The Influence of Inter-Anneal and Cold Rolling Processes On Key Lithographic Sheet Properties

The Influence of Inter-anneal and
Cold Rolling Processes on Key

Lithographic Sheet Properties
A Thesis submitted to The University of Manchester for the degree of

MPhil
in the Faculty of Engineering and Physical Sciences
2012
Michail Mariglis
School of Materials
List of Contents
Page
List of Contents 2
List of Figures 7
List of Tables 12
Abstract 14
Declaration 15
Copyright Statement 15
Acknowledgments 16
Introduction 17
1. Literature Review 18
1.1 Printing History - Offset Lithographic Printing Evolution and Plate 18

Materials
1.1.1 Printing history and significance 18
1.1.2 Printing processes 19
1.1.3 Evolution of the lithographic printing process 21
1.1.4 Practice of offset lithographic printing 23
1.1.5 The lithographic printing plate 24
1.1.6 Current status of the lithographic printing business 26
1.2 Aluminium in Offset Lithographic Printing 28
1.2.1 Aluminium material 28
1.2.2 Aluminium alloys 30
1.2.3 Aluminium alloy AA1050 32
1.3 Lithographic Printing Plate - Production Stages 37
1.3.1 Aluminium substrate production stage 37
2
1.3.2 Plate production stage 38
1.3.3 Printer’s stage; pre- and on-press 40
1.4 Critical Product Requirements (CPRs) 40
1.4.1 Strength related properties 41
1.4.1.1 High thermal stability 41
1.4.1.2 High reverse bending fatigue strength 42
1.4.2 Lack of surface defects 44
1.4.3 Flatness 45
1.4.4 Good roughening behaviour 45
1.4.5 Anodizing quality 48
1.5 Inter-annealing 48
1.5.1 Pre-annealing state 48
1.5.2 Annealing 49
1.5.3 Recovery, recrystallization and grain growth 51
1.5.4 Recovery 51
1.5.4.1 Recovery stages 53
1.5.4.2 Factors influencing recovery 54
1.5.4.3 Recovery kinetics 55
1.5.5 Recrystallization 55
1.5.5.1 Recrystallization stages 56
1.5.5.2 Laws of recrystallization 58
1.5.5.3 Factors influencing recrystallization 59
1.5.5.4 Recrystallization kinetics 61
1.5.5.5 Impact of recrystallization on material properties 63
1.5.6 Grain growth - coarsening 64
1.5.6.1 Factors influencing grain growth - coarsening 65
1.5.6.2 Grain growth - coarsening kinetics 66
1.5.7 Annealing summary 67
3
1.5.8 Annealing textures 67
1.5.8.1 Recrystallized texture evolution theories 69
1.5.8.2 Annealing texture of AA1050 69
1.5.9 Microstructure evolution through the inter-annealing process 71
1.5.9.1 Coarse constituent particles 73
1.5.9.2 Recrystallization and precipitation during the 73

inter-annealing process
1.5.9.3 Solute change evaluation during inter-annealing 74
1.6 Cold Rolling Process 76
1.7 Literature Review - Figures 79
2. Experimental Procedure 89
2.1 Materials 89
2.2 Methods 90
2.2.1 Particle size analysis 90
2.2.2 Grain size and structure 93
2.2.3 Tensile tests and microhardness 95
2.2.4 Mathematical (annealing) model 97
2.2.5 Laboratory simulation of annealing practice IA-1 99
2.2.6 Isothermal and isochronal annealing 100
2.2.7 Electrical conductivity 101
2.2.8 Laboratory AC-electrograining 103
2.2.9 Gloss 105
2.3 Experimental Approaches 106
2.3.1 Benchmarking of pre- and post- annealed materials 106
2.3.2 Annealing modelling and laboratory annealing simulation (1): 107

typical coil position
2.3.3 Establishing the recrystallization kinetics with isochronal and 108
isothermal experiments
2.3.4 Laboratory annealing simulation (2): extreme coil positions 110
comparison
4
2.3.5 Characterization of 0.3 mm cold rolled sheet 111
2.3.6 Annealing modelling part 2: extreme coil sizes comparison 113
2.4 Experimental Procedure - Figures 114
3. Results and Discussion 121
3.1 Benchmarking of Pre- and Post-Annealed Materials 121
3.1.2 Grain structure analysis 124
3.1.3 Microhardness 126
3.2 Annealing Modelling and Laboratory Annealing Simulation (1): 126

Typical Coil Position
3.2.1 Annealing model 126
3.2.2 Laboratory annealing simulation (1): typical coil position 127
3.3 Establishing the Recrystallization Kinetics with Isochronal and 130

Isothermal Experiments
3.3.1 Isochronal experiment 130
3.3.2 Isothermal experiment 132
3.3.3 JMAK equation fitting 134
3.4 Laboratory Annealing Simulation (2): Extreme Coil Positions 136

Comparison
3.4.3 Electrical conductivity 140
3.4.4 Microhardness 141
3.5 Characterization of 0.3 mm Cold Rolled Sheet 142
3.5.1 Mechanical properties 142
3.5.4 Laboratory AC-electrograining 145
3.6 Annealing Modelling Part 2: Extreme Coil Sizes Comparison 146
5
3.7 Results and Discussion - Figures 150
4. General Summary and Conclusions 203
4.1 Conclusions 203
4.1.1 Industrial scale samples 203
4.1.2 Material recrystallization kinetics 204
4.1.3 Mathematical model predictions 204
4.1.4 Laboratory annealing simulations 205
4.1.4.1 Laboratory annealing simulation (1) - typical coil 205

position
4.1.4.2 Laboratory annealing simulation (2) - extreme coil 205
positions
4.2 General Summary 206
5. Suggestions for Future Work 208
References 210
Word count: 47,264
6
List of figures: Page
Figure 1: Schematic diagrams of the Letterpress and Flexography 79
printing processes.
Figure 2: Schematic diagram of the Gravure printing process. 79
Figure 3: Schematic diagram of the screen printing process. 80
Figure 4: Plateless process flow diagram. 80
Figure 5: Schematic diagrams of the offset lithographic printing process, 81
the waterless offset variant and the basic principles on which
these are employed.
Figure 6: Schematic diagram showing the principle behind producing an 82
offset press, functional plate.
Figure 7: The route of an offset lithographic printing plate, from D.C. 82
cast ingot to a developed plate.
Figure 8: An offset lithographic printing plate with its different layers 83
after the plate production stage.
Figure 9: The three production stages of aluminium offset lithographic 84
plate production.
Figure 10: Plot of strength in relation to temperature during annealing 84
process.
Figure 11: Hardness measurements of recovered cold rolled commercial 85
purity aluminium.
Figure 12: Plot of fraction recrystallized in relation to time, during 85
recrystallization process.
Figure 13: Plot of recrystallization effects on tensile properties. 86
Figure 14: Plot of recrystallization effects on hardness. 86
Figure 15: Schematic TTT diagram of the different possible sequences of 87
precipitation and recrystallization.
Figure 16: Influence of intermediate annealing on the iron content in solid 87
solution and the thermal stability.
Figure 17: Rolling process, parameters and details. 88
Figure 18: Plot of Yield strength with reducing gauge of AA1050 by cold 88
rolling.
Figure 19: Schematic representation of the research - experimentation 114
area.
Figure 20: Experimental attributes of in focus processes (∆ΙΑ, ∆CR) 114
establishing the changes to material characteristics in regard
to litho demands (∆CPR).
Figure 21: Sample selection for experimental work according to coil 114
width.
Figure 22: A polished pack mount, showing the polished surface of 115
examination.
Figure 23: Through sample thickness selection of imaging with SEM for 115
the particle size analysis.
7
Figure 24: The Barker’s anodizing setup for preparation of grain structure 115
examination.
Figure 25: 3D aspect of the grain structure, indicating the near-surface ¼ 116
thickness position of imaging for determination of grain size.
Figure 26: Example of grid of five equally spaced, parallel lines of the 116
same length for the determination of the mean lineal intercept
length.
Figure 27: Example of grid of equally spaced parallel and transverse 117
lines which form 100 crossing points that are used for the
determination of the fraction recrystallized.
Figure 28: The microhardness Vickers intender outline. 117
Figure 29: A microhardness test cycle profile. 118
Figure 30: Graphic representation of a coil, the coil’s sampling regions 118
and the selected positions for extracting temperature data
over time from the mathematical model.
Figure 31: Images of the layout used in the laboratory simulation of 119
annealing practice IA-1.
Figure 32: Plot of time-temperature program verification. 119
Figure 33: Images of the equipment used to perform laboratory 120
AC-electrograining.
Figure 34: Experimental setup for performing laboratory 120
AC-electrograining.
Figure 35: Representative optical micrographs of the second phase 150
particles population, size and distribution.
Figure 36: Representative backscattered electron micrographs of the 150
second phase particles population, size and distribution.
Figure 37: Graph of the mean number of second phase particles 151
measured per mm2.
Figure 38: Graph of the mean area fraction of second phase particles. 151
Figure 39: Graph of the mean particle circle diameter measured. 152
Figure 40: Logarithmic, cumulative graph of the particle size distribution 152
for sample 1 in all three planes.
Figure 41: Logarithmic, cumulative graphs of the particle size distribution, 153
in the longitudinal plane, of outer-coil samples 1 and 3, and
inner-coil samples 2 and 4.
Figure 42: Logarithmic, cumulative graphs of the particle size distribution, 154
in the longitudinal plane, of pre-annealed samples 1 and 2,
and post-annealed samples 3 and 4.
Figure 43: Logarithmic, cumulative graph, for the post-annealed particle 155
size distribution, after different annealing practices.
Figure 44: 3D optical micrographs of the grain structure evolution through 155
inter-annealing, viewed at x50 magnification.
Figure 45: 3D optical micrographs of the grain structure evolution through 156
8
Figure 46: 3D optical micrographs of fully recrystallized grain structures, 156
as those derived from different annealing practices, viewed at
x50 and at x200 magnifications.
Figure 47: Graph of the mean measured lineal intercept lengths of the 157
industrially annealed samples.
Figure 48: Histogram graphs from the lineal intercept length 157
measurements, for all measured specimens.
Figure 49: Graph of the measured Vickers hardness of the industrial pre- 158
and post-annealed samples.
Figure 50: Graph showing the mathematical model predicted curves and 158
the temperatures measured with thermocouples during a
recent furnace trial at similar coil positions.
Figure 51: Graph of the mathematical annealing model curves, for the 159
OD: 1850 mm coil.
Figure 52: Graph of the mathematical annealing model curves, for the 159
OD: 1500 mm coil.
Figure 53: Temperature contour graph from the mathematical annealing 160
model for coil OD: 1850mm, at the end of the annealing cycle.
Figure 54: Temperature contour graph from the mathematical annealing 160
model for coil OD: 1500mm, at the end of the annealing cycle.
Figure 55: Mathematical model annealing and cooling curves for coil OD: 161
1850mm.
Figure 56: Graph of the annealing and cooling curves of laboratory 161
annealing simulation (1): typical coil position, with circled
time-temperature intervals at which samples were taken for
examinations.
Figure 57: Micrographs of the grain structure evolution through annealing 162
and cooling, in the longitudinal plane, viewed at x50
magnification.
Figure 58: Grain structure micrographs highlighting the recovery phase, 163
the initiation of recrystallization and the fully recrystallized
state, in the longitudinal plane, viewed at x200 magnification.
Figure 59: Graph of the mean measured lineal intercept lengths, of the 164
fully recrystallized simulation annealed specimens and the
industrially annealed samples, in the longitudinal plane.
Figure 60: Graph of the measured hardness Vickers of the annealing 164
simulation specimens at the inner- and outer-coil positions.
Figure 61: Graph showing the heat-up rate curves for two different set 165
target temperatures.
Figure 62: Micrographs of the outer-coil, isochronally annealed 166
specimens’ grain structures, in the longitudinal plane, viewed
at x50 magnification.
Figure 63: Graph showing the fraction recrystallized against temperature 167
curves for the outer-coil and inner-coil position specimens, as
derived from the isochronal annealing experiment.
9
Figure 64: Graph showing the microhardness against temperature curve 167
for the outer-coil position from the isochronal annealing
experiment.
Figure 65: Micrographs of the outer-coil, isothermally annealed 168
Figure 66: Micrographs of the outer-coil, isothermally annealed 169
Figure 67: Graph showing the fraction recrystallized against time curve 170
from the outer-coil position specimens, as derived from the
isothermal annealing experiment.
Figure 68: Graph showing the microhardness against time curve for the 170
outer-coil position, as derived from the isothermal annealing
experiment.
Figure 69: Graphs of the JMAK equation fitting and the JMAK plot, as 171
deduced from the grain structure images.
Figure 70: Graphs of the JMAK equation fitting and the JMAK plot, as 172
deduced from the microhardness values.
Figure 71: Graph of the fraction recrystallized kinetics as measured and 173
calculated from the grain structure and microhardness data.
Figure 72: Graphs of the predicted annealing and cooling curves from the 174
mathematical annealing model, together with the verification
curves, for simulating the extreme coil positions 1 and 6.
Figure 73: Graphs comparing the model predicted and simulation 175
annealing and cooling curves of the extreme coil positions 1
and 6, also indicating distinguishing time-temperature
differences and temperature differences against time.
Figure 74: Optical micrographs in the longitudinal and transverse planes 176
of the simulated coil positions 1 and 6, viewed at x1000
magnification.
simulated extreme coil positions 1 and 6, in the longitudinal
plane, at x1000 magnification.
Figure 76: Graphs comparing the second phase particles’ number per 178
mm2, mean area fraction and mean circle diameter, between
the extreme coil positions.
Figure 77: Logarithmic, cumulative graph of the particle size distribution 179
of the simulated extreme coil positions.
Figure 78: 3D imaging representation of grain structures of the simulated 180-182
extreme coil positions, at the selected examination intervals,
viewed at x50 and x200 magnification.
Figure 79: Graphs showing the measured mean lineal intercept length of 183
the simulated extreme coil positions 1 and 6. The
corresponding histograms are also shown.
10
Figure 80: Graph of the changing electrical conductivity curves, for the 184
extreme coil positions 1 and 6, as measured at the selected
examination intervals of laboratory annealing simulation (2).
Figure 81: Graph of the microhardness values of the extreme coil 184
positions 1 and 6 at the selected examination intervals.
Figure 82: Graphs of the mechanical properties testing, as rolled and 185-186
baked (after heat treatment), showing results of the ultimate
tensile strength, yield strength, % elongation and modulus.
second phase particles population, size and distribution, after
final cold rolling, at 0.3 mm gauge, in the longitudinal plane,
viewed at x1000 magnification.
Figure 84: Graphs of the mean number of particles per mm2, the mean 188
area fraction of particles and the mean particle circle diameter,
as measured in the longitudinal plane of the 0.3 mm cold
rolled samples.
Figure 85: Logarithmic, cumulative graph of the particle size distribution, 189
in the longitudinal plane of the 0.3 mm cold rolled samples.
Figure 86: Graphs of the mean number of particles per mm2, the mean 189-190
area fraction of particles and the mean particle circle diameter,
as measured in the longitudinal plane, before annealing, after
annealing and after final cold rolling at 0.3 mm gauge.
Figure 87: Logarithmic cumulative graph of the particle size distribution, 191
in the longitudinal plane, at the inner-coil position, before, after
annealing and after final cold rolling.
Figure 88: Representative micrographs of the 0.3 mm gauge grain 192-193
structures in the surface, the longitudinal and the transverse
planes, viewed at x50 magnification.
Figure 89: 3D imaging representation of the 0.3 mm cold rolled sheet 194
samples’ grain structures, viewed at x200 magnification.
Figure 90: 3D imaging representation of the grain structure evolution, 194
through inter-annealing and final cold rolling, viewed at x200
magnification.
Figure 91: Graph of the measured current densities against time, after 195
laboratory AC-electrograining, also showing the calculated
charge densities.
Figure 92: Representative secondary electron micrographs of the 196
laboratory AC-electrograined surfaces, at 40˚ tilt, viewed at
x500 and x1000 magnification.
Figure 93: Graphs of the gloss measurements on the 0.3 mm gauge 197
materials AC-electrograined surfaces, at 20˚, 60˚ and 85˚.
Figure 94: Graphic representation of a coil, showing the, indicated from 198
the mathematical annealing models, hottest and coolest coil
positions, during annealing.
Figure 95: Graph of the maximum achieved temperatures, as those were 198
predicted from the mathematical annealing model, for all the
considered coil positions.
11
Figure 96: Graphs of the annealing curves at the investigated coil 199
positions 1, 6, 7 and 12, as those derived from the
mathematical annealing model, for ’minimum’ and ‘maximum’
coil sizes.
Figure 97: Graphs of the ∆Τ between coil positions 6 and 1 and between 200
coil positions 12 and 7 against time for the ’minimum’ and
‘maximum’ coil size.
Figure 98: Graphs comparing the mathematical annealing model curves 201-202
between the ‘minimum’ and ‘maximum’ coil sizes, at the
investigated coil positions 1, 6, 7 and 12.
List of Tables: Page

Table 1: Principal physical properties of unalloyed aluminium. 29
Table 2: Designations of wrought aluminium alloys. 30
Table 3: Chemical composition limits for AA1050 according to 33
BS EN 573-3:2007 and the Aluminum association.
Table 4: Physical properties for Aluminium Alloy 1050. 33
Table 5: Typical mechanical properties for aluminium alloy 1050. 33
Table 6: Liquid and solid solubilities of selected elements in AA1050. 34
Table 7: List of process and microstructural factors affecting 59
recrystallization.
Table 8: JMAK exponent values relevant to second phase particles 62
shape.
Table 9: Annealing summary, driving forces and kinetics mechanisms. 67
Table 10: List of provided material for experiments. 89
Table 11: Weight (%) composition of the major alloying elements in the 90
AA1050 samples.
Table 12: Annealing practice time-temperature targets. 90
Table 13: List of microhardness measurements error sources. 97
Table 14: Qualitative ranking scale of electrograining result. 105
Table 15: Samples for laboratory annealing simulation (1). 107
Table 16: Isochronal (30min) experiment temperatures. 108
Table 17: Isothermal treatment times at Tcrit. 109
Table 18: Specimens for furnace laboratory annealing simulation (2). 111
Table 19: Pre-anneal coil extreme dimensions used as input for the 113
mathematical models.
Table 20: Benchmarking of pre- and post-annealed materials; particle 122
size analysis results.
Table 21: Lineal intercept length measurements on industrially annealed 125
samples.
12
Table 22: Benchmarking of pre- and post-annealed materials; 126
microhardness.
Table 23: Laboratory annealing simulation (1); lineal intercept length 129
measurements.
Table 24: Laboratory annealing simulation (1); microhardness 129
measurements.
Table 25: Isochronal experiment; optical observation remarks and 131
fractions recrystallized.
Table 26: Isochronal experiment (30 minutes); microhardness 132
measurements.
Table 27: Isothermal experiment; optical observation remarks. 133
Table 28: Isothermal experiment; microhardness measurements. 134
Table 29: JMAK equation fitting; calculated fractions recrystallized. 135
Table 30: Calculated JMAK parameters. 136
Table 31: Calculated (linear) heating rates. 136
Table 32: Time-temperature differences during annealing simulation of 137
extreme coil positions 1 and 6.
Table 33: Annealing simulation of extreme coil positions 1 and 6; 138
particle size analysis results.
Table 34: Fraction recrystallized of the simulated extreme coil positions, 139
at 300 ˚C.
Table 35: Extreme coil positions annealing simulation, lineal intercept 139
length measurements.
Table 36: Extreme coil positions annealing simulation; electrical 140
conductivities (k) measurements.
Table 37: Extreme coil positions annealing simulation; microhardness 141
measurements.
Table 38: Mechanical properties of 0.3 mm gauge sheet, as-rolled and 142
after heat treatment (baked).
Table 39: Benchmarking of 0.3 mm gauge sheet; particle size analysis 144
results.
Table 40: AC-electrograined specimens, current (J) and charge (Q) 145
density results.
Table 41: AC-electrograined specimens, gloss measurements. 146
Table 42: Annealing modelling part 2, calculated (linear) heating rates. 147
Table 43: Mathematical annealing model, time-temperature critical 148
differences.
13
Abstract
The University of Manchester

Michail Mariglis
Master of Philosophy degree (MPhil)
The Influence of Inter-anneal and Cold Rolling Processes on Key
Lithographic Sheet Properties
2012
The aim of this research was to assess the influence of inter-anneal

and cold rolling processes on the key lithographic sheet properties. This was
performed through the properties and microstructure characterization of
industrial scale samples (annealed and cold rolled). The recrystallization
kinetics were established through laboratory annealing experiments. A
mathematical model was also used to study the annealing process and
formulate further laboratory furnace simulations. From the above, it was
shown that inter-annealing is a vital process for controlling a coil’s
microstructural uniformity. This is essential for consistent electrochemical
roughening behaviour of the lithographic sheet. Moreover, it was shown that
inter-annealing, together with final cold rolling, aids the control of the final
products’ tensile properties and thus on-press performance.
14
Declaration
I declare that no portion of the work referred to in the thesis has been
submitted in support of an application for another degree or qualification of this or
any other university or other institute of learning.
Copyright Statement
i. The author of this thesis (including any appendices and/or schedules to this
thesis) owns certain copyright or related rights in it (the “Copyright”) and he
has given The University of Manchester certain rights to use such Copyright,
including for administrative purposes.
ii. Copies of this thesis, either in full or in extracts and whether in hard or
electronic copy, may be made only in accordance with the Copyright,
Designs and Patents Act 1988 (as amended) and regulations issued under it
or, where appropriate, in accordance with licensing agreements which the
University has from time to time. This page must form part of any such
copies made.
iii. The ownership of certain Copyright, patents, designs, trade marks and other
intellectual property (the “Intellectual Property”) and any reproductions of
copyright works in the thesis, for example graphs and tables
(“Reproductions”), which may be described in this thesis, may not be owned
by the author and may be owned by third parties. Such Intellectual Property
and Reproductions cannot and must not be made available for use without
the prior written permission of the owner(s) of the relevant Intellectual
Property and/or Reproductions.
iv. Further information on the conditions under which disclosure, publication
and commercialisation of this thesis, the Copyright and any Intellectual
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the University IP Policy (see
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relevant Thesis restriction declarations deposited in the University Library,
The University Library’s regulations (see
http://www.manchester.ac.uk/library/aboutus/regulations) and in The
University’s policy on Presentation of Theses.
15
Acknowledgements
I would like to thank and express my gratitude to:
• My University supervisor, Professor George Thompson, for the opportunity to

work and deliver my thesis on this interesting topic, for supervising my work
and for his readiness, availability, experience and knowledge which he
always provided me during this work.
• My employers at ELKEME S.A. - Hellenic Research Centre for Metals, for

sponsoring me through this postgraduate course.
• Dr. Richard Hunt, for providing me with the appropriate materials for
experiments and all necessary process data.
• My mentors, Mr. Steve Ping, Dr. Ioannis Contopoulos, Dr. Thanasis

Dimogerontakis and Dr. Dimitris Voulgaris, for providing me with their
expertise, knowledge and inspiration.
• My colleagues at ELKEME S.A. for their support.
• I would like to especially thank my industrial supervisor, Mr. Jeremy Brown,

for his continuing help, support and encouragement during this project.
• Finally, I would like to acknowledge the support and patience of my family.
16
Introduction
The key lithographic sheet properties, considered in this thesis, are the
aluminium substrate relative requirements, which are considered essential for an
optimum on-press performance of an offset lithographic printing plate. Many of the
fabricating processes are considered critical for the evolution of these properties.
Two such processes, the inter-annealing and cold rolling, and in particular the
changes those induce to the aluminium structure, are the subject of investigation of
this research.
The offset lithographic printing plate production begins with a high quality
aluminium substrate that is electrochemically grained, anodized and coated to
produce a high quality printing plate. This plate is expected to have a robust press
performance and stable ink/water balance throughout its estimated lifetime so as to
produce high quality printed results. Environmental awareness and technological
innovations have directed the interest on plate production and development by using
less chemicals, energy and process. This is targeted so as to reduce the waste
generation and operation time without compromising the quality of the final print.
Suitable control of the heating range, annealing temperature and cooling rate
of the coil afterwards could promote inter-annealing as the key process for
controlling the solute composition and coarse constituents, second phase particles
distribution before final cold rolling. In this sense, inter-annealing possibly plays a
vital role in enhancing the substrate properties for lithographic printing plate
production. A good control of the solute levels, especially those of iron, through the
inter-annealing procedure could enhance the final gauge product properties, thus
improve the aluminium sheet for use as a substrate for lithographic printing plates.
17
1. Literature Review
This section covers the history and evolution of printing. The focus is on the
offset lithographic printing process and its present day status. A detailed description
of the material used and of its fabrication into lithographic printing plates is also
given. The lithographic printing plate product requirements and their significance are
then explained. Finally, a detailed description of the inter-annealing and cold rolling
processes of the aluminium sheet used as plate substrate is given.
The research aims to clarify the interactions between the product

requirements and the inter-annealing and cold rolling processes in order to assess
the in-service performance of the product.
1.1 Printing History - Offset Lithographic Printing Evolution and Plate

Materials
Printing has been one of the most significant technological developments in

human history. Communication prior to printing was literally limited. Many historians
credit the invention of printing with the end of the middle ages and the beginning of
the Renaissance and modern history. What had forced the invention of printing was
the need to pass on knowledge and transfer ideas. All humans are entitled to
knowledge as this is one of the most basic human rights [DPS, 2012].
1.1.1 Printing history and significance
The earliest attempt of man to communicate through drawings dates back to

35000 BC. Man drew on cave walls (pictographs), which represented real objects.
Later Phoenicians developed ideographs and, circa 900 BC, assigned sounds to
those. Greeks adopted and evolved the Phonetic system, which was later borrowed
and expanded from Romans to create Latin and, subsequently, known as the
Roman alphabet [Fleming, 2004].
Printing appeared in China and Korea in the 11th century. The oldest known
printed text dates to 1397 AD. In 1440, Gutenberg invented a form of printing with
ink on paper. Although paper and ink were not unknown at that time, Gutenberg is
considered to be the pioneer for establishing printing as a commercial and cultural
process of graphic reproduction. The first known book to be printed was the “Holy
Bible” however, Gutenberg went bankrupt. Printing was introduced in England about
18
1476 by Caxton. In America printing was used to promote colonization, with the first
printing press found in Massachusetts in 1638 [DPS, 2012].
It is impossible to imagine the World today as we know it without printing. It

is universally present and plays a vital role in everyday living. Prints are largely
produced using sustainable materials. Printing is highly effective, has impact,
longevity and authority. Printing is an important vehicle for advertising, education,
entertainment and information. Moreover, printing is an advanced manufacturing
sector [BPIF, 2011].
The printing industry today is one of the largest industries. This is because of
innovations in technology, particularly electronics, computers, chemistry, optics and
mechanics. Printing has gradually been transformed from an art to a science. The
printing industry is today amongst the first manufacturing industries worldwide. The
printing companies scale from big colossal companies like Toppan and Dai Nipon of
Japan, Donneley R.R. & Sons Co. and Quad Graphics Inc of United States,
Quebecor of Canada, DS Smith (UK Print, Paper & Packaging) and Williams Lea
Group of United Kingdom and Rexam PLC of Germany, to small corner print shops
which cover everyday printing needs. Printers could be designated as commercial,
trade shops, special purpose, quick printing, in plant, publishing and packaging.
Additionally, there are several other industries providing materials to the printing
industry, such as paper, ink, film, plate material, press and peripheral equipment
[Encyclopedia of Business 2nd ed. 2011; Fleming, 2004].
1.1.2 Printing processes
The printing industry is very diverse and in the majority driven by the
customer, commodity or product demand. The printing processes that are presently
available are used to print mainly on paper, but also on other substrates. The six
major categories are [PNEAC, 2012]:
• Letterpress
• Flexography
• Gravure
• Screen printing
• Plateless printing and
• Lithography
19
Letterpress is the oldest of the printing methods, developed centuries ago by
the Chinese. It is a relief printing process, where ink is applied to the top surface of
the raised image area and pressed against the substrate to transfer the image.
Letterpress was the first printing process to be utilized and was extensively used
until the mid-1940s. Typical examples of media printed with this method nowadays
include newspapers, labels and books. However, this is a less and less used
process that has been suppressed by other more efficient printing methods. Figure
1a shows a schematic diagram of the letterpress printing process [Claridge, 2005;
PNEAC, 2012].
Flexography is an evolution of letterpress. It is still a relief printing process

which differs in the ink application method. The name resembles the plate which is
flexible. Flexography today is primarily used for packaging materials, corrugated
containers, milk and beverage cartons, labels, food and candy wrappers, etc. Figure
1b shows a schematic diagram of the flexography printing process [DPS, 2012;
PNEAC, 2012].
Gravure printing, also known as Rotogravure or Intaglio, is a recessed

printing process. The impressions to be printed are laser etched, cut, engraved or
photo-mechanically produced into a plate or cylinder of varying depths. The
recessed image is then flooded with ink and the surplus is removed from the surface
of the plate or cylinder to create an impression. Gravure is used for long run, high
quality printing producing fine and sharp images without degradation on a variety of
substrates. Typical gravure printing products include print packaging, magazines,
wallpaper, gift wrap etc. Among the most interesting applications are those of money
and post stamps printing [Claridge, 2005; PNEAC, 2012]. Figure 2 shows a
schematic diagram of the gravure printing process.
Screen printing is a further printing method. It is a stencil printing method

where the image is cut, photo-masked or etched through a sheet of paper, card,
fabric or other material in order to allow ink to pass through to the substrate. Screen
printing is arguably the most versatile of all printing processes. It can be used to
print on a wide variety of substrates, including paper, paperboard, plastics, glass,
metals, fabrics, and many other materials. Some common products from the screen
printing industry include posters, labels, decals, signage, and all types of textiles and
electronic circuit boards. The advantage of screen printing over other print
processes is that the press can print on substrates of any shape, thickness and size
[Claridge, 2005; PNEAC, 2012]. Figure 3 shows a schematic diagram of the screen
printing process.
20
Plateless printing is the newest of the processes, also referred to as
non-impact printing due to the absence of printing plates or any other type of
physical image carrier. Plateless printing relies on sophisticated computer software
and hardware to control the printing elements. Commercial plateless printing
technologies include: laser printers, ink-jet printers, dye sublimation printers, thermal
transfer printers, and others. Because of the association with digital computers, non-
impact printing is often referred to as digital printing. Because all of these devices
print directly from digital files, it is just as easy to print a single copy as many copies.
This has made possible on-demand and variable data printing [Fleming, 2004;
PNEAC, 2012]. Figure 4 shows a flow diagram of the plateless printing process.
Lithography is currently by far the most used method for printing. It is well
suited for printing both text and illustrations in short to medium length runs with up to
1.000.000 impressions. It is a planographic printing process where the image areas
and the non image areas exist on the same plane. Lithography, often referred to as
offset or “litho”, is used for a great variety of printed products, including newspapers,
magazines, books, business forms, financial and legal documents etc [Claridge,
2005].
According to standard [BS 4277:1968 (2007)], lithographic printing is a

planographic printing process in which the non-image areas of the printing plate are
made hydrophilic and the image areas are made hydrophobic. The basic principle
behind lithography is that oil and water do not mix. Using this basic chemical
principle, image areas are made water repellent and ink receptive, while the non
image areas are made water receptive and ink repellent [DPS, 2012]. Figure 5
shows schematic diagrams of the lithographic printing process.
1.1.3 Evolution of the lithographic printing process
The history of the lithographic printing process comprises four milestones

