformation is governed by regions of localized flow, often termed shear bands. The
debate centers around whether the shear banding is due to shear induced disordering
or thermal effects. In crystalline alloys, adiabatic shear bands exist and a corollary
in metallic glasses was suggested by Leamy et al. [15]. In this explanation, the tem-
perature in the shear band rises to a temperature higher than Tg due to the release
of strain energy and thus flows viscously until failure. However, if the shear banding
events are assumed to be adiabatic, the calculated displacement rate in an individual
shear band is six orders of magnitude larger than rates which have actually been
observed [3]. Additionally, Lewandowski and Greer [16] used a fusible layer on the
surface of a metallic glass which melted at a known temperature to calculate an upper
bound for the temperature rise in a single shear localization. The temperature dif-
fusion area for this highest possible temperature rise is an order of magnitude larger
than observed shear bands, which gives further evidence that temperature rise does

14
not control shear band thickness.
On the other side of the argument is shear induced disordering. Under this theory,
a critical shear event occurs in a very localized region, which softens the local region.
This softening allows another shear event, which further softens and continues at an
accelerated rate as described by Argon [17]. The area of plastic deformation in this
model consists of a layer of low viscosity material between two solid planes. The
mathematics behind modeling this shear induced disordering have been extended [18]
to include shear banding kinetics, and show good correlation with data in the cases
of two metallic glasses made from very different elements.

2.4 Developments in model viscous material ex-

periments

As mentioned in section 2.3, shear induced disordering in metallic glasses creates a

thin layer of lower viscosity material between two solid layers. It was first reported
by Pampillo [19] in 1974 that this situation is analogous to grease between plates of
materials. Pampillo did a set of model experiments with grease between glass slides
and referenced the Taylor instability [20] as the cause of the “fingers” or “veins” which
develop.
The Taylor instability indicates that when a viscous fluid is driven through a void
by a lower viscosity medium, the interface between the two fluids becomes unstable
and develops fingers. In the case of metallic glasses, the low viscosity metallic glass
in the shear band is pushed between the layers of high viscosity metallic glass (this
is the pore) by the air (the lower viscosity medium from Taylor). A schematic of this
process was produced by Spaepen [4] and is reproduced in figure 2.3. This provides an
interesting opportunity for model experiments with grease between plates to better
understand the Taylor instability.

15
Figure 2.3: Schematic of veins developing via the Taylor model in a viscous material
[4]

Spaepen [4] followed up the Taylor instability idea with an analysis of the wave-
length between the tributaries and established a relationship between the fracture
stress and the spacing between the veins. Argon [21] took this model further by mod-
ifying it for non-linearity stemming from non-Newtonian behavior in the fluid. Much
more recently, Pan [22] used Argon’s analysis to analyze vein patterns and fracture
strengths seen in a Mg65 Cu15 Ag5 Gd10 metallic glass, concluding that for the particu-
lar Mg alloy studied, multiple voids were opening up ahead of the crack tip to create
very small veins.

16
Chapter 3

Experimental procedures

In this chapter, the experimental methods used in this thesis are described. The chap-
ter is divided into two main sections. Section 3.1 details the experimental procedures
used to determine the effect of changes in test conditions such as stress state and tem-
perature on the fracture appearance of different greases strained in tension between
two plates. Section 3.2 describes the methods used in the testing and characterization
of magnesium metallic glass ribbons.

3.1 Effects of test conditions on viscous fracture

3.1.1 Materials preparation and characterization

Three greases were used in this set of experiments. Dow Corning Silicon Vacuum
grease, Jet-Lube AP-1 multipurpose grease, and Ultra-High Temperature synthetic
grease distributed by McMaster Carr supply. The viscosity of the greases was mea-
sured by an Anton Paahr 501 parallel plate viscometer in the Macromolecular Science
and Engineering department at Case Western Reserve University. A 300 micron gap
between the plates was used. Figure 3.1 is a picture of the experimental setup. The
rotational shear strain rate was varied from 0.1 to 100 1/s over a period of 1 minute,

17
then held at 100 1/s for 3 minutes and finally ramped back down to 0.1 1/s as per-
formed by Yongaggang et al [23]. The final cycle of the viscosity measurement was
performed in the same way, but only ramping up to 50 1/s. See figure 3.2.

Figure 3.1: Parallel plate rheometer setup

3.1.2 Substrate design

The substrates for testing the grease were designed in 2 geometries, as seen in figures
3.3 and 3.4. The aspect ratio of the rectangular substrate was varied from 1:1, 1:2,
to 1:10 to mimic the aspect ratio of metallic glass ribbons. Additionally, the angle of
the surface with respect to the tensile axis was varied from 0 to 75◦ in most cases.
This change in angle allowed varying amounts of shear stress to be present in the
specimen. The schematic in figure 3.5 shows the sample dimensions and variables

18
 Figure 3.2: Procedure for rheology of all greases

for each of the designs. With the cylindrical test specimens, this was achieved with
different substrates cut at varying angles (see figure 3.3), while the angle that the
rectangular substrates were clamped into the apparatus was varied as seen in figure
3.4.

Figure 3.3: Cylindrical substrates: a) 0◦ ; b) 30◦

3.1.3 Mechanical tests

The substrates were clamped into a refurbished Instron 1026 tabletop testing appara-
tus as seen in 3.6, and pulled apart in tension at a rate of 1000 mm/min. Tests were

19
Figure 3.4: Rectangular substrates: a)10:1, 2:1, and 1:1 substrates; b) 1:1 substrate
clamped at 30◦

Figure 3.5: Schematic of substrate design showing variables changed. a) cylindrical

substrates, α varied from 0 to 75◦ b) rectangular substrates, L varied from 0.75” to
7.5”

20
performed at 100◦ C and -50◦ C as well as room temperature. The low temperature
tests were performed with the aid of liquid nitrogen on an MTS 810 20 kip system.
The low temperature tests were performed at a rate of about 500 mm/min.