[Waite, 2011]:
i. Invention and early use,
ii. introduction of photography to the process,
iii. addition of the offset press and
iv. revolution of the lithographic plate.
The invention was the outcome of a man’s will to achieve a cheaper method
of reproducing his scripts of theatre plays. However, although the intention was
21
artistic and noble, it was pure chance that made it possible, together with a “laundry
list”. The inventor, Alois Senefelder, was a German actor and writer, who set on
finding a way of reproducing his writings. Senefelder invented the art of lithography
in 1798. He had begun his trials earlier by trying to use reverse imaging on copper
so as to create his own copperplate engravings. Soon he had to turn to slabs of
Bavarian limestone, rather than the pricey copper, to practice his engraving. One
day, when he lacked a piece of paper to note a clothing list for the laundry shop, he
took some crayon and wrote on a piece of limestone.
That is how Lithography got its name, from the ancient Greek words “λίθος”
and “γραφείν” which mean “stone” and “writing” respectively. Senefelder, however,
preferred the term chemical printing. From then on, he used his intuition and
expertise to make his first printings and further develop his technique by designing a
press for it. All of his efforts and knowledge were reflected in his handbook of the art
of Lithography. At the onset, the lithographic printing process was slow due to the
flat bed design of the presses. The limestone substrate could not be bent in order to
use it around a cylinder in a rotary method. Senefelder had managed by
experimenting to use chemically treated plates of metal, thus allowing the use of
rotary presses [Senefelder, 1819; Waite, 2011; Print Wiki, 2012].
Stone lithography was used as an artistic mean for picture printing before it
became a mass printing process. Many well known artists including Delacroix,
Gericault, Goya, Degas, Toulouse-Lautrec and others, used lithography for their
work in the 19th Century. During the 20th Century, artists like Calder, Matisse, Miro
and Picasso practiced with the art of lithography in Paris.
The process, however, changed when lithography was associated with

photography to create lithographic printing plates by photographic means. It became
possible to combine pictures, including photographs, with text, on a single printing
plate. Niepce, a pioneer in photography, experimented with lithography in 1826. In
1855, photolithography was invented by the French chemist, Louis Poitevin.
Lithography was the first printing process to make use of the same plate to combine
text together with graphics photographically and photo-mechanically. Some of the
first metal printing plate materials included iron, zinc and aluminium. The ability to
print in colour was developed in 1837 by the Engelmanns, father and son [Waite,
2011; Fleming, 2004; Encyclopedia of Business 2nd ed. 2011].
One of the most important evolution steps of the lithographic printing process
was the use of the offset method. According to standard [BS 4277:1968 (2007)],
22
offset printing is a method of printing in which the image is transferred to the final
substrate using an intermediate surface. The lithographic offset press originated
from England at about 1875. It was Rubel from New Jersey, USA however, who was
credited with the first use of the offset process in the early 1900’s. The offset press
eliminated contact between plate and paper by the addition of a rubber blanket
surface. This was achieved while feeding a flat stone bed press equipped with a
rubber support cylinder with paper. When a worker missed feeding the press with
paper, the image was printed on the support rubber cylinder and the next paper was
printed on both sides, one in the usual way and its reverse side from the rubber
cylinder. It was noticed that the “mistakenly” printed image was much sharper and
had improved quality compared to the original. Later, Harris developed the offset
rotary press. Due to the fact that the offset method removed the direct touch of the
plate and paper, the plate could last longer than previously. In addition, the offset
method using the rotary cylinders made offset lithographic printing faster, thus
advancing the lithographic printing process to a commercial printing process [Waite,
2011; Print Wiki, 2012].
1.1.4 Practice of offset lithographic printing
The way that offset lithography works is illustrated in the schematic diagrams
of Figure 5. A series of wetting rolls lay down a film of water-based solution on the
printing plate. This dampening solution is commonly referred to as fountain solution
and consists of: Water, an acid or base to give the desired pH, a gum such as gum
Arabic, a corrosion inhibitor to prevent the solution from corroding the metallic plate,
an alcohol base wetting agent to reduce surface tensions, a drying stimulator which
is related to the ink drier, an antimicrobial agent to prevent growth of microbial
population and an antifoaming agent. The water film is laid down on the non-image
areas which are hydrophilic.
The ink rollers subsequently transfer ink from the ink fountain to the printing
plate image areas. They lay down a film of oil-based ink over the plate, which is
rejected by the already hydrophilic (non-image) areas but attracted by the
hydrophobic (image) areas. Offset inking systems may have up to ten different
rollers with the purpose of transferring the ink to the printing plate, breaking the
viscous ink down to thinner, workable film and preventing faint reproductions. This
results in an inked image on the printing plate, which is transferred to the blanket
cylinder [Print Wiki, 2012].
23
The offset blanket usually comprises of synthetic rubber and should have a
smooth surface that releases the impressions with ease. The image is transferred
from the blanket onto the substrate, paper, carton, plastic, etc, depending on the
printed matter, which is also on a cylinder, the impression cylinder. Apart from the
above, other units of the offset lithographic process are the feeding and sheet
control. The sheet –fed presses print one sheet at a time at very high speeds and
web fed presses print on a continuous roll which is later cut to the desired size.
According to the type of the ink and the way it dries, two more types of offset printing
exist, the heat-set and the non heat-set [Lovelace and Thom, 2002; Beguin, 2011].
1.1.5 The lithographic printing plate
The lithographic printing plate is one of the key aspects of quality printing
with the offset lithographic process. Originally the medium was limestone, which was
heavy, non-bendable and it was part of a rather slow printing process. Metal plates,
which were lighter and could be bent around a cylinder, thus making them suitable
for the offset method, were introduced later in the nineteenth century. Zinc was the
first used metal for this purpose and the process was termed “zincography”. This
technique was patented by Breugnot in 1834. Other thin and flexible metal sheets
used as printing surfaces apart from zinc included aluminium, stainless steel,
bimetallic and polymetallic plates. However, one of the most important parts of the
lithographic plate evolution occurred during the 1940s. Previously, all preparation of
the metal surface was performed by the lithography printer in his work shop.
Scientists experimented and developed a method to create uniform and consistent
pre-coated (or pre-sensitized) plates, ready to be sold. The first were paper based
but were not suitable for long runs [Beguin, 2011].
The first pre-sensitized offset printing plate was presented in 1949 by the
company Hoechst / Kalle, and in 1951 3M developed the first practical aluminium
plate. The aluminium substrate was selected at that time for its inherent
characteristics of light weight, flexibility, resistance to corrosion and cost compared
to others [Agfa Graphics, 2011; Waite, 2011].
Subsequently, many innovations have managed to enhance the performance

of the lithographic plate medium. Today, the majority of lithographic plates are made
of thin aluminium sheet with a chemically roughened surface. Other plate materials
include stainless steel, plastic, polyester, paper and multi-metal as base. The
multi-metal materials commonly used today are copper plated onto stainless steel or
24
aluminium and chromium plated on copper. These types of plates are
simultaneously the most durable and expensive ones. Paper and polyester plate
types are only used for small scale printing in small presses. Aluminium lithographic
plates are inexpensive compared to other printing plate media, thus making the
lithographic printing process very popular [DPS, 2012].
The plates have a chemically roughened surface, also referred to as grained

surface. The roughened surface provides water carrying properties to the plate and
stability to the image forming material. Practically all pre-coated or presensitized
plates have a layer of photopolymer coating which reacts with UV light to create
hydrophobic image areas by hardening (cross linking) of the polymer. The rest of the
polymer, which is not hardened, is easily removed [DPS, 2012]. Figure 6 illustrates
how this is achieved.
The seven major types of lithographic plates used today by the printing
industry are [DPS, 2012]:
i. Diazo (run lengths 100.000 to 250.000 impressions)
ii. Photopolymer (the most widely used plates, up to 1.000.000 impressions)
iii. Silver Halide (suitable for short and quick runs)
iv. Electrophotographic (suitable for short and quick runs)
v. Bimetal (durable but expensive)
vi. Waterless (with an added surface silicone layer and simultaneous cooling of
the printing cylinder to avoid ink drying, has higher printing resolution but is
suitable for shorter run lengths) and
vii. Computer to plate (CtP) (The most up to date plate technology which
eliminates the use of film, stripping and other normal analogue plate making
processes, thus leading to shorter pre-press times, lower production
expenses but high quality print results).
All types of plates are generally classified as negative or positive working

plates. The negative working plates are the least expensive and most commonly
used plates. They are coated with a photopolymer and the image is applied on a film
negative. The positive working plates are more expensive and use a different kind of
photopolymer, which is hardened prior to exposure and uses film positives for the
image [DPS, 2012].
25
The evolution of the offset lithographic printing plate since it was introduced
has been associated with technological innovations that offered improved
productivity and less energy consumption. The cost of plate making has risen in the
past few years because of the higher raw aluminium cost, which accounts for over
60% of a plate [Tribune, 2006]. In the beginning of the 1990s, the direct to plate
(DTP) technology was introduced. In 1993, Agfa introduced Lithostar, the first
computer to plate (CTP) printing plate and in 2004, further innovations led to
chemistry-free plates [Agfa Graphics, 2011].
Computer to plate is a technology broadly used today and has allowed offset
lithographic printing to remain competitive with the fast growing electronic media.
However, environmental concerns are currently pushing towards technologies that
could reduce the make-ready times, process steps and ink usage while still
achieving good water/ink balance and high numbers of printing impressions. In the
future, printers will increasingly turn to process-less and chemistry-free plates in
order to be cost efficient and environmental friendly, also producing less carbon
emissions. The difference between those is that processless plates get developed
on the press during preparation whereas chemistry-free plates use a gumming unit
to remove unexposed parts, thus adding an extra process step [Cox, 2008].
The commercial printing plates are currently split into two technologies:
• Analogue plates and
• digital plates, which according to their development method are further

subcategorized as follows:
o Chemistry free,
o thermal,
o UV and
o visible light.
The plate development is a major industrial issue that has risen a great
debate over which of the thermal or violet technologies is best [Gbadamosi, 2008].
1.1.6 Current status of the lithographic printing business
The customer needs and the printed product specifications define the criteria
of selecting the most suitable printing process. The last few years there is a strong
rivalry between the offset lithographic and the digital printing methods. Offset
26
lithography and digital printing are very different in their application. They both apply
a colour agent under control on the print substrate, but the way this is applied and
the nature of the ink are different for the two processes. Both printing methods are
used extensively compared to the other methods and this raises the question as to
which of the two is better [Lovelace and Thom, 2002].
Around the middle of the last century, that was exactly the case for the
letterpress and the offset litho printing methods. The letterpress was the printing
dominant and offset litho was regarded as the ‘new era’. A few years later,
letterpress diminished while offset litho continued blooming. Recently though, the
growth of digital printing has provided technical advancements, more options and.
fascinating new features for commercial printing.
The advantages of digital printing are the shorter turnaround, the similarity
and accuracy of printing, the cost for low printing volumes and the great variability
because of the ease of customization. The most important, however, is that of the
elimination of production steps such as that of plate making. There are recent
reports which show that digital printing is no longer seen as a poor equivalent of
offset printing. An approximate 12-15 % (by value) is produced digitally [Tribune,
2009; Smyth, 2008].
On the other hand, offset litho offers high image quality and lower per unit
cost. The quality and cost effectiveness, especially in high volume printing tasks, is
undisputable. The litho presses are more productive than the digital equivalents
which consist of many electronic components that consume even more resources.
The inks used in the offset methods are being formulated with vegetable oils
replacing mineral grades and eliminate alcohol with water-based coatings. If digital
printing is going to advance, only time will tell, conversely, as long as the offset litho
supply chain keeps innovating, offset litho will remain viable [Pinsnnault Creative,
2011; Smyth, 2008; Romano, 2009].
In the past decade, the printing business has suffered a major hit from the
fast growing electronic media and the economic crisis. Especially the printed
newspaper volumes, which account for billions of prints, have decreased
substantially. Many of the smaller newspapers have either shut down or gone
online. Newspapers, magazines and books represent the majority of the offset
printed media. The electronic media rivals are easy and prompt to access from all
sort of devices (computer, laptop, smart-phone, electronic tablet, TV, etc). They are
moreover accessible at all times and almost all places, usually for free. The
27
publication earnings come from either readers or advertising. Readers have turned
away to other means and advertising is also moving away (16% drop in the last two
years) [Grotans, 2009].
This is the major reason why the concern should be drawn towards the
development of new, better and more efficient ways for plate making that can
simultaneously promote environmental awareness and be production-cost
competitive with the electronic media.
1.2 Aluminium in Offset Lithographic Printing
Aluminium is a material with numerous applications. Amongst those is the

use as substrate for lithographic printing plates.
1.2.1 Aluminium material
Aluminium is considered as one of the most versatile engineering materials.

British Sir Humphry Davy, from Britain, established and named the material in 1808.
In 1825, Hans Christian Oersted, from Denmark, was the first to isolate aluminium
and, in 1845, Friedrich Wohler, from Germany, managed to produce aluminium in
small globule sizes (little balls). In 1854, Henri Sainte-Claire Deville, from France,
created the first commercial process for making aluminium. By 1856, some early
applications of aluminium as a material started and in 1886, Paul Louis Toussaint
Heroult, from France, and Charles Martin Hall, from USA, who had no prior
knowledge of each another, independently discovered the electrolytic reduction of
aluminium. Between 1887 and 1892 Karl Joseph Bayer, from Austria, introduced the
smelting process used currently [Ricks and Evans, 2006].
The abundance of required characteristics, technological developments and

innovations associated with aluminium has set it high amongst materials.
Commercially, aluminium is second only to iron. The demand for aluminium is about
29 million tones per year, 7 of which come from recycling. 85% of the aluminium
produced worldwide is used in packaging, transport, marine applications, buildings,
structures and architecture, foils, pharmaceutical, food industry, insulation and
electrical laminates. The remaining 15% is used in ladders, high pressure cylinders,
sports, machined parts, road barriers and signs, furniture and of relevance to this
study lithographic printing plates [Aalco, 2011].
28
Aluminium is the third most abundant metal in the earth’s crust and it is twice
as available as iron, which is the fourth most abundant metal. Aluminium cannot be
found “clean”, but it is extracted from the ore of bauxite. Bauxite is purified with the
“Bayer” process to produce aluminium oxide (alumina). The technique to extract
aluminium from alumina is called smelting and it is an electrolytic process during
which pure aluminium gathers at the cathode while the anode is carbon. This takes
place in a solution of liquid cryolite (sodium aluminium fluoride) at 950 °C, with the
passage of electrical current [Aalco, 2011].
Aluminium uniquely combines a series of properties to gain advantage over

or replace other engineering materials like copper, steel, zinc, paper, wood,
concrete and others. Aluminium has a density about one-third that of iron. This gives
aluminium an excellent strength to weight ratio. One of the most important
properties of aluminium is that of high corrosion resistance, since it is protected by a
thin layer of oxide which is formed instantly on exposure of the metal to the
atmosphere. Aluminium also has high conductivity, both thermal and electrical.
Further, aluminium has very good light and heat reflectivity. Aluminium is
environmentally-friendly, 100% recyclable, non-toxic and odourless. It is also
malleable and machinable, which means that it can be drawn, rolled, forged or even
extruded to desired shape. Some of the physical properties of aluminium are listed
in the following Table 1.
Table 1: Principal physical properties of unalloyed aluminium [Hatch, 1984]
Property Unit Value Note

Atomic Number 13
-3
Density, ρ kg m 2.698
Melting Point °C 660.45 <1013x10 -3 bar
Boiling Point °C 2056 <1013x10 -3 bar
Vapour Pressure Pa 3.7 x 10-3 At 927 °C
Mass internal energy, u J kg-1 3.98 x 105
Mass thermal capacity, Cp J kg-1 K-1 897 At 25 °C
-1 -1
Thermal conductivity, λ Wm K 237 At 27 °C
Linear expansion coefficient, α1 10-6 K-1 23.1 At 25 °C
-9
Electrical resistivity, ρ 10 Ωm 26.548 At 25 °C
-3
Magnetic susceptibility, K 0.6 x 10 At 25 °C
Longitudinal elasticity modulus, K M Pa 69000
Poisson’s ratio, ν 0.33
29
1.2.2 Aluminium alloys
Aluminium is alloyed with other elements to give it enhanced properties to

achieve an even greater range of applications. There are many aluminium alloys,
approximately 300, but about 50 are in common use. The alloys are divided into
wrought alloys and cast alloys. The wrought alloys use a four digit system by which
each digit represents a certain feature of the alloy, also corresponding to the
chronological order in which they were developed. The cast alloys follow a similar
system with a five digit code. The major designations according to the first of the
four digits of wrought aluminium alloys are shown in Table 2 [Hatch, 1984].
Table 2: Designations of wrought aluminium alloys
Designation Major Alloying element

1XXX None
2XXX Cu
3XXX Mn
4XXX Si
5XXX Mg
6XXX Mg and Si
7XXX Zn
8XXX Other than above
9XXX Unused
For the 1XXX series alloys, the second digit refers to intentional alloying or
otherwise [Ricks & Evans, 2006]:
• 10xx – unalloyed
• 11xx – alloyed with copper
• 12xx – alloyed with iron and silicon
• 13xx – electrical conductor grade treated with boron.
The last two digits of a 10XX alloy describe the purity levels (e.g. AA1050 is
99.5% aluminium) [Ricks & Evans, 2006].
According to the heat treatment procedure that an aluminum alloy has

undergone, a suffix is used in to describe its condition [Aalco, 2011], namely:
• F, is used for as fabricated
• O, is used for annealed wrought products
30
• T, is used for heat treated products
• W, is used for solution heat treated products and
• H, is used for non heat treated alloys which are work or strain hardened.
Heat treatable alloys have the following temper designations [Aalco, 2011]:
• T1, Cooled from an elevated temperature – shaping process – naturally aged
• T2, Cooled from an elevated temperature – shaping process – cold worked –

naturally aged
• T3, Solution heat treated – cold worked – naturally aged
• T4, Solution heat treated – naturally aged
• T5, Cooled from an elevated temperature – shaping process – artificially

aged
• T6, Solution heat treated – artificially aged and
• T7, Solution heat treated – overaged / stabilized.
The non-heat treated alloys gain their properties by work hardening or cold
working. According to the worked condition and the degree of temper, the non-heat
treatable alloys follow the designations below [Aalco, 2011]:
• H1X, work hardened
• H2X, work hardened and partially annealed
• H3X, work hardened and stabilized by low temperature treatment
• H4X, work hardened and stoved
• HX2, quarter hard – degree of working
• HX4, half hard – degree of working
• HX6, three quarters hard – degree of working
• HX8, fully hard – degree of working.
An example of the above is the H18 temper, which is a fully hard, work
hardened alloy. In particular it is interesting to mention the H19 temper, which is the
extra hard temper for products with substantially higher strengths and greater strain
hardening than obtained with the H18 temper [Hatch, 1984].
31
Aluminium can be formed into almost everything. A frequently used (more
than one-half of total aluminium production) form of aluminium is that of rolled,
semi-finished products. Rolled aluminium metal can be used in a variety of
applications from transportation, containers and packaging, building and
construction, consumer durables and of relevance to this thesis lithographic printing
plates. The reason for rolling of aluminium metal is to achieve desired dimensions
and characteristics of shape and tolerances needed for the specified final product.
1.2.3. Aluminium alloy AA1050
Aluminium is used as a substrate for lithographic printing plates. The most

common alloy used is the EN AW-1050A alloy. This alloy is traditionally used in
Europe, Asia and South America. Other alloys used are the EN AW-1100, the
EN AW-3003 and EN AW-3103 alloys. The 3XXX alloys contain manganese and are
better suited for tougher (hard duty) printing applications were greater strength is
demanded. These are traditionally used in North America, however, their
AC-electrograining response is not as good as the AA1050 and they are often used
with mechanical roughening processes [Sigli et al. (a); Smith et al. 2010; Rottwinkel
et al. 2011].
The AA1050 is 99.5 % pure aluminium and the remaining 0.5 % is natural
impurities from smelters. The chemical composition limits for EN AW 1050A are
shown in Table 3 [BS EN 573:2007 (2007); The Aluminum Association, 2009]. The
physical and mechanical properties of AA1050 are shown in Tables 4 and 5
respectively.
32
Table 3: Chemical composition limits for AA1050 according to
(a) BS EN 573-3:2007 and (b) the Aluminum association.
(a) Alloy designation

Si Fe Cu Mn Mg Cr Ni
Numerical Chemical symbols
EN AW 1050A EN AW-Al 99.5 0.25 0.40 0.05 0.05 0.05 - -
Zn Ti Ga V Others Aluminium min.
Each Total
0.07 0.05 - - 0.03 99.50
(b) Registered
International
Designation Si Fe Cu Mn Mg Cr Ni Zn Ti Ag
No Date By
1050 1954 USA 0.25 0.40 0.05 0.05 0.05 … … 0.05 0.03 …
1050A 1972 EAA 0.25 0.40 0.05 0.05 0.05 … … 0.07 0.05 …
Others Al
B Bi Ga Li Pb Sn V Zr
Each Total Minimum
… … … … … … 0.05 … 0.03 … 99.5

… … … … … … … … 0.03 … 99.5
Table 4: Physical properties for aluminium Alloy 1050 [Aalco, 2011].

Property Value
Density 2.71 g/cm3

Melting Point 650°C
Modulus of Elasticity 71 GPa
Electrical Resistivity 0.0282x10-6 Ω.m
Thermal Conductivity 222 W/m.K
Thermal Expansion 24x10-6 /K
Table 5: Typical mechanical properties for aluminium alloy 1050

[BS EN 485-2:2008].
Temper H12 H14 H16 H18 O
Proof Stress 0.2% (MPa) 85 105 120 140 35

Tensile Strength (MPa) 100 115 130 150 80
Shear Strength (MPa) 60 70 80 85 50
Elongation A5 (%) 12 10 7 6 42
Hardness Vickers (HV) 30 36 - 44 20
33
AA1050 is used as the substrate for lithographic printing plates because of
its mechanical properties and its chemical performance during AC-electrograining.
This alloy is also relatively cheap to produce as it contains alloying elements in small
amounts [Rottwinkel et al. 2011]. Minor additions of some elements (notably Fe and
Si) are added to smelter metal which enhances strength. Each element has a
different solid solubility in aluminium. The elements encountered in AA1050 and
their solid solubilities in aluminium are shown in Table 6. Elements that are added in
amounts lower than their solid solubility remain in solid solution in the aluminium
α phase and provide solid solution strengthening. Elements which are added in
amounts greater than their solid solubility produce a second phase material in the
form of the pure element, or more commonly, in the form of a compound with
aluminium and possibly other added elements. Thus, alloying elements are added
initially to increase strength although other important properties improve as well.
The suppliers of aluminium for lithographic printing plates have developed

new, improved alloys, based on AA1050, which give a rolled sheet product with
enhanced properties.
Table 6: Liquid and solid solubilities of selected elements in AA1050 [Hatch, 1984].
Temperature(a) Liquid Solubility Solid Solubility

Element
°C Weight % Atomic % Weight % Atomic %
Fe 655 1.87 0.91 0.052 0.025
Si 580 12.6 12.16 1.65 1.59
Mg 450 35.0 37.34 14.9 16.26
Ti 665(b) 0.15 0.084 1.00 0.57
Zn 380 95.0 88.7 82.8 66.4
Cu 550 33.15 17.39 5.67 2.48
Mn 660 1.95 0.97 1.82 0.90
(a) Eutectoid, (b) Peritectic
Iron is the most common impurity encountered in aluminium. The

composition limit for iron in AA1050 is 0.4 weight %. The solid solubility of iron in
aluminium is negligible (~0.05 weight % and substantially less at room temperature);
consequently iron is generally encountered in the form of compounds with
aluminium such as Al3Fe. The iron alloying addition in AA1050 serves multiple
purposes. Iron is known to reduce the grain size in wrought alloys. Iron also
provides sufficient coarse intermetallic particles which act as nucleation sites during
34
recrystallization or thermomechanical processes, thereby favoring a random texture.
These also contribute greatly as pit formation starting points, so that a uniform and
finely dispersed pit structure is achieved. The presence however of too many of
those iron particles is detrimental to AC-electrograining. Iron prevents softening
distortion since it prevents localized recrystallization. Iron also enhances the alloy’s
strength properties in both the as rolled and stoved state also being cost effective for
use in high volume production of lithographic sheet. The impact of iron on annealing
is thoroughly described at a later section [Allen et al. 1998; Hatch, 1984; Uesugi et
al. 2008; Evans, et al. 2004; Rottwinkel et al. 2011].
Silicon is the second most common impurity encountered in aluminium,

originating from the bauxite ore. In AA1050, silicon is present up to 0.25 %, although
as an impurity it ranges between 0.01 and 0.15 %. Excess silicon is associated with
ink staining and poor anodizing. The solid solubility of silicon in aluminium is 1.65 %
and it can also be encountered in the ternary α-Al-Fe-Si phase as second phase
particles, which also serve as pit initiation points. Silicon levels between
0.03 - 0.15 % promote electrograining uniformity. The iron / silicon fraction is very
important and preferably in between 2.5 - 4.5. Silicon in solid solution alters the
alloy’s reactivity during AC-electrograining. If the level of silicon is low then too many
pits form on the surface while if the level is high then too few pits form and they are
too large [Sawada, 2004; Uesugi et al. 2008; Evans et al. 2004; Rottwinkel et al.
2011].
Magnesium has high solid solubility (14.9 %), which means it is present in
the bulk aluminium α-phase. In AA1050 the composition limit is up to 0.05 %.
Magnesium is added to the AA1050 to enhance strengthening properties. It is the
element influencing the work hardening of the alloy. Magnesium increases
aluminium’s yield strength, in absence of work hardening, approximately
15 - 25 MPa per weight % of magnesium addition. Additions up to at least 0.1 %
improve reverse bending fatigue strength and recrystallization to prevent
streakiness. Excess to 0.3 % magnesium causes uneven graining. Magnesium
additions are preferably between 0.05 - 0.3 weight %. Magnesium additions in
AA1050 also improve thermal softening resistance (baking resistance), the
roughening rate and wettability during electrochemical roughening. It may provide
recrystallization already in the hot strip thus leading to a globulitic grain structure
with small grain diameters. Scamans, cited in Zhou (2010), suggested that the rates
of diffusion and oxidation of magnesium to the alloy surface increase with
temperature and form MgO which could result in surface staining [Rottwinkel et al.
35
2011; Ricks and Evans, 2006; von Asten et al. 2002; Uesugi et al. 2008; Kernig et
al. 2009; Zhou, 2010].
Titanium is used to promote grain refinement through addition of TiB2,

commonly rods, to molten aluminium. In AA1050, it is usually added at low
concentrations so as to favor a better graining result and at such a level that free
titanium does not exceed 100 ppm. Titanium additions also ensure uniform pit
formation during electrolytic treatment without streakiness. The preferable additions
when added together with boron are less than 0.01 % [Uesugi et al. 2008;
Rottwinkel et al. 2011].
Zinc has the highest solid solubility in aluminium. In AA1050, the zinc content
limit is up to 0.07 %, however, the preferred composition is between 0.013 - 0.05 %.
Zinc addition gives improved electrograining properties and in particular for
electrograining in nitric acid electrolyte. It also compensates for any of the harmful
effects on uniform electrograining of impurities in high contents. Additions above
0.5 % result in coarse pits and non uniform roughening [Ward, 2005; Coleman et al.
2010; Rottwinkel et al. 2011].
Copper is not added deliberately but only exists as an impurity. The

presence of copper hinders AC-electrograining. Others however claim that copper
additions up to 0.1 % exhibit a pit refinement effect and can improve the material
strength in both the as rolled and “baked” condition. Copper is not however a
desirable alloying addition [Komine et al. 2001; Uesugi et al. 2008; Smith et al.
2010].
Manganese is used to increase strength and control the grain structure by

increasing recrystallization temperature and promoting a fibrous structure while hot
working. For the lithographic plate application magnesium is found in solid solution
at additions in the range of 0.008 - 0.3 weight %. Manganese contributes to
improved thermal stability and increased reactivity in the electrochemical roughening
process. Manganese provides good strength and a minimum drop of strength after
stoving compared to the as cold rolled sheet [Hatch, 1984; Coleman et al. 2010;
Other elements have been suggested as minor additions (p.p.m.) to AA1050

in order to enhance strength and the roughening behaviour such as nickel, lead,
indium, tin and gallium. Other elements, such as zirconium, are not added
deliberately [Uesugi et al. 2008; Uesugi, 2009; Rottwinkel et al. 2011].
36
1.3 Lithographic Printing Plate – Production Stages
The offset lithographic printing plate is a complicated product. It is prepared

in three different stages:
• Aluminium substrate production stage.
• Plate production stage.
• Pre- and on-press, printer’s stage.
A developed plate is then mounted on the printing line to start printing.

Figure 7 shows the various forms of the aluminium material that is to become an
offset lithographic printing plate.
1.3.1 Aluminium substrate production stage
The majority of the aluminium used for lithographic plates in Europe is

generated from direct chill casting (DC casting) because this produces ingots with
suitable geometry for subsequent processing. Operations of continuous casting
(CC casting) have been suggested, however, these show unevenness and poor
presensitized plate sensitivity. During DC casting, aluminium of 99.5% purity plus
any intentional additions are melted together and poured into rectangular moulds,
the walls of which are chilled directly with water to solidify the metal. Any kind of flaw
at this production stage could survive through to the final gauge material. For
lithographic plate quality, casting is performed under strict control of grain
refinement, cast speed (which is usually slow) and alloy composition. This control
aims at ensuring that the fir tree formed zone during solidification, will be scalped off
at the next stage of scalping [Hoellrigl, 2002; Hoellrigl and Smith, 2002(a); Sawada
et al. 2007; Ricks and Evans, 2006].
The scalped ingot is then inserted in a pre-heating furnace for the next
process step of homogenization. This process step aims to achieve a homogenized
microstructure, chemical segregation of cast structures, and softening of the
material. It also reduces the internal residual stresses and allows constituents to
enter solid solution (improve workability). During homogenization, iron and silicon
redistribute more uniformly across the dendrite arms. The homogenization
temperature needs to be no less than 500°C so that the precipitation of iron and
silicon is sufficient [Uesugi et al. 2008].
37
The ingot is subsequently hot rolled to reduce its thickness and commence
shaping it into a sheet. It is then cold rolled, so as to reach an even thinner gauge,
and coiled before the next process step, that of inter-annealing. The coil is (usually)
batch annealed to achieve optimum mechanical properties.
Some patents suggest skipping the inter-anneal process for economic

reasons. However, inter-annealing helps control solute levels, grain structure,
stoving response and surface streakiness. High inter-annealing temperatures are
preferable to keep iron in high solute levels rather than allow it precipitate. The inter-
annealing process is thoroughly described in a following section [Uesugi et al. 2008;
Uesugi et al. 2009; Rottwinkel et al. 2006].
After inter-annealing, the coil is further cold rolled to the sheet’s final gauge.
The last process steps are those of leveling and surface cleaning in a degreasing
medium. Surface cleaning enhances the electrograining sensitivity and reduces the
needed charge [Kernig and Brinkman, 2008]. The sheet is finally coiled and
packaged.
1.3.2 Plate production stage
The purpose of this stage production process is to create a uniformly

convoluted surface where water is attracted to the hydrophilic anodic oxide layer
regions and ink is attracted to the hydrophobic photosensitive (organic – polymer)
layer regions.
Surface modification is a continuous process during which the aluminium

substrate is initially uncoiled and then degreased in an alkaline solution, usually
NaOH. The degreased surface is thoroughly rinsed with deionized water before it
undergoes the surface roughening process called AC-electrograining (also referred
to as graining).
AC-electrograining is driven by the application of an alternating current (AC)

across the aluminium surface in an electrolyte solution, commonly HCl, HNO3 or in
both of those sequentially. The aim of AC-electrograining is a uniformly pitted and
convoluted surface which should optimally lack any ungrained areas (plateaux),
exhibit narrow pit size distribution and no too deep pits.
During AC–electrograining the alloy is subjected to alternating anodic and

cathodic polarization, with sequential electrochemical processes of anodic
dissolution of aluminium and oxygen evolution and cathodic hydrogen evolution.
38
Significant aluminium dissolution clearly proceeds during pit growth at potentials
above the pitting potential [Koroleva et al., 2005].
Al → Al +3 + 3e − & 2H + + 2e − → H2
During the anodic charge cycle pits are initiated due to the aggressive
species in the graining solutions, namely Cl- or NO3-, and grow due to aluminium
dissolution. In HCl electrolyte, the hemispherical pits formed are composed of a
large number of fine, cubic-shaped pits. In HNO3 electrolyte, no crystallographic pits
are observed [Laevers et al. 1993].
The local pH at the pit sites increases. Above pH 10, aluminium is oxidized
as aluminate ions which consequently precipitate at the pit site, forming an unstable
hydroxide-etch film known as smut layer. The smut layer leads to a continuous
redistribution of the pitting process, which results in the creation of a
homogeneously pitted surface. After AC-electrograining, the smut layer is removed
in an acid neutralizing solution [Sigli et al (a)].
Then, anodizing follows by application of a direct current (DC) on the grained

surface in an acid electrolyte such as sulphuric, phosphoric or chromic acid.
DC-anodizing is an electrolytic process that grows a thin but strong aluminium oxide
layer on the surface. This layer is inert and improves corrosion and abrasion
resistance as well as promoting adhesion to the later applied organic photosensitive
layer [Sigli et al (a)].
The anodized aluminium substrate undergoes some post anodic treatments

which consist of dipping or spraying in solutions such as hydrophilic polymers and
zirconium salts. The silicate post anodic treatment is claimed to strongly improve the
printing performance of the lithographic printing plate. Hydrophilizing treatment is
carried out mainly with an alkali metal silicate solution or with potassium
hexafluorzirconate. This treatment aims to hydrophilise the anodized aluminium
surface and improve the adhesion of the photosensitive coating on the hydrophobic
image areas of the plate, imparting high printing durability [Gaggiano et al. 2010;
Sawada et al. 2007].
The application of the photosensitive layer is the next process step. This
layer is an organic layer and it is often that more than one layer is applied. At the
end of this production stage the surface modified aluminium substrate is cut to
plates of various sizes and packaged in between protective paper before sending off
to the printers’.
39
An illustration of the different developed layers of this production stage is
shown in Figure 8.
1.3.3 Printer’s stage; pre- and on-press
At the printers’ the lithographic plate goes through two stages:
• Pre-press
• On-press.
At the pre-press, the lithographic printing plate is generally developed to

image and non-image areas or hydrophobic (ink attracting) and hydrophilic (ink
repellent) areas respectively. Depending on the polymer coating system, the plate is
afterwards exposed to cure (harden) the image areas. The pre-press uses
appropriate equipment that depends on the plate exposure and development
method. The most common method currently used is the CtP (computer to plate)
which incorporates the use of digitally developed lithographic printing plates.
After the development is complete, the plate is mounted on the printing

press cylinder ready to start printing. That is the on-press stage.
The three stages of printing plate production are shown in Figure 9.
Through the previously described production stages, the lithographic plate

product must develop certain properties, essential to the on-press performance.
These properties establish the critical product requirements, the control and
evolution of which during the inter-annealing and cold rolling processes, is the
subject of this literature review and the thesis overall.
1.4 Critical Product Requirements (CPRs)
The aluminium substrate must fulfill a series of specifications so that the final
product is of high quality. The aluminium sheet properties, as those evolve through
process, should establish that high quality result.
The material properties can be broadly categorized as follows:
• Physical properties (e.g. density, electrical and thermal conductivity etc)
• Chemical - Electrochemical properties (e.g. corrosion behaviour)
• Mechanical properties (e.g. yield, UTS strength, hardness, plasticity etc)
40
A critical product requirement is a material related property which is
considered essential to the product’s performance.
The aim of this study is to examine the aluminium lithographic substrate

material critical product requirements and the way those are affected by the
production process. Of particular interest is the evolution of the microstructure
through process and the effect those microstructural changes have on the final
properties of the material.
In order to properly understand the significance of the critical product

requirements it is first necessary to identify them and secondly to measure them.
The latter is the most difficult task as not all of the critical product requirements can
be quantified. Nevertheless, some kind of control should at least be performed. Next
follows a description of the major critical product requirements for the aluminium
rolled sheet used as substrate for the production of offset lithographic printing
plates.
1.4.1 Strength related properties
The strength of the AA1050 aluminium substrate can be described by many

different aspects, such as ultimate tensile strength, proof strength, hardness, plastic
behaviour etc. The above are greatly associated with the microstructure evolution
during the fabrication process starting from casting down to the final cold rolling. The
most critical of the strength related product requirements include the following.
1.4.1.1 High thermal stability
Printing plates should lose as little as possible of their strength during baking
of the photosensitive coating, because softened plates cannot be handled without
buckling. The baking step, also known as stoving, is a heat treatment which aims to
stabilize the hydrophobic exposed areas by hardening those so that the wear
resistance of the photosensitive coating is improved and the plate’s lifetime is thus
extended. It has been found that the material’s strength is reduced after baking
because of the inevitable occurrence of recovery and recrystallization on the heavily
cold worked aluminium sheet. This may cause plate distortion. The degree of
softening increases with both time and temperature of baking. The overall change in
strength, the isotropy of strength, the specified geometric stability and the absolute
thickness (gauge) are features that measure thermal stability. This requirement is
41
proportional to the number of barriers to dislocation movement [Smith et al. 2010;
The thermal stability is examined by means of tensile testing. The tensile test
specimens originate from final gauge, as rolled aluminium sheet, in both the
longitudinal and transverse to rolling lines directions. These are subjected to
elevated temperatures (~240 - 280°C) for time inter vals between 2 and 10 minutes.
The strength related properties are measured before and after the baking test. Of
particular interest is the drop of strength between the “as rolled” and the “baked”
state [Smith et al. 2010; Rottwinkel et al. 2011].
The measurement of the material strength reveals whether the aluminium

microstructure has evolved properly. According to von Asten, the measured tensile
strength should be higher than 145 MPa and according to Kernig at least 150 MPa
transversely to or in the rolling direction, after a heating process of 10 minutes at
240 °C. Further means of measuring this property is with the hardness value. This
property is directly associated with the amount of gauge reduction during the final
cold rolling towards the target gauge [von Asten et al. 2002; Kernig et al. 2009].
Iron contents of 0.3 - 0.4 %, with a high iron to silicon ratio, were found to
have a positive effect on thermal stability. It has been claimed that a final cold
reduction of more than 90 % and a following baking for 10 minutes at 250 °C, would
exhibit a higher strength printing plate. Small amounts of magnesium and
manganese enhance strength and thus the resistance to softening after baking while
still allowing suitable graining in hydrochloric acid. The intermediate annealing
process step is a critical process for retaining the iron and manganese in solid
solution. High inter-annealing temperatures and rapid coil cooling after annealing,
even with air quenching, are preferable in order to achieve this [von Asten et al.
2002; Hoellrigl and Smith, 2002(b); Rottwinkel et al. 2004; 2011].
However, recent technological developments in the photosensitive layer

composition have led to a diminishing significance for the high thermal stability
requirement. This is because innovations in polymeric coatings have allowed baking
omission after development. Still, this kind of plate cannot yet achieve the expected
number of printed impressions as the “baked” plates.
1.4.1.2 High reverse bending fatigue strength
If a component or structure is subjected to repeated stress cycles, it may fail

at stresses well below the tensile strength and often below the yield strength. The
42
processes leading to this kind of failure are termed fatigue [Ashby and Jones, 2005].
A printing plate is mounted on-press, bent around the printing cylinder and
performing numerous of printing cycles. The high reverse bending fatigue strength is
described as the endurance of the aluminium substrate, during those printing cycles,
without cracking. The run-life of a lithographic plate on-press is highly dependent on
this requirement.
This bending property is perceived as more important than strength as far as

the on-press performance but it is not as straightforward to measure. The reverse
bending fatigue strength is measured with the bending cycle endurance test. The
thickness of the tested specimen is very important because this feature affects
greatly the deformation behaviour. As rolled samples of 100 mm length and 20 mm
width are taken longitudinally to the rolling direction. The samples are then
subjected to repeating bending cycles on a specialized device, over a radius of
30mm. The number of bends until fracture is determined. Preferably more than 3200
bending cycles in the rolling direction are required from an aluminum substrate to be
suitable for use as a lithographic printing plate [von Asten et al. 2002; Kernig et al.
2009].
This process requirement is highly dependent on the proper mounting of the

plate onto the printing machine. Exact clamping of the plate on the printing cylinder
reassures that no movement or play will occur during the printing cycles. Therefore,
there are no bending or torsional loads which could lead to plate cracking due to
fatigue fracture.
A further practical parameter is that of the printing plate direction with the
rolling direction. A plate printing in the longitudinal direction will crack substantially
less frequently than the one printing in the perpendicular direction. Recent
developments in printing machines require oversized printing plates of a width
greater than 1700 mm. This requires sometimes for plates to be taken transverse to
the rolling direction of the substrate. A value greater than 1250 cycles in a reversed
bending fatigue strength test, from a specimen taken perpendicular to the rolling
direction, is considered as an acceptable result [von Asten et al. 2002].
Elements like magnesium, copper and iron provide great characteristics for
high reverse bending fatigue strength especially when those are in solid solution
[von Asten et al. 2002].
The run life of a printing plate can be as high as one million copies. The
alloys used for such plates have fatigue strength of 10,000 psi at five hundred
43
million reversals, but with additions of elements such as magnesium, iron and silicon
plus the appropriate work hardening process, the fatigue strength can get as high as
13,000 to 15,000 psi with a tensile strength of about 25,000 psi [Pryor et al. 1975].
The substrate also experiences “environmental assisted” fatigue, under

service conditions, due to the high and low pH values of the solutions it encounters.
1.4.2 Lack of surface defects
A further critical product requirement, which is also affecting the substrate

production economics, is the lack of defects and in particular, lack of surface defects
as this is a surface sensitive product. Such defects may originate at all production
stages, either due to process mishaps, external to process factors or due to
handling before, after process or during transferring. Surface defects may produce
large volumes of rejected metal.
A clean and blemish-free surface is a major prerequisite of the rolled

aluminium sheet. The vast majority of surface defects are related to either:
• Casting inclusions: defects occurring during the DC casting such as titanium

casting inclusion from grain refiners, aluminium oxide dross, etc.
• Rolled in inclusions: defects occurring during rolling, heat treatments,

leveling and degreasing processes (also referred to as rolled in defects),
such as rolled in aluminium flakes, rolled in refractory material, etc.
• Poor lubrication control: defects which result in undesirable surface features,

such as tiling effect, severe transverse cracking, etc.
• Handling – staining: defects of mechanical nature and residual oils during the
final process stages and while transferring, such as scratches, oil stains, etc.
Some of the defects may not be visible until after the aluminium electrolytic
surface treatment of AC-electrograining. These defects may appear either as:
• Streakiness: a defect which is related to the texture evolution through the

process and appears as long bands of shadows on the grained surface.
Streaking defects during AC-electrograining are also associated to ingot
hydrogen content [Evans et al. 2004].
• Plateaux or non-grained areas: areas which were somehow passivated

during the degreasing and electrolytic graining of the plate production stage
and have a flat or ‘metallic’ appearance after the AC-electrograining process.
44
The grained surface shows larger pit formation near areas under or
non-attacked [Ward, 2005].
In general, surface cleanliness has proven to enhance the result of

AC-electrograining. Also, removal of subsurface oxide islands reduces the required
charge for a satisfactory graining outcome [Kernig and Brinkman, 2008].
1.4.3 Flatness
Flatness is another requirement from the aluminium substrate. This is

corrected right after the final cold rolling process by using a straightening machine
such as a roller or tension leveler [Sawada et al. 2007].
The term flatness implies the lack of any short of intense waviness on the
surface of the as rolled aluminium and is a prerequisite from the aluminium
substrate production stage. Flatness is both qualitatively and quantitatively
controlled and measured at the end of the aluminium substrate production stage by
scanning along the width of the as rolled sheet. The surface roughness on final
as rolled samples is also measured.
The absolute flatness of the offset lithographic printing plate substrate is of

maximum importance for the online performance of the plate during printing.
1.4.4 Good roughening behaviour
The good roughening behaviour requirement refers to the uniformly pitted

and convoluted surface which is the expected result of AC-electrograining. This
requirement is also known as AC-electrograining response or electrograinability and
it is associated with the corrosion behaviour of the aluminium substrate under acidic
conditions. This is critical for the on-press performance of the lithographic plate
because a properly electrograined surface should retain moisture and give even
more dampening and slower moisture evaporation.
A study on the variations of the anodic and cathodic potentials during

AC-electrograining has presented three distinct stages. At the first stage the anodic
dissolution of the second phase particles mainly takes place. At the second stage a
significant crystallographic attack on the aluminium substrate starts occurring. At the
third stage the potential is continuously increasing because of the hindrance on the
anodic and cathodic reactions due to the formation of the smut layer
[Dimogerontakis and Terryn, 2007].
45
As explained in 1.3.2, AC-electrograining is the controlled corrosion under
specific conditions of time, temperature and current, during which many fine pits are
created on the surface of the aluminium sheet. These pits aim to promote the
surface wetting properties. A desired graining surface is a uniform, convoluted,
structure-less, pitted surface without any surface defect, non-grained or plateaux
areas. The resultant AC-electrograining surface morphology is dependent on:
• The aluminium substrate microstructure,
• the cleaning pre-treatments,
• the mechanical and electrochemical properties of the sub-surface and
• the current conditions employed during the process [Bello Rodriguez et al.
2010].
The graining morphology is influenced by the current density and frequency

applied. By increasing the current density this results in bigger pit size, fewer pits,
more plateaux areas and more smut layer formation. The frequency increase results
in reduced pit size, increased pit population and more uniform graining morphology.
Reducing the frequency increases the formation of the smut layer. In particular, a
thin uniformly formed smut layer is preferable for a better distributed current across
the aluminium surface, also resulting in a uniform graining morphology
[Dimogerontakis et al. 2004; Campestrini et al. 2006].
The electrolytic etching behaviour of aluminium is dependent on its passive

natural formed oxide. The oxide affects the pitting initiation while electrochemical
etching in both HNO3 and HCl based solutions. In HNO3 electrolyte pitting initiation
begins only at an anodic potential of +1.65 V (Reference saturated calomel
electrode: SCE) while in HCl electrolyte pitting initiation begins at a corrosion
potential of -0.65 V (SCE) [Hoellrigl, 2002].
The presence of too many iron-containing particles is detrimental to

AC-electrograining. Iron and silicon alloy additions alter the reactivity of the
lithographic sheet surface. Low additions form too many pits while high additions
form too few pits. Both cases result in undesirable graining. Manganese in solid
solution may enhance the material strength related properties but is doesn’t promote
the graining uniformity. Alloys with zinc and magnesium additions have enhanced
mechanical properties, fatigue resistance and graining response, also reducing the
presence of undesirable effects such as streakiness and plateaux areas [Rottwinkel
et al. 2004; Laevers et al.1996].
46
The speed of a lithographic process line is a critical financial factor which is
largely influenced by the alloy’s AC-electrograining roughening behaviour. Zinc and
magnesium additions reduce the processing time. This is because when those
elements are present in solid solution they then act as pitting initiators and they
allow a more efficient electrical current distribution. Higher current densities enable
higher lithographic line speeds without compromising the final roughening result, by
addition of zinc [Sanchez et al. 2010; Ward, 2005].
Apart from the substrate and the process conditions other parameters have
been also experimented as far as their significance in enhancing the graining
response. Amongst those, Kernig and Brinkman suggested a final cold rolling pass,
during the aluminium substrate production stage, with an optimized for lithographic
applications coated roll. The roll’s coating and the rolling process parameters
achieved a dedicated surface texture which further exhibited significantly faster
graining response in both commonly used electrolytes, HCl and HNO3. This
production stage was referred to as pre-graining of the aluminium sheet.
Campestrini et al. showed that HF additions in the graining electrolyte activate the
aluminium surface and reduce the formation of smut layer [Kernig and Brinkman,
2006; Campestrini et al. 2006].
The assessment of this requirement is usually qualitative rather than

quantitative. It is generally not too straightforward to measure the number, size and
geometry of the pits created during AC-electrograining. The techniques which have
been most commonly used to characterize the result grained surface include
roughness measurements by 2D and 3D line profilometry, atomic force microscopy,
white light interferometry and scanning electron microscopy (SEM). Also, according
to Kernig the as rolled sheet before surface modification should preferably have
more than 350 grains per mm2 so as to accelerate the roughening process. This
specified density leads to a more homogeneous appearance in the roughened or
coated state. A qualitative comparative method suggests that samples of 0.5 m2 are
roughened at a constant temperature and constant flow conditions in an electrolyte
of 7 g/l HCl or 10 g/l HNO3 with alternating current of 50 Hz, in the range of 500 to
1500 C/dm2. The classification of the samples is performed subsequently according
to the roughening progress [Rivett et al. 2010; Kernig et al. 2009; von Asten et al.
2002].
47
1.4.5 Anodizing quality
The anodizing quality is an important requirement although, for example it is

not as sensitive to microstructure change as the roughening behaviour. Hence, it is
generally more easily controlled.
1.5 Inter-annealing
Of the critical product requirements, the ones that may be altered during the
inter-annealing or cold rolling processes are those that are directly related to
microstructural characteristics. The inter-annealing process in particular causes
changes in solute levels, second phase particle number, size, shape, dispersion and
the recrystallized grain size, texture. All of the above affect directly the strength
related properties and the electrochemical roughening behaviour. The rest of the
critical product requirements are less affected.
1.5.1 Pre-annealing state
One of the most important operations of the aluminium substrate production

stage is that of inter-annealing. The change of mechanical properties and the
microstructural evolution during annealing have been and still are a very important
research area driven by scientific curiosity and industrial demand. The modern
research trend concentrates on the formulation of models that describe and
characterize the structural evolution and expand through experimental and
theoretical basis the evolution of the mechanical properties during annealing of
deformed aluminium. In sequence, annealing follows the heavy deformation of hot
and cold rolling. At this point there is a significant reduction of thickness, resulting in
a heavily deformed structure, right before the first coiling [Hansen and Vandermeer,
2005].
This pre-annealed state is characterized as extremely stiff. Experiments

have proved that only a small fraction of the energy used in cold rolling, between
1 - 15 % is stored in the metal. The rest is spent as unutilized heat. During
deformation at low temperatures, the dislocation density increases and hinders the
glide of dislocations. This also affects mechanical properties of the material such as
the hardness and yield strength. It also affects the formability of the aluminium as it
is very difficult to further roll it to thinner gauges. In order to maintain the material in
a condition that it is ductile enough to see more work hardening and by so reach its
48
target gauge and properties, a softening mechanism is needed to relieve the
aluminium of its internal stresses and allow it to return to such a state that it may be
formed further with no severe difficulty [Christian, 2002].
1.5.2 Annealing
Annealing refers to the softening of wrought metal by application of heat,

which is basically the reverse of work hardening. The metal softening is required for
either allowing the continuation of metal working or for achieving final desired
strength and/or ductility required by specific products. According to Cahn, any heat
treatment intended to reduce or eliminate deformation-induced damage is termed
annealing. This behaviour of metallic materials to harden when deformed and soften
when heated is known to man since the beginning of our civilization and today is
exploited by industries of metals and alloys through thermomechanical processing
[Cahn, 1996; Ricks and Evans, 2006; Hansen and Vandermeer, 2005].
The industry demand to understand the effects of deformation and

subsequent annealing is obvious. Despite the 150 years of research in this area, no
comprehensive model describing all of the including processes has been evolved, at
least none that can guarantee reliable application for technological purposes, on the
basis of fundamental insight. The industrial annealing process is performed in
specialized annealing furnaces, either in a continuous fashion (passage of strip
through a tunnel furnace) or more often in batches (static heating of plate or coils in
furnaces) [Mittemeijer, 2010; Ricks and Evans, 2006].
The performed heat treatment to remove some or all the cold work stored
energy from prior deformation (so that desired properties may be achieved and
further deformation performed) is termed inter-annealing and is performed at an
intermediate gauge [Cama et al].
A fully annealed or fully recrystallized or fully soft or O temper material

depends on:
• Strain,
• strain rate,
• temperature of deformation,
• heating rate,
• soak time and
49
• annealing temperature.
By a full anneal practice, solid solution strengthening can be achieved

especially in Mg containing alloys [Cama et al.].
An annealed material’s strength may be increased by solid solution

hardening. For this to be achieved, the solute must:
i. have an appreciable solid solubility at the annealing temperature,
ii. remain in solid solution after a slow cool and
iii. not be removed by reacting with other elements to form insoluble phases
[Polmear, 2005].
For aluminium alloys specifically, the annealing process may be required

before or between deformation operations for relieving the work strain or reducing
the strength of alloys for age hardened tempers. The aim is usually to improve
workability for subsequent manufacturing operations. The annealing treatment,
temperature and time, is dependent on the alloy and the structure developed prior to
thermal or mechanical operations. Aluminium alloys reduce or eliminate the
strengthening from cold working by heat treating at temperatures between ~250 ˚C
and 450 ˚C for times ranging from a few seconds to several hours. However,
annealing temperatures above 415 ˚C are not desired to avoid oxidation and grain
growth. The exact time and temperature of annealing depend on the amount of
deformation and the solute concentration. A slow cooling rate after the annealing
process minimizes distortion [Starke, 2001; Dahle, 2001].
Some aluminium products are often exposed to further levels of heating as

the final product is fabricated, such as the photo-resist curing of lithographic
aluminium plates. This directly affects one of the critical requirements of this
product, the “bake softening” performance [Ricks and Evans 2006].
Annealing is the softening mechanism which results to the loss via recovery
and recrystallization of the dislocations introduced by work hardening. Both these
processes occur in order to lower the additional energy stored in the microstructure
as a result of the deformation due to the cold rolling reduction through the tandem
[Humphreys and Hatherly, 2004; Ricks and Evans, 2006].
Figure 10 illustrates that at low temperatures the loss of strength is relatively

low but at higher temperatures the strength reduces remarkably. At this point the
reduction of strength is dependent on the degree of prior deformation. At these low
temperatures, the microstructure still resembles the deformed microstructure
50
(recovery area), while at high temperatures new grains have been formed and
grown to create a new grain structure (recrystallization area). Further time at high
temperatures after recrystallization is complete results in grain size increase (also
known as grain growth) by gradual and uniform coarsening of the microstructure
(normal grain growth). This proceeds by the elimination of neighboring small
recrystallized grains due to grain boundaries mobility [Ricks and Evans, 2006;
Hatch, 1984].
1.5.3 Recovery, recrystallization and grain growth
Recovery, recrystallization and grain growth refer to the thermally activated

microstructural and sub-microstructural processes which directly affect the material’s
mechanical properties such as hardness, strength and ductility but other properties
as well like the electrical resistivity and the amount of stored energy. The complex
mechanisms that occur during those processes are core elements of the
thermomechanical process and altogether describe the softening mechanism that is
annealing. However, they are not totally dependent on one another. Recovery and
recrystallization are competitive processes as they are driven from the same force,
that of stored energy and dislocation annihilation. They depend on the nature of the
deformed state and involve the formation, removal and movement of sub- and/or
grain boundaries. On the other hand, grain growth is driven from grain boundary
energy and mobility [Hansen and Vandermeer, 2005; Humphreys and Hatherly,
2004].
The change in most of the material physical properties is nearly complete by

the end of recrystallization. This change in properties and structure may be related
directly to the time and temperature of annealing and expressed in rate equations,
however, there is no universal rate equation describing all the changes during
annealing [Christian, 2002; Hansen and Vandermeer, 2005].
1.5.4 Recovery
All things in nature want to be at a stable state. The aluminium sheet is in a

meta-stable state after cold work reduction prior to inter-annealing. Given an
external aiding agent, this is bound to change to another, more stable state. The
ability of atoms to re-arrange themselves within the crystal lattice by diffusion of
dislocations is the reason why recovery occurs, yet this requires a suitably high
temperature (~0.3 - 0.4 Tm: melting temperature). Recovery may occur in any
51
crystalline material given that it has been introduced with a non-equilibrium high
concentration of line or point defects. The hot and cold rolled aluminium sheet for
litho application is such a crystalline material [Ricks and Evans, 2006; Humphreys,
2001].
Recovery defines the changes in a deformed material which occur prior to

recrystallization. It also partially restores the material properties to their values prior
to deformation. The material properties which characterize the recovery process
greatly are those of hardness, flow stress, stored energy and electrical resistivity.
During plastic deformation processes, such as cold rolling, the defects introduced
are dislocations and point defects, as vacancies [Humphreys and Hatherly, 2004;
Hansen and Vandermeer, 2005; Mittemeijer, 2010].
Recovery is the earliest onset of crystal defects re-arrangement in the cold

worked microstructure at an elevated temperature. Restoration of the original
structure and properties may also occur through annihilation of point defects and
dislocations and by spatial re-arrangement of dislocations. Consequently the
material will soften while “recovering” some of its prior to cold work mechanical
properties. Direct comparison however is not plausible as the change in size and
shape has had its effect in the material properties as well. During recovery there is a
decrease in dislocation density which causes decrease in strength, increase in
electrical conductivity and decrease in internal stresses and stored energy.
Recovery can as well occur during deformation at high temperatures, also known as
dynamic recovery [Cama et al; Christian, 2002].
Recovery is difficult to quantify because neither the subtle microstructural

changes nor the crystallographic texture during the process can be observed by
common optical microscopy techniques. Usually a change in some physical or
mechanical property is revealing of the recovery process, such as the yield strength
or hardness. Other properties that could be employed are the dislocation density,
the subgrain size and misorientation or measurement of the stored energy using
calorimetry. The last, however, is a method in dispute due to the interference of the
measured energy with recrystallization and precipitation of alloying elements
[Humphreys, 2001; Humphreys and Hatherly, 2004; Verlinden et al. 2007; Cordovilla
and Louis 1984].
Researchers have used the hardness value to characterize the recovery

progress during annealing and have shown that for commercial purity aluminium a
large effect of the rolling strain is observed on the recovery at temperatures below
52
approximately 200 °C. In fact, the higher the strai n was the higher was the rate of
recovery [Hansen et al. 2007].
Recovery is a homogeneous process in both terms of space and time as it

progresses gradually with time and there is no identifiable start or finish of the
process. No further recovery can take place once recrystallization has initiated and
the deformed substructure has been consumed [Humphreys and Hatherly, 2004].
1.5.4.1 Recovery stages
Recovery is not a single microstructural process but a series of

micro-mechanisms that altogether comprise the initial thermomechanical process of
annealing. Three different stages take place [Humphreys, 2001]:
i. Point defect annihilation by diffusion and dislocations migration and

annihilation,
ii. Dislocations re-arrangement and subgrain formation,
iii. Subgrain growth.
Whether any of the above mechanisms occurs while inter-annealing is

dependent on the material purity, strain, deformation temperature and annealing
temperature. Often however, these occur simultaneously so that there is no clear
distinction [Humphreys, 2001].
The reduction of strain energy is the driving force for the dislocation
migration leading to different dislocation configuration and/or partial annihilation. The
dislocation mobility results into the reduction of the total dislocation energy, which is
the internal energy of the material due to strain while deforming. The elastic stress
fields of the dislocations interact and the consequent forces depend on the relative
dislocations positions and Burger’s vector. Dislocations of equivalent Burger’s
vector, but of opposite sign, annihilate or re-arrange themselves into lower energy
configurations either by glide, climb or cross slip in the form of regular arrays or low
angle boundaries. The latter mechanism is also known as polygonization.
Polygonization is driven from the reduction in the total energy of the deformed metal
and it involves dislocations of only one Burger’s vector [Mittemeijer, 2010;
Humphreys, 2001; Cama et al.; Verlinden et al. 2007].
Of the most important material parameters regarding recovery is the stacking