Figure 3.6: Setup for viscous tests in Instron testing rig

3.1.4 Data analysis/characterization

Fracture surfaces of the grease were photographed immediately after tensile testing.
The photographs were subsequently analyzed in ImageJ by counting the intercepts
of veins over a known length of line as seen in figure 3.7. This is analogous to
traditional grain size measurements for metals. The figure produced by this method
is a quantization of the feature size on the surface. Some measure of strain was
produced by taking side pictures of the fractured surface, measuring the height of
the features, and calculating a local strain from the known initial separation of the
substrates.

21
 Figure 3.7: Schematic of intercept counting method for feature size determination

3.2 Metallic glass ribbon characterization

3.2.1 Materials preparation

Mg85 Cu5 Ca10 ribbon was prepared by melt spinning technique at the University of
Virginia. For tensile tests, the ribbon was cut into 20 mm long sections, and glued
to substrates as pictured in figure 3.8. This was to prevent any twisting or bending
of the sample in the tensile fixture.

Figure 3.8: Schematic of metallic glass tensile sample

3.2.2 DSC and XRD

Differential Scanning Calorimetry was performed on a Metler Toledo DSC 822e/700

provided by the Macromolecular Science and Engineering department at Case West-
ern Reserve University. Scans from room temperature to 240◦ C were performed at
heating rates of 10 and 3◦ C/second. The 3◦ C/second heating rate was chosen to

22
mimic the heating rate of the heating chamber attached to the tensile testing appa-
ratus. X-ray diffraction was performed on a Scintag X-1 X-ray diffractometer, with
scans from 20 to 80◦ 2θ at a rate of 0.02◦ /s.

3.2.3 Tensile tests

Tensile tests were performed on a refurbished Instron 1026 testing machine. Small
hooks were clamped into the machine, then the substrate holding the ribbon was hung
on the hooks, as pictured in figure 3.9. This helped to reduce any bending or twisting
and allowed pure normal tensile stresses in the ribbon. The ribbons were tested at
strain rates from 10−3 to 10−1 . Experiments were conducted at room temperature,
80◦ C, 100◦ C, 120◦ C, and 140◦ C with the assistance of a ATS temperature control
cabinet. The control cabinet allowed for temperature control within ± 5◦ C.

Figure 3.9: Metallic glass ribbon in tensile fixture

3.2.4 Viscosity approximation

Viscosity of materials can be approximated by the following equation [24]:

σ
ν= 3˙

23
σ = flow stress
˙ = strain rate
This equation was utilized with both the viscous model materials experiments and
the tensile Mg-based metallic glass experiments to approximate the viscosity of the
materials.

3.2.5 Hardness tests

Vickers hardness tests were conducted using a Buehler MMT3 hardness indenter. A
100 gram load was used with a hold period of 10 seconds to take the data. Hardness
tests were performed on pristine samples and all samples after tensile testing and
heating. The air side of each sample was indented. The Vickers hardness numbers
obtained were then converted to approximate yield stresses, which were compared
with the results of the tensile tests.
Additional hardness tests were performed by C.K. Huang at Case Western Re-
serve University on a Nikon QM hot microhardness testing machine. The tests were
performed with a 100 gf load and the hold period of 10 seconds.

3.2.6 Bending around a mandrel

Ribbons were bent around mandrels in sizes ranging from 6.68 mm to 1.49 mm in
diameter. Stress and strain for a thin ribbon of material are calculated from the
following equations.
t
=
2ρ

σ = E

Several values of E were used to calculate bending stresses. Calculation from tensile
tests indicate a Young’s modulus of 9 GPa. However, because of inherent softness in
the testing system, it is difficult to measure Young’s modulus accurately. Many metal-

24
lic glasses have moduli slightly lower than that observed in the crystalline counterpart
of their major constituent. Therefore, both 9 GPa and 36 GPa (80% of the modulus
of magnesium) were used to calculate the bend stress. Bending was performed on
both air side and wheel side of the ribbon and shear banding at each diameter was
investigated with an SEM as detailed in section 3.2.7.

3.2.7 Fracture surface and true strain characterization

Fracture surfaces of Mg metallic glass ribbons were examined with a Philips XL30
scanning electron microscope with an accelerating voltage of 15 KeV. The obtained
images were then analyzed in the method described in 3.1.4. Additionally, strain was
measured by comparing the cross sectional area (excluding the thicker sides of the
sample) of a pristine sample with the cross sectional area of the fracture surface of a
tested sample. These images were also obtained via SEM.

25
Chapter 4

Experimental results

Experimental results from investigations into characterization of Mg85 Cu5 Ca10 melt-
spun ribbons and the fracture surfaces of the model viscous materials are detailed in
this chapter. Section 4.1 discusses the experimental results from mechanical tests on
the fracture of the model viscous materials. Section 4.2 describes the structural and
mechanical properties of the Mg-based metallic glass ribbons.

4.1 Characterization of model viscous fracture sur-

faces

Fracture surfaces of metallic glasses often show vein-like patterns which have been
compared to the surface created during the separation/fracture of a viscous material
such as grease. This section details the effects of changes in test geometry (4.1.1)
and viscosity (4.1.2) on the fracture appearance of several viscous materials in a set
of model experiments.

26
4.1.1 Geometry effects on viscous fracture

In the design of the experiments with greases on different substrates, several geometric
parameters could be varied. This section details the differences in fracture surfaces
created by changes in thickness of the viscous layer, shape of the substrate, and angle
of the substrate with respect to the tensile axis.