fault energy. Aluminium in general, has a high stacking fault energy and this limits
dislocation dissociation during deformation and leads to relatively easy dislocation
53
climb and hence recovery during annealing. Climb is usually the rate controlling
process during recovery. The highly deformed, through cold rolling, aluminium
develops a complex dislocation structure where, the dislocations are arranged in
three dimensional cells. During recovery and through dislocation energy reduction,
the cells become sub-grains and the cell walls subgrain boundaries. The formed
sub-grains react as a normal grain would by moving, rotating and coarsening.
Smaller sub-grains are consumed by larger ones and this increases the overall
sub-grain size. The sub-grains coarsen due to the remaining large amount of stored
energy and their growth is controlled by the migration of the low angle boundaries,
rotation and coalescence [Humphreys, 2001; Cama et al.; Humphreys and Hatherly,
2004].
1.5.4.2 Factors influencing recovery
Recovery is influenced by temperature and microstructural features that

inhibit dislocation motion, such as:
• Solute content in the matrix
• Second phase particles
• Strain prior to heating
• Stacking fault energy
The extent of recovery increases with temperature. Atoms in solid solution

can cause recovery deceleration interacting with dislocations within cells and
sub-grain boundaries, an effect also known as solute drag. This can occur even at
very low solute concentrations. Magnesium in solid solution also retards recovery
very effectively by pinning dislocations [Cama et al.].
Recovery is also retarded by coarse constituents. Second phase particles,

particularly in the form of very fine distributions, either pin dislocations if particle
spacing is much smaller than dislocations spacing or by sub-grain boundary pinning.
The pinning pressure of particles on unit area of sub-grain boundaries is also known
as the Zener pinning pressure [Cama et al.; Verlinden et al. 2007].
Higher strain equals higher stored energy which during rolling can result in
recrystallization at the surface. This is also called as dynamic recrystallization
(explained later on) and it does not promote recovery. High stacking fault energy
allows dislocation climb and accelerates the recovery rate [Cama et al.].
54
Some softening process could as well occur during working - rolling and this
is termed as dynamic recovery. This is observed in aluminium alloys with low levels
of alloying additions such as AA1050. A recovered microstructure is generally
inhomogeneous due to the different rates of recovery in the different paths of the
microstructure [Cama et al.].
1.5.4.3 Recovery kinetics
The rate of recovery cannot be easily demonstrated because the structural

changes occurring are not usually detected by ordinary metallographic techniques.
Experimentally, recovery is often measured according to a change in a single
property, such as the yield strength [Hatch, 1984; Humphreys, 2001].
Recovery kinetics can be summarized by the following equation:
t
∆σ = S ⋅ ln(1 + ) [Equation: 1]
t0
where, ∆σ is the drop in yield strength in time t and
S is parameter related to the activation volume
It is frequently difficult to extract a fundamental insight into recovery from

such experimental data as those of Figure 11, because the relationship of the
measured parameter to the microstructure is usually complex and because recovery
includes several coinciding or sequential atomistic mechanisms [Humphreys, 2001].
1.5.5 Recrystallization
By definition, recrystallization is the heterogeneous phase transformation,

comprising nucleation and growth of strain free grains in certain areas of the
material which grow by high angle grain boundary movement to consume the
deformed or recovered microstructure. The new grains grow in expense of the old
ones into a new, recrystallized, grain structure with low dislocation density. The new,
strain-free, formed grain population emerges from the deformed volumes until those
are consumed and the new grains impinge all upon one another. Recrystallization
occurs at high temperatures, more than 0.7 Tm (melting temperature) even without
much recovery [Mittemeijer, 2010; Cama et al.; Verlinden et al. 2007; Humphreys
and Hatherly, 2004; Hansen and Vandermeer, 2005].
55
The terms which refer to recrystallization are primary recrystallization or
discontinuous recrystallization and they are different to secondary recrystallization
(abnormal grain growth) or continuous recrystallization respectively.
Recrystallization can also occur during deformation at elevated temperatures. This
is known as dynamic recrystallization. In very pure metals, such as the AA1050,
dynamic recrystallization could as well occur during cold deformation.
Recrystallization is a microstructural transformation which can be

quantitatively measured with metallographic techniques according to
ASTM E112-10. The recrystallization process is also described by the fraction of
microstructure recrystallized. Time and temperature are significant measures of the
recrystallization process and describe the material behaviour during annealing. For
an isothermal annealing, the time (t0.5) at which the structure is 50% recrystallized is
used as a measure of the rate of recrystallization. For an isochronal annealing,
carried out for a constant time, the temperature at which recrystallization is 50 %
complete is usually defined as the recrystallization temperature (TREX)
[ASTM E112-10; Humphreys and Hatherly, 2004].
1.5.5.1 Recrystallization stages
Recrystallization includes two levels:
i. Nucleation of new grains, within preferred sites of the deformed area and
ii. growth of the new grains.
A recrystallization nucleus is the initiation point of a new grain and is defined

as the crystallite of low internal energy growing into deformed material from which it
is separated by a high angle grain boundary [Cama et al.].
Such nuclei can initiate at regions of large orientation gradients such as:
• Grain boundaries
• Second phase particles (larger than 0.8 um)
• Deformation bands
• Large sub-grains
• Strain-free regions of grains.
At the above regions the microstructure is very heterogeneous and there are
large lattice misorientations and dislocation densities. The high angle grain
56
boundaries are more mobile than the sub-grain boundaries and can therefore sweep
through the structure. The strain induced grain boundary migration is the dominant
recrystallization mechanism for low reduction i.e. <20 %. The nucleation rate is not
always constant during recrystallization but can be described by the following
equation:
dN
Nucleation, N = [Equation: 2]
dt
where, N is the number of nuclei per unit volume.
The velocity of nucleus growth is dependent on the driving force, which is the
strain energy of dislocations, the boundary mobility, which depends upon
misorientation, and the location dependence due to pre-existing heterogeneities
[Cama et al.].
Strain-induced grain boundary migration is initiated at the high angle grain

boundaries in the still deformed microstructure. There, the dislocation density is
significantly different between the two sides of the grain boundary, due to the
previous cold deformation. This crystal orientation dependence of a grain is the
consequence of cold rolling. The grain boundary migration is also influenced by
diffusion, according to temperature, and by impurity or solute atoms. The latter
influences recovery as well because the atoms in solute segregate to moving grain
boundaries to cause a retardation effect known as impurity or solute drag. Finally,
the grain boundary migration is influenced by the atomic (elastic) misfit, which is the
lattice disorder at the boundary. The grain growth velocity depends on the driving
force of recrystallization, thus the reduction in stored energy and the boundary
mobility (misorientation) [Mittemeijer, 2010; Cama et al.].
The velocity of a high angle grain boundary is representative of the new

grain growth rate, also given by the following equation:
Growth, v = G = M ⋅ P [Equation: 3]
where, v is the high angle grain boundary velocity,
G is the growth rate,
M is the boundary mobility and
P is the net pressure on the boundary.
The various aluminium alloys recrystallize after different time-temperatures

and this depends on the alloy composition and prior strain. With heat, the
57
dislocations re-arrange themselves to form a recovered microstructure and new
recrystallized grains form within the recovered structure. These grains grow through
the migration of high angle grain boundaries to form a new grain structure. The
driving force of recrystallization is:
• the stored energy from deformation, energy associated with
• dislocation density and total grain boundary energy.
Both recovery and recrystallization share the same driving forces which
make them competing processes. Recrystallization may overlap recovery, beginning
before the sub-grain growth stage of recovery.
Earlier research on the growth of recrystallized grains during the early stages
of recrystallization of commercial purity aluminium, deformed to high levels of strain,
showed a rapid growth rate inside the deformation zones around large particles
[Furu and Nes, 1993].
1.5.5.2 Laws of recrystallization
Mehl (1948) and Burke and Turnbull (1952), cited in Humphreys and
Hatherly (2004), summarized the so-called laws of recrystallization which describe
qualitatively the effects of initial grain size and process parameters on the time for
recrystallization and on the grain size after recrystallization [Humphreys and
Hatherly, 2004]. According to those:
i. A minimum deformation is needed to initiate recrystallization.
ii. The temperature at which the recrystallization occurs decreases as the time
of anneal increases.
iii. The temperature at which recrystallization occurs decreases as strain

increases.
iv. The recrystallized grain size depends primarily on the amount of

deformation, being smaller for large amounts of deformation.
v. For a given amount of deformation, the recrystallization temperature will be

increased by:
o A larger starting grain size.
o A higher deformation temperature.
58
1.5.5.3 Factors influencing recrystallization
Recrystallization is affected by both process and microstructure factors. The

following Table 7 lists those factors [Cama et al.]:
Table 7: List of process and microstructural factors affecting recrystallization
Process Microstructure
Temperature Initial grain size
Heating rate Size distribution and coherency of second phase particles
Rolling strain Solute content
Strain rate Texture before and after deformation
Recrystallization is a thermally activated process so the rate of

recrystallization is affected by the annealing temperature and the heating rate.
During rapid heating there is less recovery occurring, thus allowing more driving
force for recrystallization and results to a rapid recrystallization rate. During a slow
heating rate recrystallization may be hindered by precipitation that occurs prior to
recrystallization, as explained later on. Also, a slow heating rate during annealing
will result into a much larger grain size compared to a rapid rate of heating.
Commercially pure and low alloyed aluminium alloys, such as AA1050, create a
nearly equiaxial recrystallized grain shape [Hatch, 1984].
Furthermore, the deformed structure affects recrystallization. This is

characterized by the mode of deformation, the strain path changes and the original
amount of strain. Those are measures of the stored energy, the heterogeneities of
the microstructure and the number of effective nuclei. Increased deformation (high
rolling strain) prior to recrystallization increases the rate of recrystallization and
results into a more refined grain size in contrary to small amounts of cold work which
result into larger grain sizes. An increased strain rate, while hot rolling deformation,
also increases the recrystallization rate.
A finer initial grain size increases the rate of recrystallization and results into
a finer grain size. The grain size of the recrystallized state can be related to the yield
stress by the Hall - Petch equation [Hansen and Vandermeer, 2005]:
59
σ γ − σ 0 = kD −0.5 [Equation: 4]
where, σγ is the yield stress,
σ0 is the yield stress of a non-deformed single crystal or of a very coarse

non-textured polycrystal,
k is a constant and
D is the grain size.
The composition of the alloy influences the recrystallization process greatly.

Almost any addition of impurity or alloying element in solid solution can increase the
recrystallization temperature substantially. The recrystallization of a given alloy is
dependent on whether the second phase is present prior to deformation or
precipitates during annealing. Dispersed phases such as coarse constituent
particles, precipitates and dispersoids may either accelerate or retard the
recrystallization process according to their size, inter-particle spacing and stability at
the annealing temperature [Nes, 2001; Hatch, 1984].
The presence of hard, non-deformable second phase particles during

deformation may in particular increase the internal stored energy by:
• Creating an extra particle - matrix interface,
• trapping dislocations and/or
• increasing coherency strain.
Prior to deformation, these second phase particles will affect recrystallization

depending on the volume fraction, size and spatial distribution. Large particles
(larger than 0.8 um) act as nucleation sites. This is called particle stimulated
nucleation and is referred to as PSN. Particles also affect significantly grain
boundaries by pinning those. The rate of recrystallization is dependent on both size
and spacing of the particles and usually retarded by the presence of fine or closely
spaced particles. Furthermore, the formation of deformation zones occurs at
particles larger than ~2 um and these zones can act as nucleation sites due to high
dislocation density and fine sub-grains. Moreover, fine dispersed particles affect
recrystallization through their interaction with the moving high angle grain
boundaries and, in particular, by pinning those through a process called Zener
Pinning or the Zener drag effect. Zener drag affects both the nucleation of new
grains and their following growth, so larger particles can be effective as
60
recrystallization nucleation sites while smaller, finer, particles act as grain
boundaries motion inhibitors [Nes, 2001].
Solute additions can also retard recrystallization as solute atoms interact with
grain boundaries and inhibit their motion. This process is called solute drag. The
growth of the new grains is seriously affected by the size and distribution of fine
dispersoids and less by the elements in solid solution [Cama et al.].
The overall recrystallization rate is also dependent on both the starting and
the deformed texture. The initial grain orientation and the orientation path during
deformation affect the microstructure and stored energy of a deformed grain, which
is the driving force of recrystallization. Additionally, different texture components
lead to different rates and inhomogeneous recrystallization [Cama et al.].
1.5.5.4 Recrystallization kinetics
The kinetics of recrystallization can be shown with the curve in Figure 12.
The relevant stages discerned are [Ricks and Evans, 2006]:
• Incubation period - when recovery is taking place,
• nucleation of new grains,
• growth of new recrystallized grains and
• grain impingement.
The plot of Figure 12 is representative of the formal kinetics of primary

recrystallization which can be described by the JMAK (Johnson - Mehl - Avrami -
Kolmogorov) equation:
Xv = 1 − exp[ −(kt ) n ] [Equation: 5]
where, Xv is the fraction recrystallized,
t is the annealing time,
n is a numerical constant (JMAK exponent) and
k is a temperature dependent, reaction rate constant, measure of growth

rate, nucleation rate and shape of recrystallized grains dependent on the
number of nuclei per volume and on grain size if nucleation occurs at grain
boundaries [Anil Virkar, 2011; Cama et al.].
61
The numerical constant “n” is a significant factor that depends on the
dimensional shape of the second phase particles, as shown in Table 8.
Table 8: JMAK exponent values relevant to second phase particles shape
3D Spherical n=3
2D Disk shaped n= 2
1D Rod shaped n=1
If nucleation occurs together with growth, then for a 3D spherical particle, n

can be 4 or 5 under various conditions [Humphreys and Hatherly, 2004].
 1 
The data representation of ln[ln ] against ln(t ) is known as the JMAK
 1− Xv 
plot and it is used to compare experimental results with the JMAK kinetics model.
The JMAK plot follows the following equation:
1
ln[ln ] = n ⋅ ln(t ) + n ⋅ ln(k ) [Equation: 6]
1 − Xv
This should lead to a straight line of slope equal to the JMAK exponent “n”
and the intercept is “nln(k)”, thus extracting k.
The essential feature of the JMAK approach is that the nucleation sites are
assumed to be randomly distributed. The JMAK model describes both the nucleation
and growth processes of the new-formed grains. It is in fact very unusual to come
across experimental data which, on detailed analysis, show good agreement with
the JMAK kinetics model. This deviation of the recrystallization kinetics from the
JMAK plots is due to the inhomogeneity of the microstructure (rather than the
recovery process).This results into non-randomly distributed nucleation sites and a
grain growth rate which is decreasing with time [Humphreys and Hatherly, 2004].
An attempt to improve the JMAK approach was performed in 1989 by

Vandermeer and Rath with the Microstructural Path Methodology (MPM). This
model was extended to include the effects of recovery during the recrystallization
anneal and allowed a more detailed extraction of nucleation and growth rates
information. Nonetheless, both models showed inconsistencies due to two factors:
the inhomogeneous recrystallization and the concurrent recovery [Vandermeer,
1992].
62
Vandermeer and Jensen studied analytically the recrystallization behaviour
of AA1050 and determined that the recrystallization process is growth-controlled by
the boundary migration rate. Moreover, the activation energy for grain boundary
migration was calculated 172-183 kJ/mole, suggesting the operation of a grain
boundary mechanism limited by solute levels. The recrystallization microstructural
path was found to be isokinetic. Two recrystallization stages were observed, an
early transient-like stage characterized by decreasing growth rates and a later stage
which approached the Avrami kinetics during which the average growth rates were
approximately constant. The first stage observed may be attributed to steep,
deformation-induced stored energy gradients surrounding precipitate particles,
where a large majority of grains are nucleated, while the second occurs outside the
deformation zone of influence of the precipitate [Vandermeer and Jensen, 2001].
Particle stimulated nucleation is regarded by many researchers as the chief

mechanism for nucleation of new grains in the recrystallization process of AA1050,
especially after cold deformation. A comparison of a hot versus a cold deformed
AA1050 showed that the recrystallization temperature for the hot deformed was
120 °C higher. The hot deformed also had fewer recr ystallization nuclei which
resulted into a higher (3 - 4 times) fully recrystallized grain size, compared to the
cold deformed [Vandermeer and Jensen, 2003].
The development of models which could predict the recrystallization

behaviour and final microstructure was not always successful due to precipitation of
solute iron in AA1050 on dislocations and grain boundaries. Sæter et al., cited in
Hagström et al. (2000), have analyzed commercially pure aluminium and found that
the rate controlling mechanism was solute pinning and not climb at temperatures
like 250 °C. The results are explained by the fact that the alloy tested contained
much more iron in solution [Hagström et al. 2000].
1.5.5.5 Impact of recrystallization on material properties
Recrystallization has a significant effect on material properties such as

tensile strength, hardness and electrical conductivity, as shown in Figures 13 and
14. All of the above are critical to the evolution of properties for the aluminium
substrate used in the offset lithographic plate production. The mechanical properties
and behaviour of aluminium depend on the dislocation content and structure, the
grain size and orientation (texture). The grain size and texture can be highly
determined by recrystallization, so control of this process is vital for any subsequent
63
cold forming. Figures 13 and 14 illustrate the effects of recrystallization on tensile
properties and hardness according to literature. The electrical conductivity rises
back to pre cold work levels because the excess vacancies and interstitials anneal
out during recrystallization [Humphreys and Hatherly, 2004; Cama et al.].
An optimum recrystallization process for the aluminium substrate used in the

offset lithographic plate production would result with non-equiaxed recrystallized
grains of fine grain size. High strain, fine initial grain size and low recrystallization
temperatures are needed for a fine grain size. Presence of second phase particles
and anisotropic grain growth are required for non-equiaxed grains.
1.5.6 Grain growth - coarsening
Through heating continuation of recrystallized polycrystalline

microstructures, results in their spontaneous coarsening. After the nucleation and
growth of the new recrystallized grain structure, the primary recrystallization process
is completed, yet another process follows which is termed as grain growth and is
described just like that, coarsening of the new recrystallized grains [Miodownik,
2001].
The newly-formed grain boundaries are regions of high atomic disorder and
therefore sources of internal energy, yet thermodynamically unstable. After
recrystallization the recrystallized larger grains given sufficient thermal activation
and atomic mobility, grow more in expense of the smaller grains which are
eliminated. The grain growth process occurs due to migration of the grain
boundaries which are regions of high atomic disorder, thus sources of internal
energy [Humphreys and Hatherly, 2004; Hansen and Vandermeer, 2005].
The reduction of grain boundary energy and the boundary mobility comprise
the driving force of grain growth, during which the grain boundaries assume a lower
energy configuration. The driving force of grain growth is two times lower than that
of recovery and recrystallization which means that grain growth is a much slower
process and occurs usually at higher annealing temperatures. Conclusively, the
velocity of the migrating grain boundaries is smaller compared to that during
recrystallization [Verlinden et al. 2007; Mittemeijer, 2010].
Theoretically, grain growth should continue until all of the material becomes
a single crystal or at least until the grains reach up to the sheets dimensions. If the
mean grain size increases with time, but the grain structure remains self-similar, the
grain growth process is called normal grain growth. Another grain growth process
64
category is that of abnormal grain growth during which a few grains grow very large
at the expense of all the rest. This discontinuous growth of certain grains shares
much kinetics and microstructural similarities with primary recrystallization and it is
often termed as secondary recrystallization. Such a case would have detrimental
effects on litho plate substrates. Grain growth is technologically important because
certain properties and mechanical behaviour is dependent on grain size [Christian
2002; Miodownik, 2001; Martin, 2001; Cama et al.].
1.5.6.1 Factors influencing grain growth - coarsening
In general there are three factors influencing grain growth:
i. microstructural features,
ii. process parameters and
iii. specimen size.
Microstructural features such as grain size distribution after recrystallization,

solute atoms, second phase particles and the crystallographic texture, can influence
grain growth in many ways. There is a critical grain size for grain growth to occur.
The opposing forces of reduction in dislocation stored energy and increase in grain
boundary area reveal that a grain with diameter less than ~2 um will not grow.
Solute atoms have a slowing factor as they hinder grain boundary mobility, also
known as solute drag, as they segregate to grain boundaries and they reduce the
grain boundary energy. Even small amounts of impurities may reduce the
boundaries mobility by several orders of magnitude. Second phase particles hinder
grain boundary motion thus inhibiting grain growth as well. There is in fact a critical
average particle size and volume fraction combination at which grain growth ceases
to occur due to this particle limitation on low and high angle grain boundary
movement, also called the Zener drag effect. Many low angle grain boundaries are
found within a strongly textured material, which reduces the driving force for grain
growth [Cama et al.].
Temperature is a process parameter that is necessary for grain growth.

Indeed, significant grain growth is only encountered at very high temperatures. The
specimen size dictates the extent of grain growth as grains can grow up to the
specimen surface [Humphreys and Hatherly, 2004].
A further significant factor of grain growth rate is the distribution of the type of
grain boundaries in the material and the texture. The low energy (low angle)
65
boundaries offer a smaller driving force and thus a smaller boundary velocity than a
high energy (high angle) grain boundary. Recrystallization and subsequent grain
growth are engineered in order to achieve optimum microstructures, yet even until
today most of this work is performed practically on an empirical basis. The gap of
knowledge concerns the atomic structure of, in particular moving, high angle grain
boundaries [Mittemeijer, 2010].
1.5.6.2 Grain growth – coarsening kinetics
Grain growth requires migration of high angle boundaries so the kinetics is

dependent on temperature and boundary mobility. .According to Burke (1949) and
Turnbull (1952), cited in Humphreys and Hatherly (2004), the driving pressure on a
boundary arises only from the curvature of the boundary. Surface tension induces
grain boundaries to move towards their center of curvature and follow parabolic
kinetics. Many theoretical models have analyzed grain growth behaviour in 2D or 3D
simulations. It should be noted however that ideal polycrystalline materials with
isotropic boundary energies and mobilities do not exist [Humphreys and Hatherly,
2004; Miodownik, 2001].
The energy per unit volume that drives grain growth is:
3 γb
Energy per unit volume = [Equation: 7]
2R
where, R is the grain radius and
γb is the boundary energy per unit area.
Grain size growth can be related to the starting recrystallized grain size by:
R n − R n0 = k ⋅ t [Equation: 8]
where, n is a numerical constant, grain growth exponent (usually > 2),
R0 is the initial radius,
k is a constant dependent on temperature and material and
n is a grain growth exponent
The grain growth exponent value, n, has been the centre of much argument,
with the most experiments showing typical values between 2.5 and 4 due to impurity
effects [Miodownik, 2001].
66
1.5.7 Annealing summary
The summary of the annealing process is shown in Table 9, which defines

recovery, recrystallization and grain growth - coarsening based on the combination
of driving force and occurring mechanism [Verlinden et al. 2007].
Table 9: Annealing summary, driving forces and kinetics mechanisms
Driving force (energies)
Mechanism (kinetics) Point Subgrain Grain

Dislocations
defects walls boundaries
Low
Point defect diffusion
temperature
Dislocation Climb Recovery
Sub-boundary migration High

and coalescence temperature
Grain
Grain boundary migration Recrystallization
growth
Recovery and recrystallization are in certain circumstances competing

processes. It is possible to suppress recrystallization by extended recovery which
results in a relatively fine and uniform grain size through homogenous subgrain
growth [Verlinden et al. 2007].
1.5.8 Annealing textures
The annealing process incorporates the control of microstructure and texture

evolution which is of major economic importance. During annealing of deformed
materials the crystallographic texture, i.e. the preferred crystallographic orientations,
may or may not change during the processes of recovery, recrystallization and grain
growth. The either consecutive or simultaneous order of these processes makes
prediction of the annealing textures even harder. However, understanding the
texture evolution and its influence on the final product properties could lead to
financial and energy savings [Jensen, 2001; Mohamed et al. 2004].
67
During recovery, the texture is predominately maintained as none of the
changes in the microstructure alters the orientation of the deformed grains
substantially. The recovered microstructure retains the normal textures associated
with cold rolling (copper, brass, S). If subgrain coarsening occurs during recovery,
some measurable change in texture may be observed [Ricks and Evans, 2006].
During recrystallization, very large changes in texture take place as the

deformed structure is completely replaced by an entirely new, recrystallized
structure. Recrystallization can develop preferred orientations, mainly as a result of
oriented nucleation from:
• Transition bands (copper and brass)
• Shear bands
• Strain induced grain boundary migration
• “Random” textures from PSN sites.
In particular, PSN will contribute to a rather random texture but under certain
conditions, in aluminium sheets, it can also contribute to the P-component
({011} ) 122 [Ricks and Evans, 2006].
These will be competing reactions and the final annealed texture will be a
mixture of these textures depending also on factors such as:
• The material’s composition, initial grain size and presence of precipitates
• Process, including the deformation level and temperature
• Annealing process conditions, such as the heating rate and temperature.

(These however are considered only secondary compared to the material
and prior process ones) [Ricks and Evans, 2006].
The annealing textures of AA1050 depend on:
• the heat treatment prior to cold rolling,
• the Fe/Si ratio and
• the annealing temperature.
Even small amounts of iron may change the annealing texture significantly.
Very low iron concentrations favor the cube texture, while greater amounts of iron
lead to precipitation and slower growth of the dominant cube grains [Humphreys and
Hatherly, 2004].
68
During grain growth, very great change may occur after abnormal grain
growth, whereas little to none may occur during normal grain growth. The important
parameters affecting the change in texture during the grain growth process are the
presence of solutes and second phase particles, the recrystallization texture and the
annealing temperature [Christian, 2002; Jensen, 2001; Ricks and Evans, 2006].
1.5.8.1 Recrystallized texture evolution theories
Two compelling theories may be used to interpret the resulting recrystallized

textures:
i. Oriented nucleation, according to which there is nucleation of new grains

with preferred, particular orientations and
ii. Oriented growth, according to which nuclei with specific preferred orientation
interactions to the surrounding deformed matrix grow faster than other nuclei
and thus contribute more strongly to the recrystallization texture.
The two approaches have been used to extract models to simulate the
development of annealing textures during recrystallization. The orientations of the
nuclei are restricted to those present in the deformed state, yet both the oriented
nucleation and the oriented growth are considered responsible for the annealing
texture development. Although it has been a matter of controversy, it is generally
accepted that both mechanisms can occur and their significance depends upon the
specifics of the material deformation and recrystallization parameters. The overall
trend goes towards accepting both theories. The modelling challenges that are still
pursued are to incorporate both microstructural and orientation information towards
a correct nucleation prediction [Jensen, 2001; Christian, 2002; Engler et al. 1996].
1.5.8.2 Annealing textures of AA1050
The grain orientation influences pit growth direction during