Thickness of viscous layer

The thickness of the viscous layer has a large effect on the appearance of the resulting
fracture surface. Figure 4.1 quantitatively shows how the thickness of the viscous layer
of AP-1 grease changes the feature size. The two other greases showed similar trends.
0.02 mm was chosen for the remainder of the experiments because it showed the best
veins for photographing.

Figure 4.1: Effect of thickness of viscous layer on feature size in AP-1 grease

27
Shape of substrate

The shape of the substrate also has a large effect on the appearance of the fracture
surface. In figure 4.2, the feature sizes of all three greases at room temperature on
the four substrate shapes are plotted. In the photographs at the bottom of figure 4.2,
the width of each substrate remains constant at 0.75 inches. It can be seen that the
shape/edge effects seem to play an important role in the fracture surface morphology,
transitioning from multiple intersecting vein features to a single branching center vein.

Figure 4.2: Effect of substrate shape on feature size and character produced by on

Angle (stress state) of fracture surface

The final geometry factor which was varied in the model experiments was the angle
of the fracture surface with respect to the tensile axis. This allowed the tests to be
conducted under different stress conditions with varying amounts of shear and normal
stresses. Figure 4.3 shows the influence of fracture angle on the feature size of the

28
materials. In figure 4.3, the solid arrows indicate data sets where the feature size
increases perfectly from low to high angle (increasing amounts of shear stress), while
the dashed arrows indicate data which show a general increasing trend. There data
show that as fracture angle increases, the feature size increases, transitioning from
more equi-axed features to long, river-like veins (figure 4.3).

Figure 4.3: Effect of test angle on feature size in model feature experiments

Figure 4.4: Effect of test angle on feature size in AP-1 grease on square substrate: a)
0◦ , b) 30◦ , c) 45◦ , d) 60◦

29
4.1.2 Rheology of grease

Intuitively, it would seem that viscosity should have a significant effect on the fracture
morphology of a viscous material. To determine if this was the case, the viscosity of
each grease was measured at several temperatures. The results are plotted in figure
4.5. Vacuum grease has the highest viscosity at all temperatures, while AP-1 and
synthetic grease possess lower viscosity and are very similar to each other.

Figure 4.5: Viscosity of three greases as a function of temperature

4.1.3 Temperature effects on viscous fracture

When the actual viscosity of each grease at various temperatures was measured using
the rheometer, the results could be compared to the effects of changes in temperature
(and therefore viscosity) on the fracture surfaces. Figure 4.6 shows the feature size as a
function of grease viscosity (changed by temperature and determined from figure 4.5)

30
for all three greases. The x-axis on the plot represents the viscosity of each grease as
a percentage of the highest viscosity measured (vacuum grease at -10◦ C). The general
trend is that viscosity decreases produced an increase in feature size. Synthetic grease
seems to undergo some sort of phase transition at very low temperatures and behaves
very differently, as can be seen in the inset photograph in 4.6. The behavior of the
synthetic grease at low temperature could be described as “taffy-like”, while AP-1
and vacuum grease both retain their typical grease-like character.

Figure 4.6: Feature size of three greases as a function of viscosity

4.1.4 Viscosity calculation from tensile data

Finally, the viscosity was calculated from tensile data from the grease using the
method described in 3.2.4. The results are shown in figure 4.7. The viscosity calcu-
lated from the tensile data is significantly higher than that measured in the rheometer.
This is even more evident in figure 4.8, where the calculated viscosity from the tensile

31
measurements is divided by the measured viscosity from the rheometer and plotted
against temperature. The viscosity acquired from tensile data is from 2 to 12 times
larger than the viscosity measured via the rheometer. One potential reason for this
large difference is that viscosity of greases varies as

η = η0 eξp

with changes in pressure, where ξ ranges from 0.7 to 4, depending on the specific
grease [25]. This shows that hydrostatic pressure has a large effect on viscosity. The
rotating disc rheometer used puts the grease under conditions of nearly pure shear.
However, the tensile tests introduce some component of tensile hydrostatic pressure.
This should cause the grease viscosity to decrease, similar to arguments used to predict
flow localization in metallic glasses tested under different stress states. The data for
viscosity estimated from the tensile tests are larger, suggesting that the measurement
technique used for the yield stress measurements in the tension tests may overestimate
the actual point of yielding/flow of the greases.

4.2 Characterization of Mg based metallic glass

ribbon

Characteristics of the Mg85 Cu5 Ca10 metallic glass ribbons are examined in this sec-
tion. Structural characteristics are determined by XRD and DSC analysis in section
4.2.1. Mechanical properties are determined via microhardness (4.2.2), tensile tests
(4.2.3), and bending over a mandrel (4.2.5). Finally, the viscosity of the Mg-based
glass is investigated in section (4.2.6).

32
Figure 4.7: Viscosity plotted as a function of temperature, comparing viscosity mea-
sured with rheometer to viscosity calculated from tensile tests.

4.2.1 Structure of materials

DSC conducted on as-received Mg-based metallic glass revealed a slight glass transi-
tion at 100◦ C when heated at 3◦ C/min with the first crystallization event beginning
at 120◦ C as seen in figure 4.9. The first crystallization event is completed by 140◦ C.
This DSC trace reveals a relatively large region between Tg and Tx , about 40◦ C,
providing the potential for large plastic strains if testing is conducted between Tg
and Tx .
XRD examination of as-received Mg-based metallic glass samples shows a broad,
diffuse peak characteristic of amorphous materials as seen in figure 4.10. This confirms
that the as-received samples demonstrate the lack of long range order characteristic
of amorphous materials.
Samples were heated at 3◦ C/min to 110, 140, 170 and 250◦ C, then removed from

33
Figure 4.8: Ratio of measured viscosity to calculated viscosity versus temperature.

Figure 4.9: DSC trace of Mg metallic glass ribbon heated at 3◦ C/min

34
 Figure 4.10: X-ray diffraction patterns from as-received metallic glass

heat about 2 minutes after reaching the desired temperature to investigate the evolu-
tion of structure as the sample is heated. The DSC results indicate that crystallization
should commence at 120◦ C. Figure 4.11 shows the XRD traces of the samples which
had been heated to various temperatures. The specimen heated to 110◦ C exhibited
the broad diffuse peaks similar to as-received material, while the specimen heated to
140◦ C shows that structure has evolved. Recall from figure 4.9 that the first crystal-
lization event has completed at 140◦ C. Further heating to temperatures higher than
140◦ C increases the number of peaks and sharpens existing ones.