AC-electrograining. The AA1050 rolled sheet prior to annealing is a heavily rolled
f.c.c. metal with a high stacking fault energy. Recrystallization in such materials
typically leads to cube texture development with a {100} plane parallel to the rolling
plane and a ‹100› direction along the rolling direction. This cube texture
development is significantly dependent on the addition of alloying elements and is
even more highlighted upon further annealing, during grain growth [Jensen, 2001].
69
There is little correlation between the rate of recrystallization of hot rolled
AA1050 and the deformation texture component. The recrystallized state is
dominated by the cube texture while the deformed regions constitute of Brass and S
grains. The S component shows high rates of recrystallization during early
annealing. The progress of recrystallization in Brass grains is observed later on,
once most of the S component is vanished. According to experiments with
commercial purity aluminium, the development of cube texture oriented nucleation is
the dominant texture mechanism. Cube texture nuclei can be formed in cold
deformation by the formation of copper textures and associated
deformation/transition bands more favored in high purity aluminium (1xxx). The f.c.c.
metals, such as aluminium, develop recrystallization textures which are relevant to
the prior deformation textures by rotations about the ‹111› axes [Mohamed et al.
2004; Christian, 2002; Ricks and Evans, 2006].
Investigations on the development of the recrystallization texture in

commercial purity aluminium, containing large Al3Fe particles, revealed that the
recrystallization texture develops from the competition between Cube-oriented
grains, which nucleate at the Cube bands, R-oriented grains, which originate from
the grain boundaries between the former deformed grains, and randomly oriented
grains due to particle stimulated nucleation. The Cube texture is favoured because
of two opposite effects: (i) its rapid nucleation due to its preferred recovery and (ii)
its optimum growth conditions. The excellent growth conditions of the Cube
orientation are more evident at high strains and high annealing temperatures. The
R-orientation arises when the Cube orientation is less pronounced. A large fraction
of randomly oriented grains is attributed to particle stimulated nucleation [Engler et
al. 1996].
A fine dispersion of small particles may promote notably the cube texture in
recrystallization of aluminium sheet due to the reduced Zener pinning effect on the
low-energy Σ7 boundaries between cube and S-grains. During processing of
aluminium alloys, increasing the dispersion level of small particles has a strong
effect on grain size and promotes additionally the cube recrystallization texture,
which is an undesirable texture for the litho sheet application [Nes, 2001].
During recrystallization at low annealing temperatures of commercially pure

aluminium, large grain sizes and high intensity of the cube texture component are
observed. The cube intensity becomes lower and the grain size smaller by
increasing the annealing temperature. This is due to the strong influence of
70
precipitates which may be created during recrystallization (explained at a later
section) [Sæter and Nes, 1998].
1.5.9 Microstructure evolution through the inter-annealing process
During annealing, the thermal energy received by the aluminium sheet does
not only soften it through recovery and recrystallization, but it also changes its solute
content. This is because the cold rolled aluminium sheet prior to inter-annealing is in
a super-saturated state. The AA1050 is very dilute and the vast majority of its
alloying elements (depending on their solid solubility and diffusion rates in
aluminium) are found within the solid solution after the sequential processes of
casting, homogenization, hot rolling and cold rolling.
Iron and silicon are encountered in commercial purity aluminium at very low
(impurity) levels, yet they have great effects on the recrystallized grain size and the
anisotropy of cold rolled sheet. Those elements can be also present in intermetallic
compounds such as coarse constituent particles, formed during solidification, and as
fine precipitates, formed during homogenization pre-heating, hot rolling and
annealing [Shoji and Fujikura, 1990].
Iron is contained in all commercial aluminium alloys both as an impurity and

as a deliberate addition. It is primarily encountered in the form of coarse intermetallic
particles that form during solidification and in solid solution. The solid solubility of
iron in the aluminium matrix is very low (maximum of ~ 0.04 % at 655 °C decreasing
to <0,001 weight % below ~430 °C). Under equilibriu m conditions the iron in excess
of its solid solubility in aluminium will be present as Al3Fe. Equilibrium is not
however usually reached, so iron is commonly present in supersaturated solid
solution and in non-equilibrium intermetallics phases [Marshall and Ricks, 1993;
Ambat et al. 2006].
In AA1050, iron is the major alloying element (~0.3 %) and it is encountered

not only in solid solution but also in the form of coarse constituent intermetallic
particles that form during solidification or that precipitate during later production
processes. Another element that could form second phases in AA1050 is silicon in
the form of α-AlFeSi, but those particles are very few compared to the iron
containing intermetallic particles The iron content of the alloy, both as particles and
in solid solution, is very important for the evolution of the microstructure during
processing. The iron content in solid solution is initially controlled during the casting
71
process. The level of dissolved iron is higher at continuous casting compared to
DC casting.
The intermediate annealing also influences greatly the iron content in solid
solution. The recovery and recrystallization behaviour are controlled by the iron and
other elements in solid solution and by the iron containing particles. Precipitation of
iron during a thermal treatment can lead to dislocation pinning and result in high
thermal stability [Hasenclever, 2006].
The iron atoms precipitate from the supersaturated solid solution in the as
cast, solidified, aluminium matrix at temperatures between 400 and 620 °C, in the
form of needle shaped metastable phases. The precipitation of iron in commercial
pure aluminium reaches a maximum in the temperature range between 350 - 400 °C
during an isochronal annealing. The effect of prior cold rolling for rather high
annealing temperatures on the precipitation amount of Al3Fe is not significant
because the precipitation of Al3Fe for commercial pure aluminium takes place after
recrystallization is over [Lendvai, 1990; Komatsu et al. 1990; Shoji and Fujikura,
1990].
Precipitates of intermetallic particles from a supersaturated solid solution

form preferably along dislocations or grain boundaries, following three stages
[Szabό et al. 1990]:
i. Nucleation, dependent on the level of supersaturation
ii. growth and
iii. ripening of precipitates.
During annealing and above a specific temperature iron may start diffusing.
The diffusion of iron occurs because the iron content needs to be near its
equilibrium at that specific temperature. This is a continuously changing relationship
between temperature and iron content in and out of solid solution. At high enough
temperatures iron containing particles may start dissolving thus getting more iron
into solid solution. At lower than dissolution temperatures iron atoms may diffuse
within the lattice but could as well precipitate out of the solid solution in the form of
fine precipitates also known as dispersoids.
The properties of many rolled aluminium products, including the litho sheet
substrate, depend heavily on their microstructure evolution through processing. The
annealing response, recovery, recrystallization start and finish temperatures,
softening rate, grain size and texture development are all highly dependent on the
72
intermetallic particles and solute levels. This establishes iron as the controlling key
element for the modulation of the critical properties of the final gauge rolled
aluminium sheet, to be used as substrate for lithographic printing plates. High iron
levels in solid solution account for high annealing temperatures and for
strengthening of both the as rolled and the annealed sheet, regardless of the particle
content. The softening rate is enhanced by the presence of coarse particles and
even more with increased particle volume fraction [Marshall and Ricks, 1993].
1.5.9.1 Coarse constituent particles
At the previous to annealing deformation stage, the second phase particles

affect the deformed microstructure and texture by increasing the dislocation density,
producing large heterogeneities (at larger particles) and altering the homogeneity of
slip e.g. shear bands. The role of second phase particles is important during
inter-annealing and especially on recrystallization kinetics, microstructure and
texture evolution. The second phase particles control the grain size and texture
development during thermomechanical processing. During annealing, the particles
could be categorized as large particles (>1 um) and small or closely-spaced
particles.
The larger particles are formed during casting, solidification and following
break-down through hot rolling. Due to the deformation heterogeneities at those
larger particles, these could become sites at which recrystallization may originate,
thus the name particle stimulated nucleation (PSN). The contribution of PSN to the
recrystallized microstructure and texture is not clear as the fraction of large particles
at which PSN successfully occurs is low (~1 %). Amongst the reasons for this is the
early stage preferential growth, such as cube grains.
The smaller particles originate from the breakdown of larger ones during
rolling operations or from precipitation during processing. Their influence on
annealing depends on whether those were present during deformation or whether
they were formed subsequently during annealing. The closely spaced particles pin
grain boundaries, thus hindering their mobility (Zener pinning) [Doherty et al. 1997].
1.5.9.2 Recrystallization and precipitation during the inter-annealing process
During annealing of a supersaturated solid solution, the interaction between

precipitation and recrystallization may be very complex. It depends on whether
73
precipitation occurs before, after or concurrently with recrystallization. At high
annealing temperatures, recrystallization is completed before any precipitation
occurs, so the precipitates do not influence the recrystallization microstructure and
texture. At lower temperatures precipitation may generally occur before
recrystallization completion thereby inhibiting both recovery and recrystallization.
The interaction between precipitation and recrystallization of a supersaturated solid
solution can be characterized schematically by the TTT (Temperature - Time -
Transformation) diagram of Holm and Hornbogen, shown in Figure 15. This diagram
shows three temperature ranges at which: I) recrystallization precedes precipitation
and is consequently unaffected, II) precipitation begins during recrystallization and
impacts its progress and III) precipitation precedes recrystallization or occurs
simultaneously, in which case recrystallization is slowed [Doherty et al. 1997;
Lendvai, 1990].
Sæter and Nes have shown that for cold rolled and subsequently annealed
aluminium AA1070, precipitation occurs concurrently with recrystallization and this
influences the texture development. On an earlier work they had shown that
recovery and recrystallization at low temperatures are more susceptible to
precipitation compared to high temperatures [Sæter and Nes, 1998].
1.5.9.3 Solute change evaluation during inter-annealing
The subsequent change in solute levels due to precipitation occurrence (or

not) during inter-annealing is most commonly defined by electrical
resistivity - conductivity measurements. Little to none correlation is however possible
with the microstructure. Researchers have used eddy current measurements to
monitor the changes in electrical conductivity. Iron in solid solution has a very large
contribution to the electrical resistivity of commercial pure aluminium. The change of
electrical resistivity by heat treatments, such as the inter-annealing, at temperatures
above 400 °C is solely attributed to the iron conce ntration. Increase of resistivity
above 500 °C is attributed to re-dissolution of iro n compounds. Measurements of the
electrical conductivity (reciprocal of electrical resistivity) on commercially pure
aluminium, demonstrated a slight increase during recovery and recrystallization
annealing. The increase of conductivity is predominately attributed to variations in
solute levels and volume fraction of precipitates. The influence of dislocations and
stored energy in electrical conductivity is only slight. The relationship between the
electrical conductivity and the reduction of the solid solution content can be
74
quantified by using the Matthiessen rule (Equation 9). The solid solution content on
a commercial purity aluminium alloy, after cold rolling and subsequent annealing,
was found to be 0.025 weight % for iron and 0.12 weight % for silicon [Doherty et al.
1997; Komatsu et al. 1990; Sæter and Nes, 1998].
1
= 0.0267 + 0.032 ⋅ Fe + 0.0068 ⋅ Si [Equation: 9]
k
Hasenclever has employed resistivity to measure the content of iron in

Al-Fe-Si alloys, using the factor 3.2 µohm / weight % for iron. He found out that the
content of Fe in solid solution increased with the amount of iron alloy addition and
that a smaller thickness of the rolling ingot helped retain more iron in solid solution.
The influence of inter-annealing on the content of iron in AA1050, as illustrated in
Figure 16, shows a clear relation between the amount of iron in solution before
annealing and the resulting tensile strength after “baking” (annealing 280 °C / 1h).
The thermal stability is better when the material has high solute levels prior to
annealing [Hasenclever, 2006].
Another way of measuring the precipitation and diffusion properties of the

iron content in aluminium is the measurement of thermoelectric power (TEP). Not
much work has been performed on commercial purity aluminium alloys as these do
not contain enough alloying elements that precipitate as those in e.g. 3XXX series.
The concentration of a particular element in solid solution is calculated from the
experimental TEP data, by using the relationship between TEP and resistivity of the
particular element in and out of solution. The TEP depends on the material matrix
and not on its form or shape. It is the measure of interaction between an applied
electrical potential or temperature and the created flux of electrons, relevant to a
reference metal. Such measurements in high purity aluminium alloys with low iron
additions have shown an approximate reduction of iron in solid solution after a 50 %
annealing. Annealing, in general, increases the number of intermetallic particles per
unit area of a size range within 0.1 - 0.5 µm. The significance of the reduction of iron
in solid solution is as high as the content of iron in the alloy [Ambat et al. 2006;
Szabό et al. 1990; Pelletier and Borrelly, 1982; Miroux A. et al. 2004].
A qualitative and quantitative solute iron analysis method which is less used
is the Phenol dissolution method, by which the second phase iron-containing
particles are extracted, filtrated and measured with atomic absorption methods.
Nevertheless, this method incorporates numerous safety factors [Komatsu et al.
1990].
75
The iron-containing intermetallic particles that may precipitate during
annealing have an adequate strong effect on the corrosion behaviour of the
aluminium. This also affects the material’s property of reactivity during the
subsequent electrolytic graining and anodizing processes. Annealing increases both
the cathodic and anodic reactivity of aluminium. Iron rich phases, such as the Al3Fe
encountered highly in AA1050, are preferential sites for cathodic reactions and for
nucleation of pits. The crevice between the particle and the matrix is the pit
nucleation site. A higher number of intermetallic particles should extend more pit
initiation sites. The cathodic reactivity is measured with the open circuit potential
(OCP). The solute content reduction during annealing also increases the anodic
reactivity. However, the correlation between solute content and anodic reactivity is
not well defined. The corrosion of aluminium is influenced even by low levels of iron
hence its electrochemical behaviour can be controlled by heat treatment.
[Thompson, 2006; Ambat et al. 2006].
1.6 Cold Rolling Process
After the inter-annealing step, the coil is left to cool down to room
temperature. The duration of this period is dependent on the coil storage conditions
and is highly associated with the following process step, the final cold rolling. The
cold rolling process is performed on a thin strip mill, utilizing flatness and thickness
control measurement technologies, at speeds in excess of 1000 m/min.
Rolling is used extensively in a wide range of manufacturing industries, to

produce raw material with such properties which are desired for the best
performance of whatever final product. The rolling process is a bulk deformation
process during which the sheet’s thickness is reduced by compressive forces
exerted by two opposing rolls. The rolls rotate to pull and simultaneously squeeze
the sheet between them, as shown in Figure 17. Rolling is a plane strain process,
which means that only two of the sheet’s dimensions are changing, its thickness and
its length. The sheet’s width should not be altered.
There are two types of rolling, namely hot and cold rolling. The difference
between hot and cold rolling processes is the metal temperature. When rolling is
performed above the metal’s recrystallization temperature, the process is termed hot
rolling and when rolling is performed at temperatures below the metal’s
recrystallization temperature, the process is termed cold rolling [Naser and Yelich,
2008].
76
Aluminium can be rolled to specific gauge with specified mechanical and
other properties. Especially for the lithographic printing plate product, the final cold
rolling of the aluminium substrate is a process step of great significance for its
critical property requirements.
Cold rolling manipulates the work hardening or strain hardening

phenomenon which is one of the strengthening mechanisms for wrought aluminium
alloys such as the AA1050. The deformation of aluminium proceeds by normal
crystallographic slip processes. Strain hardening increases the material’s flow stress
significantly but on the other hand reduces its formability. Furthermore, the change
from cube to a rolling texture suggests anisotropic behaviour [Hirsch].
Through cold rolling at ambient temperatures, the multiplication of

dislocations occurs at a faster rate than those are annihilated by dynamic recovery
within the metal structure. Initially, the dislocations can move through the metal
structure while the gauge of the material reduces. As rolling continues, the
movement of the dislocations becomes more difficult because when two or more
dislocations meet, the movement of one tends to interfere with the movement of the
other. The more dislocations there are, the more they will hinder each other's
movement. Moreover, the movement of dislocations is similarly hindered by grain
boundaries [Marshall et al.].
Deformation through cold rolling increases the strength of the metal and
makes it stiffer also. Therefore, it becomes less malleable and ductile. The metal
deformation during cold rolling generates heat which may achieve metal
temperatures of ~100 - 150 °C. In multi-pass cold r olling sequences the coil is
allowed to cool in between passes so as to avoid high temperature levels in the
following passes. During this cooling period, recovery takes place in some extent
depending on alloying elements, exit temperature, cooling conditions and previous
pass reductions [Hirsch].
Addition of specific alloying elements can increase the initial strength and
enhance the rate of work hardening. Of those, magnesium is the most effective
because it also inhibits dynamic recovery and promotes a more uniform dislocation
structure [Marshall et al.].
During cold rolling, high levels of tension are employed to control loads etc.
The cold rolling process’ most significant function is to reduce the aluminium gauge
to the final desired thickness, control the sheet’s strength and determine its
mechanical properties. Figure 18 shows how this is achieved for AA1050 and how
77
strength increases rapidly with strain. The final cold rolling is usually described by
the terms of % reduction or % cold work. These terms associate the material’s initial
and target thicknesses to give an estimation of the reduction achieved or the cold
work applied respectively. However, reduction applies only to a single pass [Ricks
and Evans, 2006].
Apart from the control of gauge and strength, cold rolling may also control
metallurgical features such as anisotropy and formability. The geometrical attributes
of the rolled coil such as the length, width and flatness are also controlled. Cold
rolling may also control surface features like topography, brightness, colour and
defects. The amount of cold work can influence the distribution of alloy constituents
and the magnitude of residual stresses in some aluminium alloys. As a
consequence, the type and rate of localized corrosion can be greatly affected by the
degree of cold work. On the other hand, the physical and chemical properties of
aluminium are only marginally affected by strain hardening [Ricks and Evans, 2006;
Hatch, 1984].
In recent years, a series of rolling simulation models have been developed

so as to fulfill the customer’s needs for materials of tight geometrical tolerances and
within specified property limits. The economics of rolling indicate rolling at high
speeds with minimum idle periods [Crumbach, 2006].
78
1.7 Literature Review - Figures
(a) (b)
Figure 1: Schematic diagrams of (a) the letterpress printing process and (b) the
flexography printing process. The images show the different ink application method
[DPS, 2012].
Figure 2: Schematic diagram of the Gravure printing process showing the principle
on which this process works [DPS, 2012].
79
Figure 3: Schematic diagram of the screen printing process showing the manner in
which this process is employed on paper [PNEAC, 2012].
Figure 4: Plateless process flow diagram [PNEAC, 2012].
80
(a) (b)
(c)
Figure 5: Schematic diagrams of (a) the offset lithographic printing process, (b) the
waterless offset variant and (c) the basic principles on which the offset lithographic
printing process is employed on multicolor printing [DPS, 2012] [PNEAC, 2012].
81
(a)
(b)
Figure 6: Schematic diagram showing (a) the principle of the modern offset plate
and (b) exposing a plate to UV light to produce an offset press, functional plate
[DPS, 2012].
Figure 7: A printing route from a) a D.C. cast ingot, to b) the rolled sheet in a coil, to
c) a lithographic printing plate, to d) a developed offset lithographic plate and to e) a
final printed sheet [Courtesy of Dr. R. Hunt].
82
Surface
Cross Section
Figure 8: An offset lithographic printing plate with its different layers after the plate
production stage, as viewed from the surface and in cross section.
83
Hot and cold rolling
Figure 9: The three production stages of aluminium offset lithographic plate

production.
Figure 10: Plot of strength in relation to temperature during annealing process

[Ricks and Evans, 2006].
84
Figure 11: Hardness measurements of recovered cold rolled commercial purity
aluminium. The straight lines correspond to regions of recovery while subsequent
rapid decrease corresponds to early recrystallization (after Nes 1995) [Humphreys,
2001].
Figure 12: Plot of fraction recrystallized in relation to time, during recrystallization

process [Ricks and Evans, 2006].
85
Figure 13: Plot of recrystallization effects on tensile properties [Cama et al.].
Figure 14: Plot of recrystallization effects on hardness [Cama et al.].
86
Figure 15: Schematic TTT diagram of the different possible sequences of
precipitation and recrystallization [Lendvai, 1990].
Figure 16: Influence of intermediate annealing on the iron content in solid solution
and the thermal stability [Hasenclever, 2006].
87
Figure 17: Rolling process, parameters and details [Naser and Yelich, 2008].
Figure 18: Plot of Yield strength with reducing gauge of AA1050 by cold rolling.
The RR point is the pre-cold rolling strength while the P1,2,3… indicate the strength
after 1, 2, 3 etc cold roll passes. Strength increases quickly after first pass and then
changes marginally [Ricks and Evans, 2006].
88
2. Experimental Procedure
The literature review has pointed out the significance of inter-annealing and
cold rolling during the aluminium substrate production for lithographic printing plates.
This Thesis researches the influence of these processes on the key lithographic
sheet properties. The research focus was on the following:
i. the inter-annealing process variables,
ii. the cold rolling process variables and
iii. the material properties evolution through the above processes.
The experimentation concept was to examine how these processes affect

the sheet’s performance, as a final product, at the printer’s. Figures 19 and 20 show
graphically a typical commercial production route, the research focus area and the
experimental variables.
This section presents the materials and techniques employed in performing

the experimental procedure. All described experimentations were carried out using
the equipment at the Hellenic research centre for metals (ELKEME S.A.).
2.1 Materials
Table 10 lists the industrial scale materials used for experimentation. The
process stage is relevant to where the samples were collected from.
Table 10: List of provided material.

Sample Gauge Annealing
Process stage Position (1)
number (mm) practice
S1 1.5 Pre-annealing IA-1 Outer-coil

S2 1.5 Pre-annealing IA-1 Inner-coil
S3 1.5 Post-annealing IA-1 Outer-coil
S4 1.5 Post-annealing IA-1 Inner-coil
S5 0.3 Final cold rolling IA-1 Outer-coil
S6 0.3 Final cold rolling IA-1 Inner-coil
S11 0.3 Final cold rolling No anneal Inner-coil
(1).
The position stated is always in reference to the coil post-annealing.
89
All samples were from the same cast batch of the AA1050 type alloy, the
composition of which is provided in Table 11.
Table 11: Weight % composition of the major alloying elements in the AA1050
samples.
Fe Si Mg Others Al
0,33 0,06 0,045 < 0,02 99,51
The samples were treated with different developmental annealing practices,

the details of which are described in Table 12.
Table 12: Annealing practice time-temperature targets.
Total treatment time Target metal

Annealing practice
(hours) Temperature (°C)
IA-1 7 400-430
IA-2 9 400-430
IA-3 9 450-480
The received A4 sized samples corresponded to the full width of the coil. The
experimental specimens were all selected and prepared accordingly from the 2nd A4
sheet which corresponded to the ¼ of the width, as Figure 21 illustrates. This was
performed in order to have similar yet representative material for all the
experiments.
2.2 Methods
The following section describes the methods and instruments employed in

the experimental procedures.
2.2.1 Particle size analysis
Particle size analysis is the measure of the second phase (Aluminium - Iron)
which is a microstructure characteristic very closely related to the material properties
and behaviour. The particle size was measured at anneal gauge (both pre and post)
and at 0.3 mm gauge (cold rolled). Specifically, the quantities and parameters
measured were:
90
• The number of particles per unit area (mm2) - N,
• the volume fraction - A % and
• the size (um) of the second phase particles - Dc.
Aluminium pieces, of dimensions of 30 x 30 mm, were cut with a band saw

using forced air cooling to avoid any local heating while cutting. The specimens
were trimmed to remove burrs and mounted in pack mounts of longitudinal and
transverse directions. A further set of samples was mounted using double-sided
adhesive tape for surface plane polishing. The pack mounting technique allows
multiple thin samples to be polished, etched or anodized simultaneously. All
specimens were placed on their desired plane of examination and thin (0,05 mm)
aluminium foil sheets were placed between them. Harder and thicker aluminium
alloy pieces were used at both the mount’s sides as backup plates. The mount was
held with a vice in order to drill a hole through all the pack-mount’s constituents. For
this purpose, a specialized for aluminium 3 mm drill was used, together with forced
air cooling, as aluminium is soft and sticky when drilled. All specimens were bolted
together. The goal was to achieve a void free, conductive polishing plane [ELKEME
S.A.].
The pack-mounts were then mounted using Struers Clarofast hot mounting
resin so that the end result was a transparent mount without any cracks or voids.
The mounting was performed on a Struers ProntoPress-20 hot mounting press. The
prepared metallographic mounts were then polished on a Struers RotoPol-35
automatic grinding and polishing device using small loads (30N) so as to avoid
severe deformation. The sequence of grinding with silicon carbide papers used 80,
220, 500 and 1200 grit sizes. The grinding times were usually not longer than two
minutes per grinding paper, although that was dependent on the polishing outcome
of each previous grinding stage. The final polishing was performed initially on a
Struers MD-Mol cloth using Struers Dia-Pro 3um diamond suspension and
afterwards on a Struers MD-Nap cloth using Struers OP-U polishing suspension.
The polishing times were ten minutes per polishing cloth [ELKEME S.A.]. A final
step was performed by polishing on a Struers MD-Chem cloth using Struers OP-S
polishing suspension for a few (2-3) minutes. Figure 22 illustrates a polished
pack-mount.
The as-polished samples were then examined with a Nikon SMZ Epiphot
300 inverted light optical microscope and with a Philips XL40 SFEG scanning
electron microscope (SEM). For the particle size analysis, SEM offered better
91
contrast between second phase particles and the aluminium matrix. It was also
easier to identify any possible artifacts arising from the polishing stage.
The scanning electron microscope exploits the interaction between electrons

and matter. An electron gun produces a beam of electrons which are accelerated to
a specific energy (keV – kilo electron Volts) by an electric field and focused through
electro-magnetic lenses onto the sample surface. The electron penetration depth
into the sample can be as great as a micrometre and the beam diameter range
5 - 100 nanometres. The finely focused beam of electrons interacts with the
specimen’s surface. The electrons emitted include low energy secondary electrons
knocked from the orbital shells of the sample’s atoms. The secondary electrons are
useful for showing the specimen’s surface topography. These are detected with the
secondary electron (SE) detector. Also emitted are high energy backscattered
electrons, which originate from the original beam and are scattered by the atomic
nuclei. The backscattered electrons are useful for showing up differences in atomic
number on the specimen’s surface. These are detected with the backscattered
electron (BSE) detector. The scanned surface is projected via the software which
controls the SEM and can be then captured as an image. It is possible to obtain
images showing various aspects of the specimen, such as the surface topography,
average atomic number, surface potential distribution, magnetic domains, crystal
orientation and crystal defects in a solid specimen [Wells, 2001].
A series of different instrument conditions were tested. The spot and

aperture size were both fine-tuned for the best possible imaging result. The
backscattered electron detector (BSE) was selected because it offered much better
resolution and distinction between the matrix and the second phase particles.
Furthermore, 10 keV electron energy was selected in order to be more surface
feature concentrated. A total of 10 images per specimen from sequential fields were
captured at x1000, covering an area of:
10 × (712 × 484 ) pixels or 10 × (119 × 90 ) µm 2 = 0.107mm 2
All images were captured from the second upper quarter of the cross
sections in the longitudinal and transverse directions, as shown in Figure 23, in
order to be as close as possible to the final gauge top surface. The goal was to
measure at least 1000 particles per direction, per sample.
All captured fields were processed with the image analysis software Image
Pro Plus v.7, to extract measurement data. For this purpose, a specific macro was
written which consisted of the following major steps:
92
• Flattened background (100pixels),
• filtered bright objects (second phase particles) in grayscale 130 to 255 and
• minimum particle size comprised of 5 pixels (area = 0.15 µm2).
The software allows the extraction of many different size and shape parameters.
The parameters selected for this analysis were:
For each field:
• N, the number of particles per field and
• A %, the area fraction of the second phase particles,

Total particle area
A% = × 100
Field area
For each particle:
• A, the particle area, which was used to calculate the circular equivalent
A
diameter (Dc), the diameter if all particles were circles, Dc = 2 ⋅
π
2.2.2 Grain size and structure
A material’s grain structure is characterized by the size, the shape, the

appearance, the extent of crystallization and the amount of deformation. Each of
these is characteristic for a different production stage and together all describe the
material’s process, properties and behaviour [Vander Voort, 1999].
In order to examine the grain structure of an aluminium sample, the sample

may be prepared according to the ASTM standard E407-99. The mounted and
polished sample undergoes an electrolytic etching in a 5 g HBF4 - 200 ml water
solution. A pure aluminium, lead or stainless steel sheet is used as a cathode. The
anode is the aluminium sample, which is anodized for 1-3 minutes, using
20-45 Volts direct current. This technique is also known as anodizing with Barker’s
reagent (1.8 % Fluoboric acid in water). It is widely applicable for revealing the grain
structure in wrought alloys, but there needs to be a conductive path
[ASTM E407-1999; Vander Voort and Manilova]. Figure 24 illustrates the setup used
to anodize these experimental samples.
The anodized specimens were examined with a Nikon SMZ Epiphot 300
inverted light optical microscope. In particular, the specimens were examined using
93
polarized light microscopy. The microscope is equipped with a polarizer, positioned in
the light path somewhere before the specimen, and an analyzer placed in the optical
pathway between the objective rear aperture and the observation tubes. This is a
contrast-enhancing technique that improves the quality of the image obtained with
birefringent materials when compared to other techniques such as dark-field and
bright-field illumination. Polarized light microscopes have a high degree of sensitivity
and can be used for both quantitative and qualitative analysis of anisotropic
specimens. Polarized light microscopy is capable of providing information on colour
absorption and optical path boundaries between minerals of differing refractive indices,
in a manner similar to bright-field illumination, but the technique can also distinguish
between isotropic and anisotropic substances. Furthermore, the contrast-enhancing
technique exploits the optical properties specific to anisotropy and reveals detailed
information concerning the structure and composition [Robinson and Davidson].
For each specimen, a series of five consecutive fields from the near-surface,
¼ thickness position, were captured at x200 magnification. Figure 25 illustrates the
imaging position.
The average grain size is estimated according to ASTM standard E112-10.

The grain size number (G) is defined as the number of grains per square inch at
x100 magnification. The three basic procedures for grain size estimation are
[ASTM E112-2010]:
i. the comparison procedure (comparison of the grain structure to a series of

graded images),
ii. the planimetric procedure (actual count of the number of grains within a
known area) and
iii. the intercept procedure (actual count of the number of grains intercepted by
a test line of known length or the grain boundary intersections within a test
line).
For these experiments, the intercept procedure was preferred although the
grain size was not attributed numerically. Instead, the mean lineal intercept length
( l ) was calculated by measuring the number of intercepts and dividing that to the
line’s length. For this purpose, a grid of five equally spaced, parallel lines of the
same length was created and all captured images were measured with that. Such a
grid example is illustrated in Figure 26. The lineal intercept length was measured for
all five lines of every captured field and an average mean lineal intercept length ( l )
94
was calculated for each sample. The histograms of the measurements were also
created in order to monitor the data distribution [ELKEME S.A.].
The grain size could be measured on fully recrystallized, post annealed

materials. Heavily cold-worked materials, such as the pre-annealed and final
cold-rolled ones, could not be measured due to the significant amount of
deformation. The grain structure analysis for those could only be qualitative.
Partially recrystallized structures, such as those during the inter-annealing

process, were not measured as far as grain size but only as far as fraction
recrystallized. The fraction recrystallized equals the volume fraction of newly formed,
equiaxed grains in a specified deformed structure area. The fraction recrystallized
was averaged from five consecutive fields captured at x200 magnification,
representative of an area of ~1.07 mm2. A grid consisting of 100 equally distributed
points, illustrated on Figure 27, was created and all captured fields were measured
with that. The fraction of points coinciding with a recrystallized (new) grain is an
estimate of the area fraction recrystallized of the image field. This area fraction is a
good estimate of the recrystallized volume fraction [Russ, 1986].
2.2.3 Tensile tests and microhardness
The tensile testing aims to measure a material’s mechanical properties such

as the yield strength (YS), the ultimate tensile strength (UTS) and the percentage
elongation (% EL). The yield strength (YS) corresponds to the applied stress
required to cause permanent plastic deformation and is measured in Pascal
(1 Pa = 1 Nm-2). The ultimate tensile strength (UTS) is the applied stress required to
cause failure of a material in a tensile test and has the same units. The percentage
elongation (% EL) after fracture is used to describe the tensile specimen’s change in
length after fracture, expressed as a percentage of its original length. The Young’s
modulus (E) is also a property extracted from tensile testing and it characterizes a
material’s stiffness. The Young’s modulus is the ratio of the stress to the strain in the
elastic region. Those tests are performed on tensile test specimens that are
prepared on hydraulic cutting presses and have the characteristic “dog-bone” shape
[Leppin et al].
All samples were tested transversely to the rolling direction according to the
plate maker’s specifications. The samples were measured with a Zwick / Roell
ZMART PRO hydraulic testing machine, at ambient temperatures and according to
standard [BS EN ISO 6892-1:2009, 2009].
95
Hardness is the measure of resistance to plastic deformation, correlated with
both yield and tensile strength. In general, harder materials exhibit higher strength
while softer materials exhibit lower strengths. Because hardness is one of the
material strength related properties, it is thus closely associated to the material’s
microstructure. It is also termed as a material’s ability to resist indentation. Hardness
is used extensively as a quality control test. There is a wide range of different
hardness tests such as Brinell, Meyer, Vickers, Rockwell, etc. However, the principle
is the same. If a hard object under specific load is pressed into the surface of a
softer material with sufficient force to produce an indentation, the indentation size
will depend on the magnitude of the load and the hardness of the indented material.
Hardness is defined as the load applied divided by the projected area of indentation.
In practice, the size of the indentation is measured and then related to a hardness
value [Vander Voort, 1999; Leppin et al.].
When smaller indenters and lower loads are used, the term is referred to as
microhardness. According to ASTM standard E384-99, loads from 1 to 1000 gf
(9.8 x 10-3 to 9.8 N) indicate the microhardness ranges. Microhardness is commonly
used to evaluate the local hardness. The Knoop and Vickers hardness indenters are
widely used for determining microhardness. The Vickers indenter was preferred for
performing the microhardness measurements of the examined samples because it
is less sensitive to surface conditions. The Vickers indenter, illustrated in Figure 28,
is a diamond ground to the shape of a square-based pyramid with an angle of 136˚
between faces. The depth of the indent it makes is about 1/7 of its diagonal length
[Instron, 2000]. The hardness Vickers (HV) is calculated by:
a
2 ⋅ L ⋅ sin 
2
HV = 2
[Equation: 9]
d
where, d is the mean diagonal in um,
L is the load in gf and
a is the face angle (136˚).
There is a useful approximate relationship between hardness Vickers and

yield strength, which is widely used, but not always strictly correct [Leppin et al.].
This relationship states that:
Hardness Vickers (HV) ≈ 0.3 × Yield stress (MPa) [Equation: 10]
96
During the test, the indenter is lowered until it contacts the specimen’s
surface. Then, a test force is applied that ramps up to the total selected test force
over time (t1) and holds this force for a selected time (t2). The first time scale (t1) is
referred to as the “apply” time and the second (t2) as the “dwell” time, also shown in
Figure 29 [Instron, 2000].
The microhardness measurements are susceptible to various sources of

errors. A list of those is given in Table 13.
Table 13: List of microhardness measurements error sources [Vander Voort 1999].
Instrument errors Measurement errors Material errors
Calibration of measuring Non-uniformity of

Accuracy of the load
device microstructure and chemistry
Inertia effects, speed of
Resolving power of objective Orientation effects
loading
Vibrations Magnification Quality of polish
Angle of indentation Operator bias Low reflectivity, transparency
Lateral movement of the Inadequate image quality,
indenter or sample non-uniform lighting
Indentation time
All microhardness measurements were performed on either the polished

surface or on the mounted in the longitudinal plane of direction, cross sectioned
samples. An Instron indentation hardness tester, Tukon 2100 instrument, was used
to perform all indentations and diagonal measurements, according to ASTM
standard E384-99 and ISO standard 6507-1. At least five measurements were
performed per sample using 200 gf, apply time 3 s and dwell time 10 s. The
indentation marks were examined and measured at x200 magnification
[ELKEME S.A.; ASTM E384–99, 1999; ISO 6507-1:2005, 2005].
2.2.4 Mathematical (annealing) model
Mathematical modelling has been used extensively in many fields including

materials science. The wide variety of applications and their use in industry have
defined modelling as a strategic tool of great importance. Amongst the reasons for
this are:
• An increase in understanding of the modeled system.
97
• The prediction of the system’s behaviour under certain conditions that is
otherwise difficult to control and/or measure.
• The capability for carrying out technical and quantitative computations for
control design, out of which process optimization can be obtained [Nguyen,
2010].
The inter-annealing production stage has many process parameters. It is

difficult to test all of those parameters without substantial energy consumption and
material waste. A mathematical model can predict with good accuracy the
temperature variation through a coil during inter-annealing. Such a model was
created for the purposes of this thesis by Dr. Ioannis Contopoulos of ELKEME S.A.
A three dimensional computational fluid dynamics (CFD) model was created to
simulate typical thermal cycles performed in an industrial batch-annealing furnace.
The model was created with the ANSYS Fluent 13.0 software, which is capable of
modelling heat transfer in complex geometries, such as that of a coil enclosed in a
furnace.
To create this model, the following input data were required:
• A schematic showing the following features of the annealing furnace:
o enclosure dimensions,
o burner positions,
o air fan positions,
o fan type of operation and
o air circulation (inlet, outlet)
• Coil size: outside diameter (OD), width and gauge.
• Steel spool size: OD, thickness and width.
• Annealing practice: time–temperature program.
The data were selected to be industrially realistic. Some features of actual

annealing practice are considered confidential and hence are not presented here.
For the efficiency of the model, some assumptions regarding the geometry of
the coil and the furnace had to be made. The coil was considered symmetric with
respect to the oven mid-plane and all furnace zones were considered equivalent.
The variables of the furnace’s air velocity and the coil’s thermal conductivity
were adjusted within the model to give a good fit with previously measured metal
98
and furnace air temperatures from an instrumented coil with thermocouples at
various coil positions. The aluminium coil thermal conductivity is anisotropic and
dependent on the surface roughness, the air gaps and residual rolling oil entrapped
within the coil wrappings and the tension of coiling before annealing. It was hence
calibrated for the coil’s tangential, axial and radial direction.
The air flow and temperature in the area where coils are left to cool after
removal from the annealing furnace were estimated to be typical of ambient
conditions.
Figure 30 illustrates the coil’s sampling regions and the selected positions to
extract temperature data over time from the mathematical model of both the
annealing and cooling cycles. Specifically:
• Positions 1 to 3: 0° horizontal, 50mm from coil fr ont edge.
• Positions 4 to 6: 45° from horizontal, 50mm from c oil front edge.
• Positions 7 to 12: Vertical, middle of coil.
o Positions 1, 4, 7 and 10: 50mm from steel spool.
o Positions 2, 5, 8 and 11: 1/3 of radial distance from steel spool to surface.
o Positions 3, 6, 9 and 12: 50mm from surface.
The temperature data were collected and plotted as temperature against

time to show the variability of the selected positions in the coil. The plots created
consisted of the heating (annealing) and the cooling curves. Examples are shown in
detail in later sections.
2.2.5 Laboratory simulation of annealing practice IA-1
A very important parameter, which is not easily monitored but needs to be

controlled during the inter-annealing process, is that of microstructural homogeneity
throughout the coil. As previously stated, this is difficult to test in an industrial scale
without having to reject the coil afterwards. The difficulty lies in taking samples
throughout a coil during the annealing process. The mathematical model-simulation
is the first step to solving this issue.
Based on the model’s temperature over time predictions and the

annealing-cooling curves plotted for each of the specified coil positions, a simulation
of the inter-annealing cycle was performed in the laboratory. This simulation
targeted various coil positions as explained later. Pre-annealed samples 1 and 2
99
(Table 10) were used in these experiments. The samples were prepared by cutting
small coupons with a band saw, simultaneously using a flow of continuous
compressed air cooling so as to avoid any local heating, softening or deformation.
The specimens were inserted in a Nabertherm N60/85HA chamber furnace

with air circulation, equipped with a C40 programme controller. They were then
taken out at various time intervals specified by the experiment and quenched
straightaway by immersion in a tank with common tap-water. The laboratory furnace
programme controller regulates the furnace temperature. The controller implements
a step by step program. Each step consists of a starting and the target temperature.
It also includes the time during which the target temperature is reached. A
time-temperature programme was created according to each of the experiments and
was used as the laboratory furnace input. This programme, however, needed to be
verified instrumentally before any experimentation. A Hanna HI 98804 thermocouple
thermometer was used to monitor both the metal and the air furnace temperature
during the verification process and the experiments. The metal temperature was
monitored by drilling a hole and placing a thermocouple into an aluminium specimen
of the same alloy and dimensions as the experiment samples. Figure 31 illustrates
the instruments used in this experimentation series.
The instrumented verification goal was to achieve metal temperatures as

close as possible to those predicted by the mathematical model. Some temperature
lagging or hastening during the trial suggested that a fine-tuning of the laboratory
furnace time-temperature programme was needed so as to avoid any hysteresis
phenomena. Figure 32 shows the result curves of such a verification trial.
2.2.6 Isothermal and isochronal annealing
The implementation of isothermal and isochronal annealing experiments

aims to offer information on microstructure and property evolution under specified
heating conditions. Isothermal and isochronal experiments have been used
extensively by researchers in order to examine some of the material’s aspects such
as solute, texture, etc. after heating. On the annealing process specifically, such
experiments are useful to predict a material’s critical temperatures at which the
related annealing phenomena occur. Researchers have used these experimental
results in addition with modelling, so as to predict:
100
• Kinetics of recrystallization [Vandermeer, 1992; Vandermeer and
Jensen, 2001; 2003].
• Texture development after annealing [Alvi et al., 2004; Sæter and Nes,
1998].
• Grain size and growth rates of recrystallized grains [Furu and Nes, 1993;
Hagström et al., 2000].
• Effects of alloying elements during annealing [Shoji and Fujikura, 1990;

Ohno, 1981; Takei et al., 1981; Lendvai, 1990].
Isochronal and isothermal tests employ respective equal time and

temperature heating intervals. In the majority of experiments [Sæter and Nes, 1998;
Furu et al. 1995; Alvi et al. 2004] the samples are immersed for the specified time at
temperature in specialized salt baths which offer immediate heat transfer and very
good temperature accuracy. This immersion technique is also known as fluidized
bed. In this set of experiments a simpler technique was used, according to which the
samples were inserted in the furnace, described in 2.2.5, for the specified time at
temperature and then removed and instantly quenched by immersion in a tank with
common tap-water. Prior to experiments, a test was performed to calculate the time
necessary, for samples to reach the target temperature, once inserted into the
furnace. The results of this test are given in a later section.
Specimens from samples 1 and 2 (Table 10) were prepared similarly to

2.2.5. During the isochronal test, all specimens had a 30-minute dwell in the
furnace, set at various temperatures. During the isothermal test, all specimens were
inserted together in the laboratory furnace which was set at the critical temperature
specified by the previous isochronal experiment. The specimens were removed from
the furnace after specified time durations at temperature.
The isochronal and isothermal experimental samples were subsequently

used to extract grain structure, fraction recrystallized and microhardness data as
described at previous sections. The resultant data from the isothermal experiment
were used to fit the JMAK equation. The fraction recrystallized and the
microhardness results were used for this purpose.
2.2.7 Electrical conductivity
The electrical conductivity (k) is described as the reciprocal of the electrical

resistivity (ρe).
101
1
Electrical conductivity (k ) = [Equation: 11]
Electrical resistivit y (ρ e )
The electrical conductivity is a measure of how well a material

accommodates the movement of an electric charge. It is the ratio of the current
density to the electric field strength [NDT Resource centre]. The following equation
12 describes the relationship between electrical conductivity, resistivity and material
size.
R⋅A 1 l l
ρe = ⇒ = ⇒k= [Equation: 12]
l ρe R⋅A R⋅A
Where, R is the material resistance (Ω),
A is the cross-sectional area (m2) and
l is the length (m).
Electrical conductivity is measured in Siemens per metre (S m−1). A common

alternative unit is the reference against high purity annealed copper conductivity,
that is 58 MS m−1 or “100% IACS” (International Annealed Copper Standard) at
20 °C. All other lower conductivity values are rela ted back to this conductivity of
annealed copper, expressed as % IACS. Aluminium ranges between 26-69 % IACS.
Conductivity values in (S m−1) can be converted to % IACS by multiplying the
conductivity value by 1.7241 x10-6 [NDT Resource centre; Sigli et al (b)].
A material’s electrical conductivity depends on several factors, such as its

chemical composition and the stress state of its crystalline structure. When an
electric field (voltage) is applied, the electron mobility amongst atoms determines
the current flowing. When such a voltage is applied to an aluminium specimen, the
free electrons accelerate but are scattered by imperfections in the crystal lattice
such as solute atoms, vacancies and by the thermal vibration (phonon scattering) of
the alloy’s atoms themselves. The sum of the above characterizes the alloy’s
resistance (R). Dislocations also influence a material’s resistivity but their effect is
much lower compared to the solute’s effect because the dislocation spacing is much
larger compared to the solute atom spacing. The second phase particles of the alloy
influence the material’s electrical conductivity only very slightly because their usual
low volume fraction gives rise to little or no electron scattering [Sigli et al (b)].
As already described in section 1.5.9.3, researchers have used the changes

in electrical conductivity to evaluate the iron and silicon levels in solid solution after
102
heat treatments of commercial purity aluminium [Sæter and Nes, 1998]. The
change in electrical conductivity is however predominately attributed to variations in
iron solute level.
The electrical conductivity for sheet or plate samples can be measured with
eddy current techniques. The eddy currents are induced in the material by a high
frequency magnetic field and are then detected by a secondary electromagnet. Eddy
current devices use a flat-ended cylindrical probe. The probe is accurately calibrated
against standards such as high purity copper. Temperature changes in the
measured material affect the resistivity, hence the measurement’s accuracy. The
experimental samples were measured at ambient temperatures with a Foerster
Sigmatest D-2.068 instrument, at 480 kHz. All measurements were performed with a
14 mm probe kit on the surface plane, measured in % IACS.
2.2.8 Laboratory AC-electrograining
AC-electrograining is used industrially to create a uniformly pitted and

convoluted surface suitable for lithographic printing plates. The aluminium sheet is
roughened through a controlled corrosion process which aims to improve the
wettability of the substrate. The most common electrolytes used commercially are:
hydrochloric acid, nitric acid or both of the above sequentially [Laevers et al, 1993].
The experimental technique is not based on a standard method but is a

laboratory simulation of the industrial process. Nonetheless, it is very difficult to
accurately simulate an industrial AC-electrograining process in the laboratory
because the sizes and volumes are extremely different. The degreasing-cleansing
stages are far more effective and uniform and the electrolyte parameters of flow,
temperature and composition are monitored constantly throughout the industrial
process. A laboratory version of AC-electrograining needs to compromise with not
the best control over the above.
The equipment used to perform this experiment is listed in Figure 33 and

consists of:
• A Euro-Test electronic system GmbH ACS-FB power supplier.
• A HAAKE K15 water pump.
• An electrochemical cell which has:
o A double-wall glass vessel.
103
o A special PVC-PP holder for the sample and graphite counter electrode.
o A transverse stirrer.
• Common laboratory, glassware equipment.
The experimental layout is illustrated in Figure 34. The power supply

provides the current to the circuit. The device is connected to a computer unit with
software that controls and records the experiment electrical parameters. These
parameters are the voltage, a maximum current limit, the frequency and the time of
experiment. The water pump circulates water to the glass vessel. The temperature
of the flowing water is controlled by a thermostat.
The electrochemical cell is where the surface roughening reaction occurs.

The main components of the cell are the electrolyte solution, the sample electrode
and the graphite counter electrode and a conductive connection between those for
creating a close circuit. The special PVC-PP (polyvinylchloride - polypropylene)
holder consists of two fixed distance (23 mm) parallel sockets where the electrodes
are positioned. Those sockets allow only a specific area (60x60 mm) of the
electrodes exposed to the electrolyte. The transverse stirrer provides constant flow
of the electrolyte between the electrodes with a stirring speed of 600 rpm at the
vessel’s centre.
The final gauge materials were electrograined in order to compare their

roughening behaviour under similar electrograining conditions. The samples used in
this experiment were production samples (samples 5, 6, 9, 10 and 11, Table 10).
Specimens of 130x67 mm were cut with a guillotine, cleaned by acetone rinsing and
dried with filtered compressed air. Prior to AC-electrograining, each specimen was
pre-treated as follows:
• Immersion in 15 g/l NaOH at 50°C, for 10 s.
• Rinsing with deionized H2O.
• Immersion in deionized H2O, at room temperature, for 20 s.
• Immersion in diluted electrolyte (1:3), at room temperature, for 10 s.
The specimens were then placed in the special holder, which was immersed
in the 10 g/l HCl electrolyte, thermo-stated at 40 °C. The graining electrolyte was
affecting only a 60 x 60 mm surface area of the specimen. The AC-electrograining
conditions were constant for all samples, at 15 Volts, 24 Amax, 50 Hz for 23 s. The
104
goal was to achieve a current density of ~45 Adm-2 and a total charge density of
~1000 Cdm-2.
The smut layer (hydrated Al(OH)3 ) present on electrograined specimens

was removed by immersion in a 170 g/l H2SO4 - 5 g/l Al+3 solution, at 60 °C, for 120
s. The de-smutted specimens were finally rinsed thoroughly with deionized H2O and
dried with filtered compressed air.
The object of this experiment is the examination of the roughening behaviour

of the aluminium surfaces, under certain electrochemical conditions. The graining
result is difficult to evaluate quantitatively. A qualitative ranking system of the
samples, by visual inspection, is described at Table 14.
Table 14: Qualitative ranking scale of electrograining result [Smith et al., 2010]
Grade Electrograining Comment

Target electrograining performance with high uniformity
++ Very good
and ease of initiation.
Industry-accepted benchmark for electrograining
+ Good
performance.
+- Adequate Still acceptable, yet slightly deteriorated in uniformity.
Problematic in industrial scale due to noticeable

- Poor
deterioration in uniformity and initiation.
-- Very poor Poor performance, incomplete electrograining.
Researchers have further evaluated AC-electrograining results by

characterising the topography of the roughened, fully convoluted electrograined
surface. This was achieved by evaluating the pit appearance, number and size by
means of scanning electron microscopy (SEM) and inteferometry with data analysis
[Rivett et al. 2011].
2.2.9 Gloss
Gloss offers a further way of evaluating the roughening result of

AC-electrograining. Specular gloss and roughness are associated surface properties
[Ward, 2011]. Smooth or highly polished surfaces reflect the light greatly whereas
rough surfaces scatter the light in all directions. The light is directed at the sample’s
surface at a defined angle and the reflected light is measured photo-electrically. The
intensity of the reflected light depends on the material and the angle of illumination.
105
Gloss is usually measured in gloss units (GU) or in % reflection of the illuminated
light. The typical illumination angles are [BYK]:
• 20˚, for high gloss materials,
• 60˚, for semi gloss materials and
• 85˚, for low gloss materials.
The AC-electrograined surfaces were measured of their gloss with a BYK

micro-TRI-gloss device, at all three angles.
2.3 Experimental Approaches
This section describes the scope of the performed experiments. All

experimentations were performed according to the previously described
experimental techniques and equipment.
2.3.1 Benchmarking of pre- and post- annealed materials
The scope of this experiment was to characterize the input and output
materials of the inter-annealing process. The aim was to develop an understanding
of the evolution of the microstructure and other properties through the industrial
inter-annealing process. The material was evaluated:
• Before and after industrial inter-annealing,
• at the outer (outer-coil) and inner (inner-coil) wraps of the coil,
• on its anisotropy (by comparison of the longitudinal, transverse and surface

plane directions) and
• for different annealing practices (based on coil size).
The benchmarking exercise was performed on provided industrial material

(samples 1, 2, 3, 4, 7 and 8 – Table 10), at anneal gauge (~1.5 mm). The samples
were measured as follows:
• Particle size analysis at all planes, searching for evidence of any possible
precipitation or particle coarsening during inter-annealing.
• Grain structure analysis on post-annealing samples at the longitudinal

direction, for determination of the grain size and shape through different
annealing treatments.
106
• Microhardness measurements on the polished surface plane, for determining
the material’s hardness after the inter-annealing process.
The results of this exercise were used as the industrial reference for
comparison with lab-scale experiments.
2.3.2 Annealing modelling and laboratory annealing simulation (1): typical coil
position
The aim of this experiment was twofold:
• Use the mathematical model to predict the metal time-temperature history for
a typical, industrial scale annealing practice.
• Simulate this thermal practice in a laboratory furnace [laboratory annealing

simulation (1)].
The model would be useful to predict the variability in the industrial process
and the laboratory annealing simulation would allow characterization of the material
at different annealing intervals.
The creation of the mathematical model was described in section 2.2.4.

Laboratory annealing simulation (1) followed the mathematical model
time-temperature annealing curves for the typical coil positions 2 and 5, also shown
in Figure 32. The samples used in this experimentation were outer- and inner-coil
pre-annealed samples (samples 1 and 2 - Table 10). Table 15 shows the different
annealing intervals at which samples were examined.
Table 15: Samples for laboratory annealing simulation (1).
Sample code Annealing time

Temperature (˚C)
Outer-coil (S1) Inner-coil (S2) (min)
Pre-annealing Pre-annealing Room temperature 0
S1_1 S2_1 150 110
S1_2 S2_2 250 190
S1_3 S2_3 300 280
S1_4 S2_4 350 345
S1_5 S2_5 420 495
S1_6 S2_6 350 720
S1_7 S2_7 300 900
S1_8 S2_8 250 1140
Post-annealing Post-annealing Room temperature -
107
The specimens were removed from the laboratory furnace after the shown
duration (annealing time). They were examined for their grain structure evolution,
fraction recrystallized, grain size and microhardness, all in their longitudinal plane of
direction. Direct comparisons were performed with the pre and post-annealed
samples from the previous benchmarking exercise.
2.3.3 Establishing the recrystallization kinetics with isochronal and isothermal

experiments
The aim of this experiment was to examine the rate of recrystallization, to

extract the specific “critical” temperature-time values for the provided material and to
perform a fitting of the experimental results with the JMAK equation. The
determination of the specific material “critical” values would be also useful on
production scale. The description of the isochronal and isothermal experiments was
given in 2.2.6.
For the isochronal experiment, all specimens had a 30 min dwell in the
furnace set at selected temperatures, shown in Table 16.
Table 16: Isochronal (30min) experiment temperatures.
Temperature (˚C) Specimens code

100 S1_1 S2_1
150 S1_2 S2_2
240 S1_3 S2_3
260 S1_4 S2_4
280 S1_5 S2_5
300 S1_6 S2_6
320 S1_7 S2_7
340 S1_8 S2_8
360 S1_9 S2_9
380 S1_10 S2_10
400 S1_11 S2_11
420 S1_12 S2_12
For the isothermal experiment, all specimens were placed in a pre-heated

furnace set at the previously measured “critical” temperature (Tcrit - the temperature
108
at which the fraction recrystallized was ~50%, after a 30 min dwell) and taken out
after specified times, as shown in Table 17.
Table 17: Isothermal treatment times at Tcrit.
Duration (min) Specimen code

5 S1_1 S2_1
10 S1_2 S2_2
15 S1_3 S2_3
20 S1_4 S2_4
25 S1_5 S2_5
30 S1_6 S2_6
35 S1_7 S2_7
40 S1_8 S2_8
45 S1_9 S2_9
60 S1_10 S2_10
The isochronal and isothermal samples were prepared in pack mounts,

polished and Barker’s anodized to examine their grain structure, fraction
recrystallized and microhardness, all at their longitudinal direction. Consequently,
the plots of fraction recrystallized and microhardness with temperature (isochronal)
and time (isothermal) were created.
The JMAK equation, according to the previous section 1.5.5.4, equation 5, is:
Xv = 1 − exp[ −(kt ) n ]
where, Xv is the fraction recrystallized,
t is the annealing time (s),
n is a numerical constant (JMAK exponent) and
k temperature dependent, reaction rate constant (s-1).
The JMAK equation fitting was performed by using the calculated fraction
 1 
recrystallized from the isothermal experiment results and plotting the ln[ln ]
 1− Xv 
against the ln(t ) , also known as the JMAK plot. The above plot is fitted by a straight
trend-line so that the JMAK equation numerical constants “n” and “k” are extracted.
109
The fitted JMAK equation was plotted together and compared to the isothermal
experiment fraction recrystallized results.
According to a different perspective, the kinetics of recrystallization may as

well be determined from microhardness values by considering the maximum and
minimum values, thus the pre- and post-annealing values respectively [Alvi et al.
2003].
The fraction recrystallized is derived from the following equation:
HV (max) − HV (t )
Xv = [Equation: 13]
HV (max) − HV (min)
where, Xv is the fraction recrystallized after time t,
HV(max) is the hardness Vickers before annealing,
HV(min) is the hardness Vickers after annealing and
HV(t) is the hardness Vickers at time t.
The JMAK equation fitting was applied similarly to previous practice.
2.3.4 Laboratory annealing simulation (2): extreme coil positions comparison
The scope of this experiment was to select two extreme coil positions and
compare their microstructures. The experiment was designed by considering the
results of the initial mathematical model for the industrial annealing process,
discussed at a later section. The aim was to investigate the microstructural
homogeneity and whether that was influenced by the different heating rates, times
and temperatures seen at the selected positions.
For this purpose, edge coil positions 1 and 6 were selected according to
Figure 30. Those two positions are not the most extreme by temperature coil
positions yet they should provide sufficient evidence of whether significant
differences exist or not. The coil positions were considered for a coil of:
• Outside Diameter (OD): 1850 mm
• Width: 1110 mm
• Gauge: 1.5 mm
On a steel spool of:
• Outside Diameter (OD): 570 mm
110
• Thickness: 33 mm
• Width: 1980 mm
The samples used for this experiment were all pre-annealed, outer-coil
(sample 1 - Table 10). The specimens were prepared similarly with the previous
laboratory furnace experiment practice and heat treated according to the
mathematical model annealing and cooling curve predictions for coil positions 1 and
6. They were removed from the laboratory furnace at selected annealing intervals
and examined so as to assess any differences. Table 18 shows the selected
annealing interval temperatures and the time at which those were achieved.
Table 18: Specimens for laboratory annealing simulation (2).
Position 1 Position 6
A/A
Temperature time Temperature time
(˚C) (min) (˚C) (min)
1 150 110 150 45
2 300 270 300 180
3 350 340 350 245
Maximum metal Maximum metal

4 490 500
temperature – 420 temperature – 450
Room temperature Room temperature
5 2500 2500
(fully annealed) (fully annealed)
After the furnace simulation, the electrical conductivity of each specimen was
measured. The specimens were then prepared in pack mounts, polished and
Barker’s anodized for further examinations. Particle size analysis and grain size
measurements were performed for the “maximum metal temperatures” and the
“room temperature” (fully annealed) specimens. The grain structure and
microhardness values were also examined and measured for all specimens.
2.3.5 Characterization of 0.3 mm cold rolled sheet
The scope of this experiment was to evaluate the influence of inter-annealing

and cold rolling processes on 0.3 mm cold rolled sheet samples, through
microstructure measurements and graining response behaviour.
111
For this purpose, typical industrial production samples were examined. The
samples had undergone different industrial annealing treatments (IA-1, IA-2 and
IA-3 practices - Table 12). The samples used for this experiment (samples 5, 6, 9
and 10 - Table 10) originated from the same coil with those used for the
benchmarking exercise of pre- and post-annealing materials, so that direct
comparisons were possible. Alongside the above samples, a non-annealed sample
at the same gauge (0.3 mm) was also included (sample 11 - Table 10).
The characterization of the above materials was performed by:
• Mechanical properties determination at the as rolled and baked (heat-treated

for 4 minutes at 280˚C) state, measuring the:
o Ultimate tensile strength (UTS)
o Yield strength (YS)
o Elongation (% EL)
o Modulus
• Particle size analysis
o At samples prepared in a pack-mount, polished and examined in the

longitudinal plane.
• Grain structure examination (evolution through cold rolling) in all three

planes:
o Longitudinal
o Transverse
o Surface plane
• Response to laboratory AC-electrograining by:
o Calculating and plotting the current (J) and charge densities (Q) for all
samples
o Graining topography examination with an electron microscope (SEM),

secondary electron detector, tilted at 40˚.
o Grained surface gloss measurements at three angles (20˚, 60˚ and 85˚).
All of the above examinations were performed according to the previously

described experimental techniques.
112
2.3.6 Annealing modelling part 2: extreme coil sizes comparison
The scope of this experiment was to identify the hottest and coolest coil
positions during industrial inter-annealing and investigate the influence of coil size
on time-temperature differences at those extreme coil positions. The results of this
experiment are of particular interest as far as the coil’s microstructural homogeneity
during inter-annealing, also suggested by results from the mathematical modelling,
discussed later on.
Two extreme coil sizes were considered for this study, listed in Table 19. The
mathematical model was applied for the IA-1 annealing practice for those extremes,
as described in 2.2.4 specifications.
Table 19: Pre-anneal coil extreme dimensions used as input for the mathematical
model.
Coil size Anneal gauge Coil dimensions

Coil width: 840 mm
“minimum” coil dimensions 1.5 mm
Coil diameter (OD): 1749 mm
Coil width: 1280 mm
“Maximum” coil dimensions 1.5 mm
Coil diameter (OD): 1812 mm
The coil positions considered for both mathematical models are shown in
Figure 30. Of particular interest were the hottest and coolest edge and centre coil
positions, for which the corresponding time-temperature annealing / cooling curves
were plotted and the relative heating rates calculated.
113
2.4 Experimental Procedure - Figures
Figure 19: Schematic representation of the research - experimentation area

(IA: Inter-annealing, CR: Cold rolling).
Figure 20: Experimental attributes of the in focus processes (∆ΙΑ, ∆CR) establishing
the changes to material characteristics, in regard to the critical product requirements
(∆CPR).
Figure 21: Sample selection for experimental work according to coil width.
114
Figure 22: A polished pack mount, showing the polished surface of examination.
Figure 23: Through sample thickness selection of imaging with SEM for the particle
size analysis (second upper quarter, along the red dashed line).
Figure 24: The Barker’s anodizing setup for preparation of grain structure
examination.
115
Figure 25: 3D aspect of the grain structure, indicating the near-surface ¼ thickness
position of imaging for determination of grain size.
Figure 26: Example of a grid of five equally spaced, parallel lines of the same length
for the determination of the mean lineal intercept length.
116
Figure 27: Example of a grid of equally spaced parallel and transverse lines which
form 100 crossing points that are used for the determination of the fraction
recrystallized.
Figure 28: The microhardness Vickers intender outline [Instron, 2000].
117
(t2)
(t1)
Figure 29: A microhardness test cycle profile [Instron, 2000].
Top-of-coil 12
11
6
10
4
Coil-interior
1 2 3
50 mm 9
Figure 30: Graphic representation of a coil, the coil’s sampling regions and the
selected positions for extracting temperature data over time from the mathematical
model.
118
Figure 31: Images of the layout used in the laboratory simulation of annealing
practice IA-1, showing the interior and exterior of the laboratory furnace used, the
thermocouples and the temperature data logger.
Verification trial of time-temperature furnace program

according to model positions 2 and 5
500
Model Position-2
450 Furnace program
400 Metal thermocouple
Air furnace thermocouple

350
Temperature ( C)
Model Position 5)
o
300
250
200
150
100
50
0
0 500 1000 1500 2000 2500 3000
time (min)
Figure 32: Plot of time-temperature program verification respective to model

positions 2 and 5.
119
Figure 33: Images of the equipment used to perform laboratory AC-electrograining.
Figure 34: Experimental setup for performing laboratory AC-electrograining.
120
3. Results and Discussion
This section presents and discusses the results of the experiments

described in the previous section.
3.1 Benchmarking of Pre- and Post- Annealed Materials
The results of the benchmarking exercise on pre- and post-annealed

industrial scale samples are shown and discussed in this section. In particular, the
results are presented according to the following measured parameters: particle size,
grain structure and microhardness.
The specimens for particle size analysis were examined with both optical
and electron microscopes. Representative optical and SEM images are shown in
Figures 35 and 36 respectively. The particle size analysis was performed on images
captured with the SEM backscattered detector, at x1000 magnification.
The parameters measured in order to characterize the particle population,

size and distribution were:
• The number of particles (N) per mm2,
• the particle area fractions (A %) and
• the particle circle diameter (Dc).
The measured data were compared as follows:
• Before (pre) and after (post) industrial inter-annealing,
• outer- and inner-coil positions,
• material anisotropy (surface, longitudinal and transverse plane) and
• different annealing practices.
Table 20 lists the results of the particle size analysis for this benchmarking
exercise.
121
Table 20: Benchmarking of pre- and post-annealed materials; particle size analysis
results.
Sample Plane N (per mm2) A % (%) Dc (um)