4.2.2 Vickers microhardness

Vickers hardness indents performed on a NIKON QM hot microhardness machine

while the specimen was heated. Figure 4.12 shows that the hardness drops off precip-
itously as the temperature approaches the glass transition temperature (e.g. 100◦ C).

35
 Figure 4.11: X-ray diffraction patterns of samples heated to temperatures shown

This is consistent with the expected softening that occurs at the glass transition tem-
perature [26]. Additionally, the microhardness indents at 50◦ C show that the material
is softening significantly while it is held at 50◦ C for three minutes.
Vickers hardness numbers can be converted to approximate flow strength by the
relation:
V ickersHardness
σ=
3

To further exhibit the effects of test temperature and any influence of changing struc-
ture on the mechanical properties of the material, Vickers hardness tests were per-
formed on samples which had undergone tensile tests at different temperatures and
the same samples which had been heated for XRD examination as shown in figure
4.11. The results are summarized in figures 4.13 and 4.14. The strengths derived from

36
Figure 4.12: Vickers microhardness of sample with heating to glass transition tem-
perature

the Vickers hardness indents in the case of the tensile tests show a gradually increas-
ing trend. Strengths from samples heated for XRD examinations show an increase at
temperatures above 140◦ C. The points at 140◦ C held for 12 minutes and heated to
250◦ C showed cracking around the indent, indicating that the samples are very brittle
and that the measured hardness/strength is lower than the actual hardness/strength.

4.2.3 Tensile tests

Effects of changes in strain rate

Tensile tests were performed at three strain rates to investigate the effects of changes
strain rate on tensile properties. The tests were performed at room temperature and
at the glass transition temperature, 100◦ C. As seen in figure 4.15, at room temperature
all of the strain rates show relatively similar properties, except that the slowest rate

37
 Figure 4.13: Vickers microhardness of samples previously tested in tensile tests

reaches a slightly higher stress and strain than the faster rates. At the glass transition
temperature, there is a much more marked difference between the results obtained
at different strain rates (figure 4.16). At the slowest rate (10−3 1/s), the material
undergoes high amounts of plastic flow at a reduced flow stress, achieving a true
strain of 0.62 before fracture. In contrast, as the strain rate increases, the flow stress
increased and the failure strain decreases significantly to 0.18 for the 10−1 strain rate
test.

Effects of changes in test temperature

Temperature effects on the tensile properties of the Mg-based metallic glass were
investigated by performing tensile tests at various temperatures. Samples were sub-
jected to room temperature, 80◦ C, 100◦ C, 120◦ C, and 140◦ C temperatures during
tensile tests at a strain rate of 10−3 1/s. The stress-strain curves of the resulting

38
Figure 4.14: Vickers microhardness of samples annealed for use in XRD experiments
(figure 4.11) *Samples exhibited large cracks around the indents, so actual hardnesses
are higher.

tests are shown in figure 4.17 and table 4.1 lists the 0.002 offset yield stresses (or
maximum stresses where yield is not applicable) and failure strains determined from
area changes measured from SEM images of each sample. As the temperature ap-
proaches the glass transition temperature, the fracture strains increase greatly, while
the strengths decrease by a factor of 2 to 3. The 120◦ C samples tended to pull out
of the glued fixture before failure, so no true fracture strain could be determined.
Furthermore, it is difficult to say what part of the stress-strain curve is the sample
deforming and what part is the specimen pulling out of the glue. However, when
the fracture surface was examined in the SEM after testing, the reduction in area
measured indicated that a plastic strain of 0.122 was retained in the sample.
Figure 4.18 shows the reduction in area in each fractured sample plotted against
test temperature. The arrows indicate the trends observed at each strain rate. It is

39
Figure 4.15: Effect of changes in strain rate on tensile properties of Mg-based glass
tested at room temperature

Temperature Yield stress (MPa) Fracture strain

25◦ C 314 0.086
80◦ C 312 0.58
100◦ C 143 1.56
120◦ C 88 0.122*
140◦ C 105 0.117
*Sample pulled out of glue in fixture and fracture did not occur.

Table 4.1: Yield stresses and fracture strains of samples at various temperatures

40
Figure 4.16: Effect of changes in strain rate on tensile properties of Mg-based glass
tested at the glass transition temperature (100◦ C)

evident that the reduction in area increases up to the glass transition temperature,
then generally decreases at higher temperatures.

4.2.4 Fracture surfaces

Fracture surfaces of the Mg-based metallic glass display several types of fracture sur-
face features depending on the temperature at which the tensile test was performed.
The various types of features observed are viscous type features, ductile rupture to
a single vein, and brittle-type fracture. Viscous type veins are seen in the samples
tested at room temperature (figure 4.19), 80◦ C (figure 4.21), and 100◦ C (figure 4.22).
Ductile type rupture is exhibited in 80◦ C (figure 4.20) and 100◦ C (figure 4.23). Brittle
fracture features are seen in the sample tested at 140◦ C (figure 4.24).