Mean σ Mean σ Mean σ
L 12358 1333 0.57 0.06 0.71 0.31
1 S 11202 1922 0.65 0.12 0.77 0.39
T 11027 1039 0.49 0.07 0.70 0.28
L 14178 1707 0.57 0.08 0.67 0.26
2 S 15075 5011 0.93 0.29 0.79 0.41
T 13485 1312 0.46 0.07 0.62 0.23
L 12422 1375 0.59 0.09 0.71 0.31
3 S 12755 1804 0.67 0.08 0.75 0.33
T 12857 2111 0.50 0.10 0.66 0.23
L 10629 985 0.53 0.08 0.73 0.31
4 S 15269 1805 0.97 0.14 0.81 0.39
T 11886 1437 0.49 0.10 0.68 0.25
L 13467 1527 0.65 0.12 0.72 0.32
7 S 15620 1952 0.84 0.14 0.76 0.33
T 11581 1439 0.50 0.10 0.69 0.28
L 11886 1128 0.57 0.07 0.71 0.32
8 S 14650 1753 0.78 0.14 0.75 0.34
T 12016 1243 0.48 0.04 0.67 0.26
L: longitudinal, S: surface, T: transverse plane
Figure 37 shows the average number of particles, (N) per mm2, for all
samples (1, 2, 3, 4, 7 and 8). All of the measured differences are within ±3000
particles per mm2, which is close to ±2 standard deviations (σ). The particle number
does not alter significantly during inter-annealing. The pre-annealed inner-coil
sample (S2) displayed slightly higher numbers of particles compared with the
outer-coil sample (S1) at all three planes. However, that was not found after
annealing. The number of particles (N), averaged from all samples, was 14095 in
the surface plane, 12490 in the longitudinal plane and 12142 in the transverse
plane. Four of the six samples revealed more particles in the surface plane
compared with the longitudinal and transverse planes. There is no measurable
influence of the different annealing practices on N.
122
Figure 38 compares the average measured volume fraction (A %) for all
samples. There is no significant change in A % during inter-annealing. The mean
A % over all samples is higher in the surface plane (0.81 %) compared with the
longitudinal (0.58 %) and transverse (0.49 %) planes. In particular, at the surface
plane of examination, the inner-coil position specimens exhibit higher volume
fractions (S2, S4: average of 0.95 %) compared with the respective outer-coil
position specimens (S1, S3: average of 0.66 %).
The mean particle circle diameter (Dc), for all samples, is compared in
Figure 39. These are similar for all the samples. The average Dc over all the
samples was 0.77 um in the surface, 0.71 um in the longitudinal and 0.67 um in the
transverse planes. There was no alteration of the average size of the second phase
particles, before and after industrial inter-annealing. There are no significant
differences in the mean particle size at the inner- and outer-coil positions. The
particle size is also similar after different annealing practices. All differences are
measured within ±1σ. There is no measurable coarsening of the second phase
particles after longer (IA-2) or hotter (IA-3) annealing practices that would suggest
intense precipitation due to the extra annealing time or the higher annealing
temperature.
The particle size distribution shows that the majority of particles are relatively
small (Dc ≤1 um) and similarly distributed in all the examined planes. As the particle
size gets larger the population reduces. Very few larger particles (Dc ≥ 2 um) are
encountered, the majority of which are present in the surface plane, less in the
longitudinal plane and the least in the transverse plane. This is in accordance with
the geometric shape (flat discs and rods) of the particles and their alignment to the
rolling direction. The above results are graphically shown with the logarithmic,
cumulative particle size distribution curves of sample 1 in Figure 40. The other
samples show similar distributions.
Figure 41 shows two logarithmic cumulative graphs of the particle size

distributions for the inner- and outer-coil positions, before and after inter-annealing,
in the longitudinal plane. There are no significant differences evident. The results
are also similar in the surface and transverse planes.
Two logarithmic cumulative graphs of the particle size distributions before

and after annealing, at the inner- and outer-coil positions, in the longitudinal plane
are shown in Figure 42. The particle size distribution is not altered through
inter-annealing. The results are also similar for the surface and transverse planes.
123
Figure 43 shows a logarithmic, cumulative graph that compares the particle
size distributions in the transverse plane after different annealing practices. The
graph shows that for this particular plane the number of large particles (Dc ≥ 1.5 um)
is marginally higher after longer (IA-2) or hotter (IA-3) annealing treatments,
compared with the typical (IA-1) annealing practice. These differences, however, are
not significant and they are therefore attributed to experimental error. This was also
the case for the other two planes.
A general comment on the particle size analysis is that there are no

significant differences in particle size, population and size distribution during
inter-annealing, between the inner- and outer-coil positions and after the different
annealing practices. There is only an anisotropy trend observed in the majority of
the investigations that showed the following:
Surface plane ≥ longitudinal plane ≥ transverse plane
It should be noted that the analysis was limited to particles of A ≥ 0.15 um2.
Thus, it is not possible to comment on the difference in dispersoids or fine
precipitates during inter-annealing. Within these analysis limitations, no particle
coarsening or precipitation mechanism, or change in solute could be identified.
3.1.2 Grain structure analysis
This section shows the grain structure results with images of all anneal
gauge samples and measures the post-annealed samples’ mean lineal intercept
lengths ( l ).
Figures 44 and 45 show the grain structure evolution through inter-annealing

in all three planes of examination, viewed at x50 and x200 magnifications. The
transition from deformed and elongated grain shapes to an equiaxed recrystallized
one is evident. The post-annealed fully recrystallized grain structure shows no
apparent visual differences between the inner- and outer-coil positions. Figure 46
compares the annealed grain structures for different industrial inter-annealing
practices. There are no visible differences.
For all the annealed samples, the grain structures are not uniform through
the coil thickness. The centerline shows a finer grain structure compared with both
upper and lower surfaces. This is explained by the non-uniform distribution of strain
through the thickness of the rolled sheet prior to annealing. During hot and cold
rolling, both surfaces attain more strain compared with the centre-thickness of the
124
sheet. Other differences such as solute or particle distribution may also play a role.
However, as already mentioned in the literature review, strain is the major factor
influencing the recrystallization progress.
The grain size of the annealed samples was evaluated by calculating the
lineal intercept lengths in all three planes of examination. The results are listed in
Table 21.
Table 21: Lineal intercept length measurements on industrially annealed samples.
Coil Annealing Lineal intercept length ( l ) - um

Sample Plane
position practice
Mean σ
L 26.9 3.0
3 Outer-coil IA-1 S 29.7 3.4
T 32.0 3.5
L 30.2 4.0
4 Inner-coil IA-1 S 34.0 4.1
T 31.6 3.8
L 30.2 4.4
T 31.8 3.9
L 34.4 4.8
T 35.5 3.8
L: longitudinal, S: surface, T: transverse plane
The mean lineal intercept lengths of the industrially annealed samples are
shown in Figure 47. Of particular interest were the differences between the inner-coil
(S4) and outer-coil (S3) positions, and between the different annealing practices
(S3, S7 and S8). The graph indicates no significant differences regardless of the
plane of examination, the coil position or the annealing practice. All measured
differences lie within ±1 σ. Thus, despite the longer (IA-2) or hotter (IA-3) annealing
practices and the different coil position geometries, there are no signs of grain
growth occurrence.
Figure 48 shows the histogram analysis from the lineal intercept length
measurements. Although most are close to normal distribution, some samples (e.g.
8T) show asymmetric distributions which may indicate the onset of grain coarsening.
This is of particular interest when considering the hotter annealed sample 7 and the
125
longer annealed sample 8. Further detailed study would be required in order to
confirm this.
3.1.3 Microhardness
The microhardness was examined on all samples and the results are listed
in Table 22.
Table 22: Benchmarking of pre- and post-annealed materials; microhardness.
Hardness Vickers (HV)

Sample
Mean σ
Surface plane
1 50.5 0.8
2 50.5 0.5
3 23.6 0.1
4 23.9 0.3
7 23.9 0.5
8 23.7 0.7
Figure 49 shows a graph of the mean microhardness of the industrial scale

samples. There is a 50 % drop in microhardness after inter-annealing, which is
consistent with the deformed (S1, S2) and fully recrystallized (S3, S4, S7, S8) grain
structures discussed earlier in 3.1.2. The result is not affected by coil position
sampling or different annealing practices.
3.2 Annealing Modelling and Laboratory Annealing Simulation (1): Typical Coil
Position
The results of this experiment are presented in two parts. The first part
shows the mathematical model predictions of temperatures over time, experienced
within a coil. The second part examines laboratory specimens that were subjected to
the typical annealing practice IA-1 at selected annealing plus cooling intervals.
3.2.1 Annealing model
Dr. Ioannis Contopoulos (ELKEME S.A.) created a mathematical model of a

typical industrial annealing furnace. Figure 50 compares the model predictions with
temperatures measured with thermocouples during a recent furnace trial at similar
126
coil positions and shows good agreement between the two. However, this annealing
model has not yet been industrially verified by an instrumented annealing cycle.
The model was used to compare two coil sizes. The coils differed only in
their outside diameters (OD), which were 1850 mm and 1500 mm. The other coil
size dimensions (width, gauge) and the steel spool size were considered to be the
same. The mathematical model predicted temperatures over time for coil positions
1, 2, 3, 4, 5 and 6, according to Figure 30.
Figures 51 and 52 compare the predicted from the model curves for each
coil position of the OD: 1850 and 1500 mm coils respectively. The large coil shows
great temperature differences between the top-of-coil (coil’s top surface) and the
coil-interior. The small coil, compared with the large coil, shows a faster initial
temperature rise and much smaller temperature differences between the coil surface
and coil-interior. The small coil surface does not heat as much as the large coil
surface, which is also shown in Figures 53 and 54.
The temperature variations within the coil are displayed in Figures 53 and
54. Each figure is a snapshot at the end of the annealing cycle. It can be seen from
these images that the large coil has a temperature difference (∆T) between the top-
of-coil and coil-interior of ~60 ˚C. The small coil shows a substantially less ∆T
between the same positions. The large coil is very close to the entrance of the
ceiling fan where the air flow is at its highest and this may produce problematic “hot
spots” at the coil’s top surface. This matter is further investigated in following
sections.
The mathematical model also predicted the coil cooling for the OD: 1850 mm
coil, following its exit from the annealing furnace. Figure 55 shows the predicted
annealing plus cooling curves for coil positions 1, 2, 3, 4, 5 and 6. These curves
were used as guidelines in performing the following laboratory annealing simulation.
3.2.2 Laboratory annealing simulation (1): typical coil position
Laboratory annealing simulation (1) is a furnace experiment that simulates

the typical annealing practice IA-1, according to the average coil positions 2 and 5.
The furnace programme created for this simulation was calibrated and verified
according to 2.2.5. Figure 56 shows the annealing plus cooling curves of the
simulation and the time-temperature intervals at which samples were taken for
examinations (also shown in Table 15). The simulation was performed on
pre-annealed outer-coil sample (S1) and inner-coil (S2).
127
Figure 57 shows a sequence of representative grain structure images from
the outer-coil position at the selected time-temperature intervals (the inner-coil
position images were alike). At 150 ˚C (110 minutes) and 250 ˚C (190 minutes) the
structure is still deformed. At 300 ˚C (280 minutes), there are signs of partial
recrystallization. This suggests that the recrystallization onset is between
250 - 300 ˚C (190 - 280 minutes). At 350 ˚C (345 minutes), the structure is fully
recrystallized; however, the grain size is not uniform through the coil thickness due
to unequal distribution of strain through the thickness of the rolled sheet prior to
annealing, as explained in 3.1.2. At 420 ˚C (495 minutes), which is the peak metal
temperature during annealing, the grain structure is very similar to the previous
interval. The grain structure does not alter during the following cooling intervals.
There are no signs of intense grain growth occurring.
The micrographs of Figure 58 present three distinct phases. The first one
shows the recovery initiation. Although both structures are heavily deformed, the
heated specimen, at 150 ˚C, shows a sharper, more well-defined grain structure.
This is attributed to the initial stages of recovery (point defect and dislocation
annihilation, re-arrangement and sub-grain formation). The extent of recovery
cannot be estimated from these images. The second one shows the recrystallization
initiation. At 300 °C, recrystallization has alread y commenced and the grain
structure is partially recrystallized. The fraction recrystallized for sample S1
(outer-coil) was measured: X v = 0.12 (± 0.015 ) . The third one compares the fully
recrystallized state of the laboratory specimen (S1_4: 350 ˚C - 345 minutes) and the
industrial scale annealed sample (S3). Full recrystallization occurs between 300 and
350 °C. However, the metal continues heating up to 420 °C. The fully recrystallized
specimen at 350 °C and the industrially annealed sa mple 3 do not show significant
structure differences. Sample 3 appears to have slightly coarser grains; however,
measurement of the lineal intercept lengths did not reveal significant differences.
Table 23 lists the results of the lineal intercept lengths for the fully
recrystallized, laboratory annealed specimens and the industrially annealed
samples. Figure 59 compares the mean lineal intercept lengths of the fully
recrystallized, laboratory annealed specimens and the industrially annealed
samples, in the longitudinal plane.
128
Table 23: Laboratory annealing simulation (1); lineal intercept length
measurements.
Specimen Lineal intercept length ( l ) - um

/ Sample
Mean σ
S1_4 27.5 4.5
Longitudinal plane
S1_5 28.4 6.9
S1_6 28.4 3.4
S1_7 27.2 2.7
S1_8 30.5 5.8
S3 26.9 2.9
S4 30.2 4.0
S7 30.2 4.4
S8 34.4 4.8
All measured mean lineal intercept lengths ( l ) are within ±1σ and, therefore,
are not significantly different.
Table 24 lists the microhardness measurements for the industrial and

simulated samples and specimens, from the outer-coil (S1, S3, S1_1-8) and the
inner-coil (S2, S4, S2_1-8) positions.
Table 24: Laboratory annealing simulation (1); microhardness measurements.
Hardness Vickers Hardness Vickers

Specimen (HV) Sample (HV)
Plane
/ Sample
Mean σ Mean σ
S S1 50.5 0.8 S2 50.5 0.5
L S1_1 49.9 1.0 S2_1 48.9 1.4
L S1_2 43.9 1.1 S2_2 41.9 0.8
L S1_3 32.5 1.5 S2_3 28.9 0.8
L S1_4 22.0 0.5 S2_4 22.6 0.5
L S1_5 22.4 0.3 S2_5 22.0 0.6
L S1_6 21.8 0.5 S2_6 22.1 0.6
L S1_7 22.0 0.3 S2_7 22.2 0.7
L S1_8 22.0 0.6 S2_8 21.6 0.4
S S3 23.6 0.1 S4 23.9 0.3
129
Figure 60 shows the microhardness decrease during the annealing plus
cooling simulation. There are no significant differences in the measured hardness
values between the inner- and outer-coil positions. The minor observed differences
during the recovery and early recrystallization period (150, 250 and 300 °C intervals)
are related to the different strain levels from the prior deformation stages. The
hardness value decreases due to softening. The microhardness curves show two
regions. The first region is a rapid decrease of microhardness due to recovery and
recrystallization occurrence. During the second region, the microhardness value
does not alter significantly. This occurs once the material is fully recrystallized
despite the fact that it remains at high temperatures and for longer times. The
slightly increased microhardness value of the industrially annealed specimens,
compared with the simulation annealed values, is attributed to measurement errors
such as those stated in section 2.2.3.
3.3 Establishing the Recrystallization Kinetics with Isochronal and Isothermal

Experiments
The results of this experiment are presented in three parts: the isochronal
experiment, the isothermal experiment and the JMAK equation fitting.
Figure 61 shows the time necessary for a specimen to heat-up to the target
temperature once inserted into the laboratory furnace. This is 2 minutes.
3.3.1 Isochronal experiment
The outer-coil (S1_1-12) and inner-coil (S2_1-12) specimens were annealed

at various temperatures for 30 minutes. Figure 62 shows the grain structures of the
isochronally annealed specimens in the longitudinal plane. The visual observation
results and the measured fractions recrystallized are listed in Table 25.
130
Table 25: Isochronal experiment; optical observation remarks and fractions
recrystallized.
Temperature Grain structure after Xv (fraction

Specimen
(˚C) experiment recrystallized)
S1_1
100 Not Recrystallized 0
S2_1
S1_2
S2_2
S1_3
S2_3
S1_4
S2_4
S1_5
S2_5
S1_6 Partially Recrystallized 0.10
300
320
S2_7 Fully Recrystallized 1
S1_8
340 Fully Recrystallized 1
S2_8
S1_9
S2_9
S1_10
S2_10
S1_11
S2_11
S1_12
S2_12
Figure 63 shows that the fraction recrystallized against temperature curves

for both the inner- and outer-coil position samples are identical. This graph also
shows that the “critical recrystallization temperature” (TREX), i.e. the temperature at
which 50% of the structure is recrystallized, after a 30 minute annealing,
is TREX ≈ 310°C . The fraction recrystallized graph is a characteristic “S” shaped
curve.
131
Table 26 lists the microhardness measurements for the isochronally
annealed, outer-coil specimens (S1_1 - 12).
Table 26: Isochronal experiment (30 minutes); microhardness measurements.
Temperature Hardness Vickers (HV)

(˚C) Specimen
Mean σ
100 S1_1 53.5 1.2
150 S1_2 54.8 0.7
240 S1_3 47.5 0.5
260 45.0 0.6
Longitudinal plane
S1_4
280 S1_5 41.1 0.7
300 S1_6 36.6 0.6
320 S1_7 29.0 0.4
340 S1_8 28.7 0.9
360 S1_9 30.2 1.3
380 S1_10 30.6 0.6
400 S1_11 30.5 0.9
420 S1_12 29.7 0.3
Figure 64 shows a graph of the mean microhardness against temperature for

the isochronal annealing. There is good correlation between the microhardness
values and the observed grain structures. Microhardness drops ~50 % once the
grain structure is fully recrystallized, and then remains approximately constant. The
points between 150 and 300 ˚C correspond to the combined recovery and
recrystallization, although these two processes are not distinguished.
3.3.2 Isothermal experiment
The target temperature for the isothermal experiment’s outer-coil (S1_1-10)

and inner-coil (S2_1-10) specimens was 310 ˚C i.e. the calculated TREX. Figures 65
and 66 show the grain structures of the isothermally annealed specimens, in the
longitudinal plane. The results of visual observation and measured fractions
recrystallized are listed in Table 27.
132
Table 27: Isothermal experiment; optical observation remarks
Time at 310 ˚C Grain structure Xv (S1)

Specimen
(minutes) after experiment Mean σ
S1_1 Partially
5 0.04 0.02
S2_1 Recrystallized
S1_2 Partially
10 0.04 0.01
S2_2 Recrystallized
S1_3 Partially
15 0.15 0.03
S2_3 Recrystallized
S1_4 Partially
20 0.14 0.04
S2_4 Recrystallized
S1_5 Partially
25 0.28 0.04
S2_5 Recrystallized
S1_6 Partially, almost

30 0.97 0.02
S2_6 fully Recrystallized

35 0.98 0.02

40 0.89 0.05
S1_9 Fully
45 1 -
S2_9 Recrystallized
S1_10 Fully
60 1 -
S2_10 Recrystallized
The grain structures (S1 vs. S2) were very similar, regardless the coil
position sampling. Signs of recrystallization were evident at this temperature even
after just 5 minutes. Figure 67 shows the fraction recrystallized against time from the
isothermal annealing experiment. The graph shows the “critical time” (t0.5) at which
50% of the structure is recrystallized. This was estimated to be t 0.5 ≈ 28 minutes at
310 ˚C, which also verifies previous isochronal experiment results. The fraction
recrystallized graph is, again, a characteristic “S” shaped curve, starting slowly then
increasing sharply and finally stabilizing.
Table 28 lists the microhardness measurements for the isothermally

annealed, outer-coil specimens (S1_1-10).
133
Table 28: Isothermal experiment; microhardness measurements.
Time Hardness Vickers (HV)

Specimen
(minutes) Mean σ
5 S1_1 38.4 0.6
10 S1_2 38.5 1.6
Longitudinal plane 15 S1_3 35.6 1.7
20 S1_4 36.3 0.7
25 S1_5 33.8 1.3
30 S1_6 28.3 1.0
35 S1_7 28.8 1.0
40 S1_8 29.9 1.4
45 S1_9 28.1 1.9
60 S1_10 27.0 0.5
Figure 68 displays the graph of these data. It shows an initial, sudden

decrease of microhardness. Once the grain structure is fully recrystallized,
microhardness doesn’t change much, similarly to isochronal annealing results. The
initial sudden drop is attributed to the prompt occurrence of recovery and
recrystallization initiation. The ‘elevated’ annealing temperature is an accelerating
factor for the softening mechanisms.
3.3.3 JMAK equation fitting
The calculated fractions recrystallized, from the isothermal experiment, were

used for the JMAK equation fitting. As described in 2.3.3, the fraction recrystallized
can be also determined by considering the microhardness values. Table 29 lists the
calculated fractions recrystallized from grain structure images and microhardness
data together with the JMAK equation calculations.
134
Table 29: JMAK equation fitting; calculated fractions recrystallized.
Calculated fraction JMAK equation

recrystallized
time Xv = 1 − exp[ −(kt)n ]
(s) (Xv)
Grain structure Grain structure
Microhardness Microhardness
images images
0 0.00 0.00 0.00 0.00
300 0.04 0.50 0.01 0.41
600 0.04 0.49 0.08 0.54
900 0.15 0.60 0.20 0.63
1200 0.14 0.57 0.37 0.69
1500 0.28 0.66 0.56 0.74
1800 0.97 0.86 0.73 0.78
2100 0.98 0.85 0.86 0.80
2400 0.89 0.81 0.93 0.83
2700 1.00 0.87 0.97 0.85
3600 1.00 0.91 1.00 0.89
Figure 69 shows the fitted JMAK equation and JMAK plot, according to the
grain structure images. The JMAK equation does not fit perfectly with the
experimental data, as anticipated by literature; however, it shows an acceptable
agreement. The reasons for the non-perfect fitting include:
• Local variations within samples, heterogeneity of the microstructure and

strain distribution throughout the sample thickness.
• Inherent sample preparation and measurement errors.
The microhardness calculated fractions recrystallized were similarly used to

create the JMAK plot and fit the JMAK equation, as shown in Figure 70.
Microhardness has been successfully used for deducing the fraction

recrystallized, during an isothermal experiment, of hot rolled (already recovered)
AA1050 [Alvi M.H. et al. 2003]. This set of specimens, however, was industrially
work hardened before laboratory annealing. The microhardness derived fractions
recrystallized showed poor consistency with the optically examined grain structures,
due to the implication of the recovery process.
Figure 71 compares the two different methodologies of calculating the

fraction recrystallized. The graph shows large differences between the two
135
methodologies. Table 30 lists the calculated JMAK parameters from both applied
methods.
Table 30: Calculated JMAK parameters.
Fraction recrystallized n k (s-1)

from (JMAK exponent) (reaction rate constant)
Isothermal
experiment Grain structure images 2.55 0.0006
Microhardness values 0.59 0.0011
3.4 Laboratory annealing simulation (2) – Extreme Coil Positions Comparison
This section investigates further into the temperature differences (∆Ts) within
a coil during industrial annealing. Section 3.2.1, covering the annealing model
results, predicted significant ∆Ts between the top-of-coil and coil-interior for the
OD: 1850 mm coil, at the end of the annealing cycle. Model positions 1 and 6,
according to Figure 30, were selected as two extreme coil positions to simulate and
examine the microstructural, thus property, homogeneity.
Figure 72 shows the model predicted and furnace programme verification

curves for the investigated positions. The specific intervals at which specimens were
selected and examined are also indicated. Table 31 shows the calculated (linear)
heating rates, up to TREX ≈ 310°C .
Table 31: Calculated (linear) heating rates.
Heating rate from 30 to 310 °C (°C/min)

Position 1 1
Position 6 1.6
The coil is heated 1.6 times faster at its top-of-coil position compared to the
coil-interior.
Figure 73 (a) compares the simulation derived annealing plus cooling curves
of the extreme coil positions. Figure 73 (b) shows the graph of the ∆Τ between the
extreme positions 6 and 1 against time, during annealing plus cooling. These data
are listed in Table 32.
136
Table 32: Time-temperature differences during annealing simulation of extreme coil
positions 1 and 6
Temperature (˚C)
∆t (min)
Pos 6 (T6) Pos 1 (T1) ∆Τ (T6-T1)
(for Pos 1 to reach T6)
150 72 78 65
300 206 94 90
350 273 77 95
450 420 30 -
The top-of-coil reaches TREX ≈ 310°C , within 175 min. The ∆Τ at that interval
is 91 ˚C. Within 230 min of the annealing initiation, the top-of-coil has already heated
up to 350 ˚C and is fully recrystallized (as shown in 3.2.2). Simultaneously, the
coil-interior is at 273 ˚C, not or just partially recrystallized. The maximum achieved
metal temperatures at the end of the annealing cycle are different by 30 ˚C.
The temperature hysteresis of the coil-interior compared with the top-of-coil

is due to the coil geometry and heat transfer. The coil-interior heating is also
dependent on a series of non-heat conductive obstacles, such as: surface
roughness, air and residual entrapped rolling oil within the coil wrappings and coiling
tension. During cooling, the coil-interior cools slower for the same reasons. It is
interesting, however, that during annealing plus cooling the extreme coil positions
stay above TREX for very similar times:
• Position 1 above 310 °C for 600 minutes.
• Position 6 above 310 °C for 590 minutes.
However, this is not the same for dwell at higher temperatures. For example,
the times spent above 350 °C and 400 °C are provide d below for the extreme
positions:
• Position 1 above 350°C for 460 minutes.
• Position 6 above 350°C for 410 minutes.
o Position 1 above 400°C for 150 minutes.
o Position 6 above 400°C for 220 minutes.
In order to assess whether the mentioned time-temperature differences have

any impact on the coil homogeneity or not, a series of examinations were
undertaken, as presented in the following sections.
137
Particle size analysis was performed at two examination intervals: the

‘maximum’ metal temperatures and after the simulation annealing. Representative
optical and backscattered electron micrographs of the simulated extreme coil
positions’ microstructures are shown in Figures 74 and 75. Table 33 lists the results
of the particle size analysis.
Table 33: Annealing simulation of extreme coil positions 1 and 6; particle size
analysis results.
‘Maximum’ metal temperatures

N (per mm2) A% (%) Dc (um)
Longitudinal plane
Position 1 14021 1180 0.53 0.08 0.62 0.31
Position 6 13688 1489 0.51 0.04 0.62 0.30
After simulation annealing

Position 1 15519 2541 0.62 0.13 0.63 0.33
Position 6 14289 1179 0.54 0.10 0.62 0.31
Figure 76 shows graphs of particle N per mm2, A % and Dc, from the
simulated extreme coil positions 1 and 6. All differences between positions 1 and 6
are measured within ±1σ; therefore, there are no significant differences in the
particle population and size between top-of-coil and coil-interior.
Figure 77 compares the particle size distribution, at both examination

intervals, between the simulated positions 1 and 6. The particle size distribution is
almost identical for the two coil positions, suggesting that the microstructure within
the coil is homogeneous. The slight variability shown after the annealing simulation,
at the coil-interior (position 1), with a higher distribution of large (Dc ≥ 2um) particles,
is considered to be within experimental error. This is because the population of large
Dc particles is rather small compared with the overall particle population.
Consequently, no precise statistical results can be provided for the larger particles.
As stated in 3.1.1, the particle size analysis was limited to particles of area
A ≥ 0.15 um2.
138
Figure 78 illustrates 3D representations of the extreme coil positions’ 1 and 6

grain structures at the selected temperature intervals, viewed at x50 and x200
magnifications. At 150 ˚C, the grain structures are still deformed for both positions
and no significant differences are detected. At 300 ˚C, some partial recrystallization
is evident. Table 34 shows the measured fractions recrystallized for both positions.
Table 34: Fraction recrystallized of the simulated extreme coil positions, at 300 ˚C.
Time to reach Fraction Standard

Extreme coil positions 300 ˚C Recrystallized deviation
(min) (%) (%)
Position 1 270 3.2 1.6
Position 6 180 4.8 0.8
The fraction recrystallized is slightly higher at position 6, despite the shorter

annealing time. This suggests that the faster heating rate is an accelerating
recrystallization factor.
At 350 ˚C, both position structures are fully recrystallized, with no significant
differences between them. The maximum metal temperatures are achieved 500
minutes after annealing initiation, being 420 ˚C for the coil-interior and 450 ˚C for the
top-of-coil. After 2500 minutes, of laboratory annealing plus cooling, the structures
from both positions are similarly fully recrystallized.
Table 35 lists the lineal intercept lengths for positions 1 and 6 at the
maximum achieved metal temperatures and after the simulation annealing, in the
surface plane.
Table 35: Extreme coil positions annealing simulation, lineal intercept length
measurements.
Lineal intercept length ( l ) - um

Sampling Maximum metal After simulation
Surface plane
interval temperatures annealing

Mean σ Mean σ
Position 1 22.8 1.1 33.6 4.3
Position 6 33.4 3.5 34.3 4.4
139
Figure 79 compares the mean lineal intercept lengths ( l ). At the maximum
metal temperatures stage, the top-of-coil grain structure is coarser compared with
the coil-interior. After laboratory annealing plus cooling, this is not evident. The l is
the same for both positions, and similar to the l of position 6 at the maximum
achieved metal temperature interval. The longer stay of position 6 (top-of-coil) at
higher temperatures does not promote grain growth. The corresponding l
histograms show normal distribution, which verifies previous assumptions.
3.4.3 Electrical conductivity
Table 36 lists the electrical conductivities (k) measured before, during and
after the lab simulation annealing of extreme coil positions 1 and 6. Figure 80
compares the curves of the changing electrical conductivity during the annealing
cycle between the simulated extreme coil positions 1 and 6. The industrial pre- and
post-annealed electrical conductivities are also plotted.
Table 36: Extreme coil positions annealing simulation; electrical conductivities (k)
measurements.
Electrical conductivity – k (% IACS)

Sampling Temperatures Position 1 Position 6
Mean σ Mean σ
150 ˚C 60.04 0.11 60.03 0.08
300 ˚C 60.52 0.03 60.65 0.03
350 ˚C 60.79 0.21 61.03 0.05
Max metal Temp 60.81 0.09 61.06 0.07
After lab simulation annealing 61.01 0.06 61.20 0.03
Pre-annealed Post-annealed
(production) (production)
Mean σ Mean σ
60.34 0.07 61.06 0.04
The effect of strain hardening (cold work) on the electrical conductivity of

aluminium is small relative to that of alloying elements (solute content). The
difference in electrical conductivity before, during and after annealing is
predominately related with diffusion of elements and solute content changes. The
140
electrical conductivity increases slightly after industrial annealing (0.7 % IACS). This
suggests little or no solute change after industrial annealing.
The extreme coil positions 1 and 6 show different k values during the
laboratory annealing simulation. The k differences are attributed to differences in
temperature and heating rate between the two positions. These are more distinct
once recrystallization has started (>300 ˚C). Position 6 reaches the maximum k at a
faster rate compared with position 1. However, after the lab simulation annealing,
the k difference is not significantly large. Therefore, the solute content is considered
to be the same for the two positions after annealing.
At 150 ˚C, the electrical conductivity, for both extreme positions, is lower
than the starting value. This behaviour (drop of % IACS) cannot be explained from
consideration of the literature. The measurements were repeatable for both extreme
coil positions. Elements such as magnesium, silicon, zinc or copper start diffusing at
temperatures close to 150 ˚C, hence, the electrical resistivity is altered. The
specimen quenching, once taken out of the laboratory furnace, might have
enhanced that behaviour. A thorough investigation of the electrical conductivity at
that range of temperatures should offer a better insight into the possible
explanations for this unexplained behaviour.
3.4.4 Microhardness
Table 37 lists the microhardness values for the simulated extreme positions
1 and 6 specimens, as quenched from the temperatures indicated.
Table 37: Extreme coil positions annealing simulation; microhardness

measurements.
Hardness Vickers (HV)

Sampling Temperatures Position 1 Position 6
Mean σ Mean σ
150˚C 53.4 0.6 50.8 2.2
300˚C 38.1 1.4 36.6 1.8
350˚C 26.0 0.3 25.5 1.3
Max metal Temp 26.4 0.9 25.6 1.1
After lab simulation annealing 26.6 1.4 25.3 1.7
141
Figure 81 compares the microhardness curves of the simulated extreme coil
positions 1 and 6. The microhardness curves show no significant differences
between the coil positions. This suggests that the hardness does not vary
significantly along the coil length during inter-annealing.
3.5 Characterization of 0.3 mm Cold Rolled Sheet
The characterization of the 0.3 mm cold rolled materials provides an insight

into the effects of the final cold rolling process and the influence of the different
annealing practices (IA-1, IA-2, IA-3), on the critical properties of the final product.
The samples examined were industrial scale annealed and cold-rolled samples, with
similar mentality as the benchmarking exercise 3.1.
The mechanical properties, particle size analysis, grain structure analysis

and response to AC-Electrograining are reported.
3.5.1 Mechanical properties
Table 38 lists the results of the mechanical properties measurements in the

as rolled and baked (heat-treated for 4 minutes at 280 ˚C) states.
Table 38: Mechanical properties of 0.3 mm gauge sheet, as rolled and after heat
treatment (baked).
UTS (MPa) YS (MPa)

Sample
As rolled Baked As rolled Baked
5 Annealed, IA-1, Outer-coil 178 147 168 143
6 Annealed, IA-1, Inner-coil 181 147 172 143
11 Non-annealed, Inner-coil 200 167 221 174
Elongation (%) Modulus (GPa)

Sample
As rolled Baked As rolled Baked
5 Annealed, IA-1, Outer-coil 2.6 1.8 60 51
6 Annealed, IA-1, Inner-coil 2.2 1.8 54 49
11 Non-annealed, Inner-coil 2.9 0.6 68 62
142
The as rolled and baked ultimate tensile strength (UTS), yield strength (YS),
elongation (% EL) and modulus are graphically shown in Figure 82. The graphs also
show the drop in strength after the thermal treatment. As explained in section 1.4.1,
ideally this drop should be a minimum.
The UTS was similar for all 0.3 mm cold rolled samples, at the as-rolled and
baked stages, regardless of the different annealing practices. This was also the
case for YS. The non-annealed sample displays higher strength values compared
with the annealed samples, due to the extra deformation. The UTS decrease after
heat treatment (average of 33 MPa) is similar for all samples. The YS decrease,
however, is significantly more for the non-annealed sample (47.5 MPa) compared
with the annealed samples (average of 33 MPa). The extra strain, which is the
driving force for recovery and recrystallization processes, enhances the softening
kinetics.
There is a much larger decrease in % EL after heat treatment for the

non-annealed sample (2.3 %) compared with the annealed samples (average of
0.5 %), as shown in Figure 82c. The modulus does not show any significant
differences between all final gauge samples, as shown in Figure 82d.
The results of mechanical properties testing reveal no significant differences

between differently annealed samples. The non-annealed sample displays higher
YS and % EL decrease after thermal treatment. This is not desirable for the
on-press performance of the printing plate. Thus, omitting the inter-annealing
process step is not ideal in terms of mechanical properties.
The particle size analysis of the final gauge materials aimed to compare the
effects of final cold rolling and the influence of different (longer and hotter) annealing
paths. The outer-coil and inner-coil positions were also compared. Figure 83 shows
representative backscattered electron micrographs of the final gauge materials.
Table 39 lists the results of the particle size analysis.
143
Table 39: Benchmarking of 0.3 mm gauge sheet; particle size analysis results.