41
Figure 4.17: Effects of changes in test temperature and strain rate on tensile properties
of Mg-based glass

4.2.5 Bending over mandrel test

Ribbon samples were bent around mandrels of different diameters to acquire a further
understanding of their mechanical properties. SEM examination of samples which
exhibited shear bands were considered to have yielded, such as shown in figure 4.25.
It was found that shear bands were not present for a mandrel of diameter 2.1 mm,
but were present when bent over a mandrel of diameter 1.87 mm diameter mandrel
for a 41 µm thick ribbon. As discussed in section 3.2.6, elastic moduli of both 9
GPa (Calculated from tensile tests) and 36 GPa (80% of crystalline magnesium’s
GPa) were used to calculate the bend stress. Table 4.2 contains the results of several
diameters tested and the stress which is produced at those diameters for a 41 µm
thick foil if either E = 9GPa or 36GPa is assumed. The assumption of 9 GPa appears
to underestimate the bend stress, which should be on the order of what is seen in

42
Figure 4.18: Effect of change in test temperature on reduction in area in Mg-based
metallic glass

Figure 4.19: Sample tested at strain rate 10−3 1/s and room temperature

43
Figure 4.20: Sample tested at strain rate 10−3 1/s and 80◦ C showing a region of the
sample containing ductile rupture

Figure 4.21: Sample tested at strain rate 10−3 1/s and 80◦ C showing a region of the
sample viscous-like fracture

44
Figure 4.22: Sample tested at strain rate 10−3 1/s and 100◦ C showing a region of the
sample displaying viscous-like fracture transitioning to ductile rupture

Figure 4.23: Sample tested at strain rate 10−3 1/s and 100◦ C showing a region of the
sample displaying ductile rupture

Vickers hardness tests, while 36 GPa seems to overestimate it. It seems likely that the
actual Young’s modulus of this material lies somewhere in the range between 9 and
36 GPa, but it is difficult to determine by conventional methods (such as ultrasonic
measurements) because of specimen geometry.

4.2.6 Viscosity determination

The approximate viscosity of the metallic glass tested was calculated as described
in section 3.2.4 from the yield stress and strain rate data available. Results of the

45
Figure 4.24: Sample tested at strain rate 10−3 1/s and 140◦ C showing a region of the
sample displaying brittle fracture

Mandrel Bend strain Bend stress (MPa) Bend stress (MPa) Shear banding
diameter (mm) for E = 9 GPa for E = 36 GPa
2.36 0.0174 156.4 664.5 no
2.1 0.0195 175.7 746.8 no
1.87 0.0219 197.3 838.6 yes
1.49 0.0275 247.7 1052.5 yes

Table 4.2: Mandrel bend test results

46
Figure 4.25: Arrows indicate shear bands present on the surface of Mg-based metallic
glass bent around a mandrel of diameter 1.87 mm
Temperature (T/Tg) Strain rate Yield Stress (MPa) Viscosity (MPa*s)
0.25 10−3 314 104666
0.25 10−3 315 105000
0.8 10−3 312 104000
1 10−3 143 47666
1.2 10−3 88 29333
1.4 10−3 89 29666
1.4 10−3 132 44000
1.4 10−3 105 35000
0.25 10−2 260.4 8680
0.8 10−2 395.7 13190
1 10−2 256 8533
1.2 10−2 95 3166
1.2 10−2 132.5 4416
0.25 10−1 114.2 380
0.8 10−1 195.9 653
1 10−1 200 666
1.2 10−1 192 640

Table 4.3: Calculated viscosities of Mg metallic glass under various conditions

calculations are available in table 4.3.

47
Chapter 5

Discussion

This chapter contains discussion of the results obtained from experiments on model
viscous materials (5.1), the mechanical behavior of a Mg-based metallic glass in sec-
tion 5.2, and a comparison of results obtained from model experiments with fracture
of viscous liquids to fracture surfaces of metallic glasses in section 5.3.

5.1 Comparison of viscous model results to model

by Spaepen [1]

As detailed in the Background (2.4), the model by Spaepen allows prediction of the
spacing of the veins in the Taylor instability model for fracture. The feature size of
three different kinds of greases pulled to failure have been measured. The analysis
of the viscosity and movement of a viscous fluid pushed by a different viscosity fluid
leads to a wavelength of perturbation on the interface of the different viscosity fluids
(air and grease).
This perturbation is described by the following equation [1]:
√ r
00
λm = 32π γL σf n

λm = Wavelength of perturbations

48
 γ = Surface energy (given as surface tension)
L” = Width of fractured surface
σnf = Stress normal to fracture surface at fracture
This equation was applied to the model grease experiments to attempt to compare
the distance between veins obtained on different viscosity greases. For greases, γ
ranges from 0.01 - 0.06 N/m [27], L” in these samples is 1.905 cm, and σnf is known
from the tensile experiments. Using those values, the distance between veins predicted
by Spaepen’s model was calculated and compared to the values measured in the
greases. The results are summarized in table 5.1 assuming 0.06 N/m for surface
tension. It is evident from the results in the table that the Spaepen model provides
estimates on the same order as what was found from the model experiments. The
surface tension of each grease was estimated as 0.06 N/m, which could introduce some
error because the surface tension probably varies as a function of temperature. The
work performed in this research also shows that the thickness of the viscous layer
used in the experiment has a significant effect on the surface features which is not
captured by Spaepen’s model. It was found that as the viscous layer decreases in
thickness, veins become closer spaced. A very thin layer is most realistic for metallic
glasses, as they are presumed to contain very thin, low viscosity layer surrounded by
non-deforming glass.

5.2 Mechanical behavior of Mg-based metallic glass

The mechanical behavior of Mg85 Cu5 Ca10 has been investigated with three types of
experiments. Unique stress-strain curve appearance is discussed in section 5.2.1 A
comparison of the results obtained in these three experiments is contained in section
5.2.2. The temperature effects on structure, fractography, and mechanical properties
are examined in section 5.2.3. The results of the mechanical tests are compared to the

49
 Grease Temp (◦ C) Substrate shape Measured λ (mm) Calculated λ (mm)
for γ = 0.06N/m
Vacuum 25◦ C 2:1 2.366 1.503
100◦ C 2:1 3.335 1.855
-10◦ C 2:1 1.840 1.195
-10◦ C round 2.690 0.801
-10◦ C square 1.780 0.974
-10◦ C square 1.780 0.723

AP-1 -10◦ C square 0.625 0.829

-10◦ C 2:1 0.392 0.822
-10◦ C round 1.491 0.736
25◦ C 2:1 1.540 1.262
100◦ C 2:1 7.636 1.855
100◦ C 2:1 7.806 1.732

Synthetic -10◦ C square 3.406 1.052

-10◦ C square 3.406 1.152
-10◦ C 2:1 1.652 1.575
-10◦ C 2:1 1.652 1.343
-10◦ C round 2.094 0.842

Table 5.1: Comparison of Spaepen’s model prediction to measured grease features

deformation map from chapter 2 in figure 2.2 in section 5.2.4. Viscosities which were
calculated from tensile tests on the Mg-based metallic glass are compared to viscosities
obtained on a Zr-based metallic glass in section 5.2.5. Finally, the behavior of the
Mg-based glass alloy is compared to other Mg-based metallic glasses from literature
in section 5.2.6.

5.2.1 Unique stress-strain curve appearance

As seen in figure 4.17, the stress-strain curves of samples which exhibited signifi-
cant plastic flow showed unique “bumpy” behavior in the plastic deformation regime.
Other researchers have attributed this to crystallization [28], however crystallization
was not observed in the bulk of samples which were subjected to XRD analysis af-
ter deformation. It is possible that very localized crystallization near the fractured
area occurred and could cause the bumps in the stress-strain curve. Another possible
cause is from pop in of shear bands, but shear bands were not observed on the sides
of the samples. The most likely cause of the behavior is some influence of the test

50
 Vickers Tensile Bend (E = 9GPa) Bend (E = 36GPa)
Strain rate (1/s) 10−5 10−3 10−2 10−1 1 10−2 10−2
Strength (MPa) 512 314 260 114 176<σ<197 747<σ<839
Strain 0.086 0.034 0.077 0.020<<0.019 0.020<<0.019

Table 5.2: Comparison of strengths and strains for mechanical tests performed at
room temperature

setup. All of the samples which showed the unique stress-strain curves were tested
at temperatures above room temperature. The bumps in stress correspond to very
small (0.2 - 0.3 lb) changes in load, which could be caused by the furnace turning off
and on.

5.2.2 Agreement between mechanical tests

Three types of mechanical tests were performed on the Mg-based metallic glass. Vick-
ers hardness, uniaxial tension tests, and bending around a mandrel tests. All three of
these tests have differing stress states and strain rates, but can all be converted into
an approximate yield strength. Table 5.2 is a comparison of the estimated strength
and strain values obtained from each type of test at room temperature.
There are inherent differences between the three types of tests performed. The
stress state in Vickers tests is compression along with hydrostatic compression. In
the tensile tests it is tensile, and in the bend test, it is compressive on the bottom
surface and tensile on the top surface. Additionally, the volume sampled by each test
is different. The volume sampled in a Vickers test is lower than what is sampled in
the bend test, which is, in turn, smaller than what is sampled in a tensile test. This
will affect the failure stress because there are flaws on the surface of the material
will have a detrimental effect in the tensile tests. Figure 5.1 is a SEM image of a
cross section of a typical ribbon which displays the non-uniform cross section and
some of the surface flaws. Failure initiating early on any one of those points would
account for the drop in stress in the tensile tests as compared to the Vickers hardness
strength approximation. Also, strain rates among the three tests are very different

51
which could effect the final stress. Although strain-rate sensitivity is not expected at
temperatures significantly below Tg , room temperature is a significant fraction of Tg
so strain rate effects could be present. Finally, the tensile test ends catastrophically,
while the bend and Vickers tests do not.

Figure 5.1: Cross section of Mg-based metallic glass ribbon, illustrating the non-
uniform cross section of the samples.

5.2.3 Temperature effects on structure, fracture surfaces, and

mechanical properties

Structural properties

The DSC results (figure 4.9) indicate that the crystallization temperature is near
120◦ C and the glass transition temperature is 100◦ C. XRD results confirm the 120◦ C
crystallization temperature by showing peak sharpening and crystallization at tem-
peratures higher than 120◦ C (figure 4.11). When a material is near or above it’s glass
transition temperature it softens, and crystallization causes embrittlement in metal-
lic glasses. This information elucidates the fractography observed with increasing
temperature.

52
Fracture surfaces

Fracture surfaces shown in section 4.2.4 show viscous-like features at temperatures

below and near the glass transition temperature (figures 4.19, 4.21, 4.22). As the
temperature approaches the glass transition temperature, parts of the samples tran-
sition to ductile rupture type fracture (figures 4.20 4.23) due to the large amount of
softening occurring. Above the crystallization temperature, samples exhibit brittle
fracture (figure 4.24) typical of metallic glasses which have crystallized.

Mechanical properties

This softening in approach to the glass transition temperature then embrittling with
increasing temperature above the crystallization temperature is supported by the
reported reduction in area in figure 4.18. It was noted that the reduction in area
increases at tests near the glass transition temperature, but decreases again after
crystallization. Behavior correlating with this was also observed with the tensile
tests displayed in figure 4.17. Hardness data taken at temperatures up to the glass
transition temperature shows significant softening (figure 4.12).
Wesseling et al. [29] studied the effect of annealing temperature on the hard-
ness of a Al-based metallic glass. It was found that when the material was held
at temperatures below and up to the glass transition temperature, then cooled to
room temperature and the hardness measured, the hardness increased slightly with
increasing temperature of anneal. This effect was attributed to loss of free volume
that was quenched in during the melt spinning process. Annealing at higher temper-
ature produced nano-precipitates and significant strengthening and embrittlement.
The former effect was observed in the Mg-based metallic glass tested presently. The
Vickers hardness increased slightly in samples which had been subjected to tensile
tests at increasing temperatures (figure 4.13). As also seen in Wesseling’s paper, with
heating to temperatures above the crystallization temperature, the hardness increases

53
significantly and embrittlement occurs (figure 4.14).

5.2.4 Comparison of data to deformation map

Schuh’s [3] deformation map provides a guide for determining what sort of flow might
occur in metallic glasses under various temperature and strain rate conditions if the
sample is not crystallizing. The deformation map is most applicable for metallic
glasses with large super cooled liquid regimes, which is not the case in the Mg-based
metallic glass. The data obtained from the Mg-based glass experiments (both tensile
and Vickers hardness) are superimposed on the plot in figure 5.2 with the values of flow
stress and fracture strain listed in table 5.3. The crystallization temperature of the
Mg-based metallic glass is 1.01 T/Tg , so the homogeneous flow regime is truncated at
that point and replaced by significant strengthening and embrittlement. In the rather
narrow homogeneous flow region which remains, it is expected that the yield stresses
should be lower and the fracture strain significantly higher. This is manifested at
the data point at 10−3 1/s at .95 T/Tg (sample j) which is the only one which falls
in the homogeneous flow regime that is not also at the crystallization temperature.
The failure strain for this sample is very large: 156%. Shear bands should be also
visible in in the samples tested in the inhomogeneous deformation regime. Figure 5.3
is a SEM image of a sample containing shear bands. This is a sample tested at room
temperature (sample a in figure 5.2 and table 5.3), which would certainly be within
the inhomogeneous flow section of the deformation map. In contrast, figure 4.23 is
the fracture surface of a sample tested at 100◦ C at a strain rate of 10−3 s−1 (sample
j in figure 5.2 and table 5.3), which should be in the homogeneous flow section of the
deformation map. The sample has actually undergone ductile-rupture type failure,
once again confirming what would be predicted by the deformation map.

54
Figure 5.2: Deformation map from Schuh [3] with Mg-based metallic glass data. Dots
mark data points. The flow stress and failure strains for each dot are in table 5.3

Point Flow stress Fracture strain Region

a) 114.2 0.116 Inhomogeneous
b) 195.9 0.182 Inhomogeneous
c) 200 0.138 Inhomogeneous
d) 192 0.339 Crystallized
e) 260.4 0.024 Inhomogeneous
f) 395.7 0.154 Inhomogeneous
g) 95 0.153 Crystallized
h) 314 0.087 Inhomogeneous
i) 312 0.581 Inhomogeneous
j) 143 1.559 Homogeneous
k) 88 0.122 Crystallized
l) 512 NA Inhomogeneous
m) 382 NA Inhomogeneous
n) 11.9 NA Homogeneous

Table 5.3: Flow stress and failure strain data for points in figure 5.2

55
Figure 5.3: Shear bands near the fracture surface of a sample tested at room temper-
ature, 10−3 s−1 . The fracture surface is at the bottom of the image.

5.2.5 Comparison of viscosity obtained to literature values

The approximate viscosities were calculated from the tensile data and tabulated in
table 4.3. Nouri [5] calculated the viscosity of a Zr-based metallic glass via the same
method, but with using data from Vickers hardness tests. The results are plotted in
figure 5.4. The viscosities range from 1.8×1013 P a·s to 1.0×109 P a·s. In comparison,
the viscosities obtained from tensile tests on the Mg-based metallic glass range from
1.0 × 1011 P a · s to 3.8 × 108 P a · s. These are reasonable ranges for viscosity of a
metallic glass, although accurate determination would require other types of testing.

56
Figure 5.4: Viscosity of a Zr-based metallic glass as a function of temperature from
Nouri [5]

5.2.6 Comparison of data with other Mg metallic glasses

Mg-based metallic glasses are in relatively early stages of development. Brittleness

seems to be a major problem with many amorphous magnesium alloys.
Mg65 Cu20 Ni5 Gd10 and Mg65 Cu20 Ag5 Gd10 are described as having a brittleness com-
parable to that of silicate glass [22] at room temperature. Table 5.4 was compiled by
Li [2]. It is a summary of room temperature compressive properties of many Mg-based
metallic glasses. When compared with these materials, some of the tensile properties
of Mg85 Cu5 Ca10 at room temperature (σ = 314 MPa,  = 8.6%) excede those of other
reported Mg-based glasses. It is not yet clear if these differences stem from chemistry,
chemistry control, or presence/absence of defects on the sample surface

57
 Alloy composition (at.%) Sample diameter (mm) σf (%) p Reference
Mg65 Cu15 Ag5 Pd5 Y10 5 770 0 [30]
Mg65 Cu15 Ag5 Pd5 Gd10 2 817 0.2 [31]
Mg65 Cu20 Ag10 Y2 Gd8 1 956 0.3 [32]
Mg65 Cu20 Ag5 Gd10 1 909 0.5 [33]
Mg65 Cu15 Ag10 Gd10 1 935 0.2 [33]
Mg65 Cu7.5 Ni7.5 Zn5 Ag5 Y10 1 832 0 [34]
Mg65 Cu7.5 Ni7.5 Zn5 Ag5 Y5 Gd5 1 928 0.57 [33]
Mg75 Cu15 Gd10 2 743 0 [35]
Mg75 Cu5 Ni10 Gd10 2 874 0.2 [36]
Mg65 Cu25 Gd10 2 834 0 [37]
Mg65 Ni5 Cu20 Gd10 2 904 0.15 [37]
Mg65 Cu7.5 Ni7.5 Zn5 Ag5 Y10 4 490–650 0 [38]
Mg58.5 Cu30.5 Y11 1 1022±28 0.35 [39]
Mg57 Cu31 Y6.6 Nd5.4 1 1188 0 [40]
Mg61 Cu28 Gd11 1 1075±35 0.40 [40]
Mg65 Cu10 Ag5 Gd10 Ni10 2 1005 0 [41]
Mg68 Zn28 Ca4 2 828 1.28 [2]
Mg85 Cu5 Ca10 NA 314 8.6 This work

Table 5.4: Summary of compressive mechanical properties from [2].

5.3 Comparison of viscous material model experi-

ments to metallic glasses

Recall that in the model viscous experiments (section 4.1.3) the feature size of the
grease in the model was found to decrease with increasing viscosity. With decreasing
viscosity the material should be less prone to flow, and therefore by Taylor’s instability
model, a larger number of smaller, more closely spaced veins should flow. Various
metallic glass ribbons tested in tension from literature have been analyzed for feature
size and their approximate viscosities calculated to investigate whether they follow the
trends noted in the model viscous experiments [42] [43] [44] [45] [29] [46]. The results
are plotted in figure 5.5. It can be seen that there is a lot of scatter in the data,
but the general trend is of decreasing feature size with increasing viscosity as was
found in the model experiments. Recall also that the model experiments were greatly
influenced by the thickness of the viscous layer, the aspect ratio of the substrate, and
the stress state of the viscous layer. All of the plotted data was derived from ribbon
shaped samples, except for Wang (3:1 aspect ratio) and Lowhaphandu (round), so

58
the aspect ratio should not have a large effect on this data. However, the angle which
the fracture occurred relative to the tensile direction and the thickness of the shear
band may have an additional effect on the feature size which is not accounted for in
this chart.

Figure 5.5: Calculated viscosities of various metallic glasses plotted against fracture
surface feature size

59
Chapter 6

Conclusions

An investigation of Spaepen’s model [1] of metallic glass fracture surfaces via model
experiments on viscous materials has been provided in this work. Additionally, the
mechanical and flow properties of Mg85 Cu5 Ca10 metallic glass ribbons have been
considered in light of a deformation map. The major findings are as follows:

Model viscous fracture experiments

1. The model for metallic glass fracture surfaces by Spaepen [ibid] can be mod-
eled by experiments with grease. The prediction of vein spacing by the model
captures what is observed in grease within the correct order of magnitude.

2. Experiments with effects of thickness of the viscous layer reveal that as the
thickness decreases, the number of veins increases and therefore the spacing
between veins decreases. This result may suggest that spacing between veins
on metallic glass fracture surfaces may be influenced by the thickness of the
viscous layer, although the proposal for metallic glasses is that a very thin layer
of viscous material develops.

3. The stress state of the viscous layer greatly influences its fracture morphology,
with increasing amounts of shear causing more widely spaced features. Metallic

60
 glasses are thought to fail by shear localization in thin layers of viscous mate-
rial. This is supported by this study, as the fracture surfaces of metallic glass
look most like the grease model experiments which failed under relatively high
amounts of shear.

4. Shape of substrates had a large effect on the morphology of the viscous fracture
surfaces. This indicates that edge effects and sample shape may be important
in the fracture appearance of metallic glasses.

5. It was found that the viscosity of the viscous layer greatly influences the fracture
appearance. Less viscous materials cause much larger, wider spaced feature sizes
in model experiments. This effect is also seen to some extent in metallic glasses
tested at temperatures near the glass transition temperature in cases where
there was no concurrent embrittlement.

Mechanical properties of Mg85 Cu5 Ca10 metallic glass ribbons

1. Mechanical testing via Vickers hardness, tensile tests, and bend around a man-
drel tests at various strain rates and temperatures indicated that the Mg-based
metallic glass has relatively high ductility at room temperature (4% strain).
However, the material is weakened by defects in tension so that the tensile stress
is only 314 MPa somewhat below the 512 MPa predicted by Vickers hardness
tests. This fracture strain is higher than any of the reviewed Mg-based glasses
reported, but the fracture stress is lower.

2. Structural and mechanical tests indicated that the Mg-based metallic glass rib-
bons show a glass transition temperature around 100◦ C. Samples deformed near
this temperature show large strains up to 62%. The crystallization tempera-
ture is near 120◦ C and once the material has exceeded this temperature the
ensuing structure evolution causes significant strengthening and embrittlement,

61
 even during the testing and test setup.

3. Analysis of features sizes and estimated viscosities of several metallic glasses

from literature revealed that the feature size generally decreases with increasing
viscosity. This corresponds with what was concluded from the model viscous
experiments.

62
Chapter 7

Future research

The research contained in this thesis has raised further questions about the appli-
cability and correlation of the viscous layer model to metallic glass fracture. Future
work should include:

1. Torsion tests on the Mg-based metallic glasses and subsequent examination of

the fracture surfaces could provide a more complete picture of what happens to
fracture surfaces under varying amounts of shear. This data could be compared
to the results of the grease model experiments which indicate more widely spaced
features with increased shear.

2. Other stress states and geometries such as notched samples and crack opening
geometries should be investigated in both the Mg-based metallic glasses and
the grease model to further understand their behavior.

3. More accurate measurements of Mg-glass ribbon viscosity may be possible with

dynamic mechanical analysis (DMA).

4. Thus far the Taylor/Spaepen [20, 1] model has only been applied to viscous
tests done at an angle of 0◦ . This analysis should be done on samples tested at
various angles.

63
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