Sample
Longitudinal plane
5 Annealed, IA-1, Outer-coil 14021 1672 0.66 0.10 0.71 0.30
6 Annealed, IA-1, Inner-coil 14594 1717 0.60 0.09 0.67 0.26
11 Non-annealed, Inner-coil 15602 1294 0.73 0.07 0.70 0.31
Figure 84 shows graphs of particle size data measured in the longitudinal

plane of the 0.3 mm gauge materials. All measured differences are considered
insignificant. Figure 85 displays the distribution of second phase particles, in the
longitudinal plane of the 0.3 mm gauge samples. The particle size distribution is not
significantly different between all samples. A minor, yet insignificant, difference in
the logarithmic, cumulative graph is the slightly higher distribution of larger
(Dc ≥ 1.5 um) particles for the non-annealed sample. The 0.3 mm gauge materials’
particle size analysis suggests that different annealing paths or annealing omission
does not affect the population, size and distribution of the second phase particles.
The literature indicates that the effect of final cold rolling on the population,
size and distribution of the second phase particles should be minimal. Figure 86
shows graphs of particle size data of outer-coil and inner-coil samples, before and
after industrial annealing and after final industrial cold rolling. All samples are from
the same coil. A non-annealed final gauge sample is also compared. The graphs
show small differences in N, but no significant differences in A% and Dc. The
average particle size is not altered through final cold rolling. The population might
be slightly increased due to the particles’ break up during rolling. Figure 87
compares the distribution of second phase particles at the inner-coil position and
indicated process stages. There are no significant differences in the size
distributions of these samples. The inter-annealing and cold rolling processes do not
affect the particles’ size distribution.
As stated in 3.1.1, the particle size analysis was limited to particles of area
A ≥ 0.15 um2.
144
The grain structure of the final gauge materials was examined in all three
planes. Characteristic images of the grain structures are shown in Figures 88 and
89, in 2D and 3D respectively.
The shape of the grains appears elongated due to the heavily deformation
imposed after inter-annealing process, during final cold rolling. There are no
differences in the grain structures of the annealed 0.3 mm cold rolled samples. The
non-annealed sample displays an even more deformed grain structure, of ‘thinner’
(more elongated) shaped grains, compared to the annealed ones. This is the result
of the extra work hardening. Apart from visual observation, no other grain structure
characteristic (value or number) could distinguish the samples apart due to their
highly deformed nature.
Figure 90 shows a 3D representation of this grain structure evolution through

the inter-annealing and final cold rolling processes for the inner- and outer-coil
positions. The different strain levels through the sheet’s thickness at anneal gauge
does not influence the 0.3 mm cold rolled grain structure.
3.5.4 Laboratory AC-electrograining
The laboratory AC-electrograining developed grained surfaces from

industrial scale lithographic printing aluminium sheet substrates. The aim was to
measure the roughening behaviour of those samples at the same graining
conditions. The average current densities (J) and calculated charge densities (Q)
are listed in Table 40.
Table 40: AC-electrograined specimens, current (J) and charge (Q) density results.
Current density (Adm-2) Charge

Sample density
Mean σ (Cdm-2)
5 Annealed, IA-1, Outer-coil 44.0 4.7 1020
6 Annealed, IA-1, Inner-coil 43.9 4.6 1017
11 Non-annealed, Inner-coil 44.4 4.6 1027
145
Figure 91 shows the variation of current density with time. There are no
significant differences between the samples in either current or charge density. This
suggests that despite the fact that the samples represent different coil positions
(outer and inner) and are from different annealing practices, the reactivity properties
are very much the same.
Figure 92 shows representative SEM micrographs of the laboratory grained

surfaces. There are no apparent differences observed. This suggests that the
AC-electrograining behaviour is very similar for all examined samples.
The AC-electrograined surfaces were also evaluated with gloss

measurements, listed in Table 41.
Table 41: AC-electrograined specimens, gloss measurements.
20° 60° 85°

Sample
5 Annealed, IA-1, Outer-coil 1.4 0.02 7.4 0.2 20.7 1.2
6 Annealed, IA-1, Inner-coil 1.4 0.01 7.4 0.3 20.2 2.2
11 Non-annealed, Inner-coil 1.5 0.06 8.7 0.3 22.3 3.1
Figure 93 compares the average gloss measurements at all three measured

angles and shows that the non-annealed sample is consistently higher compared
with the other annealed samples. This indicates an improved graining result for the
annealed samples compared with the non-annealed samples.
3.6 Annealing Modelling Part 2: Extreme Coil Sizes Comparison
The results of the mathematical model, in section 3.2.1, predicted significant

temperature differences (∆Τs) between the top-of-coil and the coil-interior during
annealing of an OD: 1850 mm coil. The model was used again to determine if these
∆Τs were observed for other coil sizes and the variations for extreme coil sizes. Two
new sets of coil size dimensions were used as input for the model. Those are listed
in Table 19, section 2.3.6
Figures 30 shows all twelve coil positions, considered for the model. Figure
94 illustrates the model predictions for both ‘minimum’ and ‘maximum’ coil sizes:
146
• Hottest coil centre width position: top-of-coil position 12.
• Coolest coil centre width position: coil-interior position 7.
o Hottest coil edge position: top-of-coil position 6.
o Coolest coil edge position: coil-interior position 1.
Figure 95 compares the maximum predicted temperatures during annealing,

for all twelve positions, from both coil sizes. The graph shows that positions 1, 6, 7
and 12 display the largest ∆Τs.
Figure 96 compares the predicted annealing curves for positions 1, 6, 7 and

12. These graphs indicate different heating rates and a large ∆Τ between the
coil-interior and top-of-coil. The differences are larger at the coil centre width in
contrast to the coil edge. The interior coil positions display a temperature lagging
compared to the exterior ones, which heat-up faster. This lag peaks at
~120 minutes, regardless of the coil position or dimensions. This is also shown in
Figure 97. The ∆Τs decrease towards the end of the annealing cycle.
Figure 98 compares the model curves, at the same coil positions, for the
‘minimum’ and ‘maximum’ coil sizes. No significant differences are observed for the
top-of-coil positions (6 and 12), yet some small differences are evident for the
coil-interior positions (1 and 7). The latter positions heat-up faster at the ‘minimum’
coil size. This result is not attributed solely to coil size differences but to other
factors as well, such us the heat conductivity of the coil. Table 42 lists the calculated
linear heating rates at the investigated coil positions. The heating rates were
considered from ambient temperature (30 °C) to abov e TREX ≈ 310°C .
Table 42: Annealing modelling part 2, calculated (linear) heating rates.
Calculated (linear) heating rate (°C/min)

Position 1 Position 6 Position 7 Position 12
Annealing model 1 –
1.1 1.6 1.0 2.1
‘minimum’ coil dimensions
Annealing model 2 –
0.9 1.5 0.9 1.9
‘Maximum’ coil dimensions
The calculated linear heating rates are higher for the ‘minimum’ coil size. The
highest rate was calculated for position 12 of the ‘minimum’ coil size and the lowest
for position 7 of the ‘maximum’ coil size. Table 43 shows the predicted critical
time-temperature differences during annealing plus cooling.
147
Table 43: Mathematical annealing model, time-temperature critical differences.
Maximum (∆T) Maximum (∆T)
[occurring at ~120 min] [at end of annealing cycle]
(°C) (°C)
Annealing Between
82 24
model 1 – Pos. 1-6
‘minimum’ coil
Between
dimensions 148 46
Pos. 7-12
Annealing Between
100 38
model 2 – Pos. 1-6
‘Maximum’ coil
Between
dimensions 154 51
Pos. 7-12
Total time above TREX Total time above 400 °C

(min) (min)
Annealing Pos. 1 520 90

model 1 – Pos. 6 540 160
‘minimum’ coil
Pos. 7 520 50
dimensions
Pos. 12 530 210
Annealing Pos. 1 480 0

model 2 – Pos. 6 480 150
‘Maximum’ coil
Pos. 7 470 0
dimensions
Pos. 12 500 200
The maximum ∆T between the hottest and coolest coil positions is 148 °C for
the ‘minimum’ coil and 154 °C for the ‘maximum’ coi l. These are extremely
significant differences, occurring at the critical recovery and recrystallization stages,
which could implicitly affect the microstructure uniformity. Nonetheless, the 3.4
section microstructure analysis showed that the ∆T of the coil edge positions 1 and
6 do not result in any significant differences after annealing. The ∆T is about
one-third lower at the end of the annealing cycle compared with the maximum ∆T.
The total time (heating and cooling) for all positions above TREX ≈ 310°C is
very similar (~500 minutes), irrespective of coil size or position. However, the total
time above 400 °C varies significantly depending on position within the coil. For the
‘maximum’ coil size, the total time is 200 minutes at position 12, while position 7
never rises above that temperature.
The second part of annealing modelling for extreme coil sizes showed that
the larger coil-interior does not always achieve the target metal temperature for the
148
target time during annealing. This could possibly evoke local solute differences and,
therefore, influence the critical product requirements of the lithographic printing
plate, despite previous results that showed no significant differences for smaller
∆Ts.
149
3.7 Results and Discussion - Figures
Figure 35: Representative optical micrographs of the second phase particles

population, size and distribution for sample 2 (upper row, pre-annealed) and sample
4 (bottom row, post-annealed), viewed at x1000 magnification and examined in the
surface (S), the longitudinal (L) and transverse (T) planes.
Figure 36: Representative backscattered electron micrographs of the second phase

particles population, size and distribution for sample 1 (upper row, pre-annealed)
and sample 3 (bottom row, post-annealed), viewed at x1000 magnification and
examined in the surface (S), the longitudinal (L) and transverse (T) planes.
150
Longitudinal
Mean Number of particles per mm2
Transverse
Pre-anneal Post-anneal Surface
25000
Outer-coil Outer-coil Inner-coil Outer-coil Outer-coil

Inner-coil
IA-1 IA-1 IA-3 IA-2
20000
15000
10000
5000
0
Sample 1 Sample 2 Sample 3 Sample 4 Sample 7 Sample 8
Figure 37: Graph of the mean number of second phase particles measured per
mm2. The error bars indicate ± one standard deviation (1σ).
Mean Area Fraction % Longitudinal

Transverse
1.40
Outer-coil Inner-coil Outer-coil Inner-coil Outer-coil Outer-coil
IA-1 IA-1 IA-3 IA-2
1.20
1.00
0.80
0.60
0.40
0.20
0.00
Sam ple 1 Sam ple 2 Sam ple 3 Sam ple 4 Sam ple 7 Sam ple 8
Figure 38: Graph of the mean area fraction of second phase particles. The error
bars indicate ±.1σ.
151
Longitudinal
Mean circle diameter (Dc / um)
Transverse
0,9
Outer-coil Inner-coil Outer-coil Outer-coil
Outer-coil Inner-coil IA-1 IA-1 IA-3 IA-2
0,9
0,8
0,8
um
0,7
0,7
0,6
0,6
0,5
Figure 39: Graph of the mean particle circle diameter measured. The error bars
indicate the upper and lower 95 % confidence limits (95 % CI).
Logarithmic cumulative particle size distribution

10000
Pre-annealed, sample 1 1L
L: Longitudinal 1S
S: Surface 1T
T: Transverse
1000
N/mm > Dc
2
100
10
0 1 Dcircle (um) 2 3
Figure 40: Logarithmic, cumulative graph of the particle size distribution for sample
1 in all three planes.
152
Logarithmic cumulative particle size distribution (a)
10000
Pre-annealed, longitudinal plane 1L
Sample 1: Outer-coil 2L
Sample 2: Inner-coil
1000
N/m m > Dc
2
100
10
0 1 2 3
Dcircle (um)
Logarithmic cumulative particle size distribution (b)

10000
3L
Post-annealed, longitudinal plane
Sample 3: Outer-coil 4L
1000
N /m m 2 > D c
100
10
Figure 41: Logarithmic, cumulative graphs of the particle size distribution, in the
longitudinal plane, of outer-coil samples 1 and 3, and inner-coil samples 2 and 4, (a)
before and (b) after inter-annealing.
153
Logarithmic cumulative particle size distribution (a)
10000
Outer-coil, longitudinal plane 1L
Sample 1: Pre-annealed 3L
Sample 3: Post-annealed
1000
N/mm2 > Dc
100
10
Logarithmic cumulative particle size distribution (b)

10000
Inner-coil, longitudinal plane 2L
Sample 2: Pre-annealed 4L
Sample 4: Post-annealed
1000
N /m m 2 > D c
100
10
Figure 42: Logarithmic, cumulative graphs of the particle size distribution, in the
longitudinal plane, of pre-annealed samples 1 and 2, and post-annealed samples 3
and 4 at (a) the outer-coil position and (b) the inner-coil position.
154
10000
3T - IA-1
Post-annealed, transverse plane
8T - IA-2
Sample 3: annealing practice IA-1
7T- IA-3
1000
N/mm > Dc
2
100
10
Figure 43: Logarithmic, cumulative graph, for the post-annealed particle size
distribution, after different annealing practices.
Figure 44: 3D optical micrographs of the grain structure evolution through

155
Figure 45: 3D optical micrographs of the grain structure evolution through
Figure 46: 3D optical micrographs of fully recrystallized grain structures, as those

derived from different annealing practices, viewed at x50 (top row) and at x200
(bottom row) magnifications.
156
Mean Lineal intercept length Longitudinal
Trans vers e
Surface
45
Outer-coil Inner-coil Outer-coil Outer-coil
IA-1 IA-1 IA-3 IA-2
40
35
30
Ī - (um)
25
20
15
10
0
Sample 3 Sample 4 Sample 7 Sample 8
Figure 47: Graph of the mean measured lineal intercept lengths of the industrially
annealed samples. The error bars indicate ± 1σ.
3L 4L 7L 8L
50 50 50
50
40 40 40 40
30 30 30 30
20 20 20 20
10 10 10
10
0 0
0
% Frequency
20 24 29 35 40 0 20 22 24 28 30 34 36 38 40
20 22 24 28 30 34 36 38 40 20 22 24 28 30 34 36 38 40
50
3T 4T 7T 8T
50 50 50
40 40 40 40
30 30 30 30
20 20 20 20
10 10 10 10
0 0 0 0
20 22 24 28 30 34 36 38 40 20 22 24 28 30 34 36 38 40 20 22 24 28 30 34 36 38 40 20 22 24 28 30 34 36 38 40
3S 4S 7S 8S
50 50 50 50
40 40 40 40
30 30 30 30
20 20 20 20
10 10 10 10
0 0 0 0
20 22 24 26 28 30 32 34 36 38 40 20 22 24 28 30 34 36 38 40 20 22 24 28 30 34 36 38 40 20 22 24 28 30 34 36 38 40
Mean lineal intercept length (um)
Figure 48: Histogram graphs from the lineal intercept length measurements, for all
measured specimens.
157
Microhardness benchmarking - Before and after annealing
60
Pre-annealed
50
HV (Hardness Vickers)
40
30
Post-annealed
20
10
0
Figure 49: Graph of the measured Vickers hardness of the industrial pre- and
post-annealed samples. The error bars indicate ± 1σ.
Annealing cycle IA-1 - OD:1850mm
Model Predictions (similar coil positions) Thermocouples (annealing furnace trial)

500
450
400
350
Temperature /˚C
300
250
200
150
100
50
0
0 100 200 300 400 500 600
time / min
Figure 50: Graph showing the mathematical model predicted curves (red) and the
temperatures measured with thermocouples (green) during a recent furnace trial at
similar coil positions.
158
Annealing model – OD: 1850 mm
Annealing cycle A07 - OD:1850mm
Model-Pos1 Model-Pos2 Model-Pos3 Model-Pos4 Model-Pos5 Model-Pos6
500
450
400
350
300
Temperature /˚C
250
200
150
100
50
0
0 100 200 300 400 500 600
time / min
Figure 51: Graph of the mathematical annealing model curves, for the
OD: 1850 mm coil. Each curve represents a different coil position. The arrows
indicate specific regions of interest.
Annealing model – OD: 1500 mm

Annealing cycle A07 - OD:1500mm
Model-Pos1 Model-Pos2 Model-Pos3 Model-Pos4 Model-Pos5 Model-Pos6
500
450
400
350
Temperature / ˚C
300
250
200
150
100
50
0
0 100 200 300 400 500 600
time / min
Figure 52: Graph of the mathematical annealing model curves, for the
OD: 1500 mm coil. Each curve represents a different coil position. The arrows
indicate specific regions of interest.
159
Figure 53: Temperature contour graph from the mathematical annealing model for
coil OD: 1850mm, at the end of the annealing cycle. The thin blue lines indicate the
air flow.
Figure 54: Temperature contour graph from the mathematical annealing model for
coil OD: 1500mm, at the end of the annealing cycle. The thin blue lines indicate the
air flow.
160
Bridgenorth annealing/cooling
Annealing cycle A07
and cooling curves
Air Model-Position1 Model-Position2 Model-Position3
Model-Position4 Model Position5 Model Position6
500
400
temperature (˚C)
300
200
100
0
0 500 1000 1500 2000 2500 3000
time / min
Figure 55: Mathematical model annealing and cooling curves for coil OD: 1850mm.
Each curve represents a different coil position. The black dashed line represents the
furnace air temperature.
500
Laboratory annealing simulation (1): Typical coil position Model Pos-2
450 Furnace program
(420 ˚C – 495min)
Metal (1.5mm) temprature
400 Air (furnace) temperature
Model Pos-5
(350 ˚C – 720min)
350
(350 ˚C – 345min)
Temperature ( C)
o
(300 ˚C – 900min)
300 (300 ˚C – 280min)
(250 ˚C – 1140min)
250 (250 ˚C – 190min)
200
150 (150 ˚C – 110min)
100
(Benchmarked)
50
(Benchmarked)
0
0 500 1000 1500 2000 2500 3000
time (min)
Figure 56: Graph of the annealing and cooling curves of laboratory annealing
simulation (1): typical coil position. The circles highlight the time and temperature
intervals at which samples were taken for examinations.
161
Heating Heating
Heating Heating Heating
Heating Cooling Cooling
Cooling Cooling
Figure 57: Micrographs of the grain structure evolution through annealing (red arrows)
and cooling (blue arrows). Images captured in the longitudinal plane of direction, full
thickness and viewed at x50 magnification.
162
(a)
(b)
(c)
Figure 58: Grain structure micrographs highlighting (a) the recovery phase, (b) the
initiation of recrystallization and (c) the fully recrystallized state. All images are
captured in the longitudinal plane and viewed at x200 magnification.
163
Mean Lineal intercept length - Longitudinal direction
45
40
35
30
Ī - (um)
25
(S1, 250 ˚C – 1140min)

(S1, 300 ˚C – 900min)
(S1, 350 ˚C – 345min)
(S1, 420 ˚C – 495min)
(S1, 350 ˚C – 720min)

20
IA-1 – (Outer-coil)
IA-1 – (Inner-coil)
15
10
Simulation annealed Post-annealed
Figure 59: Graph of the mean measured lineal intercept lengths, of the fully
recrystallized simulation annealed specimens and the industrially annealed samples,
in the longitudinal plane. The error bars indicate ± 1σ.
Microhardness - Laboratory annealing simulation (1): typical coil position

55
Room Temperature Sample 1: Outer-coill
150 °C
50
Heating Temp
HV (Hardness Vickers)
Cooling Temp
45
250 °C
40
35
300 °C
30
Room Temperature
25
420 °C 350 °C 300 °C 250 °C
350 °C
Slight increase of HV
20
0 500 1000 1500 2000 2500 3000
min
Figure 60: Graph of the measured hardness Vickers of the annealing simulation
specimens at the inner- and outer-coil positions. The industrial pre- and
post-annealed samples hardness values are also plotted. The error bars indicate
± 1σ.
164
Laboratory furnace - Heat-up rate chart
Target 380˚C Target 200˚C
400
360
320
280
Temperature / ˚C
240
200
160
120
80
40
0
0 20 40 60 80 100 120 140 160 180 200
time / s
Figure 61: Graph showing the heat-up rate curves for two different set target
temperatures.
165
Figure 62: Micrographs of the outer-coil (S1_1-12), isochronally annealed
specimens’ grain structures, in the longitudinal plane, viewed at x50 magnification.
166
Isochronal (30 min) experiment
S1 S2
1
0,9
0,8
Fraction recrystallized
0,7
0,6
0,5
0,4
0,3
0,2
0,1
0
100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420
TCRIT ~ 310˚C
Temperature / ˚C
Figure 63: Graph showing the fraction recrystallized against temperature curves for
the outer-coil (S1) and inner-coil (S2) position specimens, as derived from the
isochronal annealing experiment. The error bars indicate ± 1σ.
S1 - Outer-coil - Isochronal (30 min) annealing experiment
60
55
Hardness Vickers / HV
50
45
40
35
30
25
100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420
Temperature / ˚C
Figure 64: Graph showing the microhardness against temperature curve for the
outer-coil position (S1) from the isochronal annealing experiment. The error bars
indicate ± 1σ.
167
Figure 65: Micrographs of the outer-coil (S1_1-10), isothermally annealed
specimens’ grain structures, in the longitudinal plane, viewed at x50 magnification.
168
Figure 66: Micrographs of the outer-coil, isothermally annealed specimens’ grain
structures, in the longitudinal plane, viewed at x200 magnification.
169
Isothermal at 310 ˚C experiment
1,0
0,9
0,8
Fraction recrystallized
0,7
0,6
0,5
0,4
0,3
0,2
0,1
0,0
0 10 20 t0.5 ~ 28min 30 40 50 60 70
time / min
Figure 67: Graph showing the fraction recrystallized against time curve from the
outer-coil position (S1) specimens, as derived from the isothermal annealing
experiment. The error bars indicate ± 1σ.
S1 - Outer-coil - Isothermal experiment (310 ˚C)
55
50
Hardness Vickers / HV
45
40
35
30
25
0 10 20 30 40 50 60 70
time / min
Figure 68: Graph showing the microhardness against time curve for the outer-coil
position (S1), as derived from the isothermal annealing experiment. The error bars
indicate ± 1σ.
170
Is othe rm al 310°C
(a) Re crys tallization k ine tics from calculate d fraction re crys tallize d
1
0.8
Fraction recrystallized / Xv
0.6
0.4
0.2
JMAK fitting
0
0 500 1000 1500 2000 2500 3000 3500 4000
tim e / s
y = 2.5482x - 18.83 JM A K plot

(b)
R2 = 0.858
3
1
ln[ln(1/1-Xv)]
-1
-2
-3
-4
-5
6 6 7 7 8 8 9
ln(t)
Figure 69: Graphs of (a) the JMAK equation fitting and (b) the JMAK plot, as
deduced from the grain structure images.
171
(a) Isothermal 310°C Recrystallization kinetics from
microhardness variation
1
0.8
0.6
Xv
0.4
0.2
JMAK fitting
0
0 500 1000 1500 2000 2500 3000 3500 4000
time / s
y = 0.5869x - 3.9991 JM AK plot

(b) 2
R = 0.8235
1.000
0.800
0.600
0.400
ln[ln{1/1-Xv)]
0.200
0.000
-0.200
-0.400
-0.600
-0.800
-1.000
5.000 5.500 6.000 6.500 7.000 7.500 8.000 8.500
ln(t)
Figure 70: Graphs of (a) the JMAK equation fitting and (b) the JMAK plot, as
deduced from the microhardness values.
172
Microhardness related fraction recrystallized Calculated fraction recrystallized
1.2
1
Fraction recrystallized / Xv
0.8
0.6
0.4
0.2
0
0 500 1000 1500 2000 2500 3000 3500 4000
tim e / s
Figure 71: Graph of the fraction recrystallized kinetics as measured and calculated
from the grain structure and microhardness data.
173
Laboratory annealing simulation (2): Extreme coil positions
Position 1
500
Position 1
450 (Max Temp: 420 ˚C – 490min) Furnace Prog for Pos.1
L13 metal Temp
400 L13 air Temp
350
(350 ˚C – 340min)
temperature / ˚C
300
(300 ˚C – 270min)
250
200
150
(150 ˚C – 110min)
100
(Fully annealed – 2500min)
50
0
0 500 1000 1500 2000 2500 3000
tim e / min
Position 6
500
Position 6
(Max Temp: 450 ˚C – 500min)
450 Furnace Prog for Pos.6
L10 metal Temp
400 L10 Air Temp
350
(350 ˚C – 245min)
temperature / ˚C
300
(300 ˚C – 180min)
250
200
150
(150 ˚C – 45min)
100
(Fully annealed – 2500min)
50
0
0 500 1000 1500 2000 2500 3000
time / min
Figure 72: Graphs of the predicted annealing and cooling curves from the
mathematical annealing model, together with the verification curves, for simulating
the extreme coil positions 1 and 6. The circles indicate the specific sampling
intervals.
174
Positions 1 & 6 Comparison
(a) 500
Position 1 - model prediction
(Max Temp at ~ 500min)
450 Position 6 - model prediction
(∆T ~ 30 ˚C)
Position 1 - Sample temperature
400
Position 6 - Sample temperature
350
(∆t ~ 95 min)
temperature / C
300
(∆t ~ 90 min)
250
200
(Fully annealed at ~ 2500min)
150 (∆t ~ 65 min)
100
50
0
0 500 1000 1500 2000 2500 3000
time / min
Positions 1 & 6 Comparison

(b)
"Extreme" positions 1 - 6 (∆Τ)
120
100
80
60
∆Τ / °C
40
20
-20
-40
0 500 1000 1500 2000 2500 3000
tim e / m in
Figure 73: (a) Graph comparing the model predicted and simulation annealing and
cooling curves of the extreme coil positions 1 and 6. The most distinguishing
time-temperature differences are indicated. (b) Graph of the ∆Τ (Pos 6 - Pos 1)
against time.
175
(a)
(b)
Figure 74: Optical micrographs in the longitudinal and transverse planes of the
simulated coil positions 1 and 6, viewed at x1000 magnification. The images were
captured at (a) the maximum achieved metal temperatures and (b) after the
simulation annealing.
176
(a) (b)
Figure 75: Representative backscattered electron micrographs of the simulated

extreme coil positions 1 and 6, at x1000 magnification. The micrographs are in the
longitudinal plane at (a) the maximum achieved metal temperatures and (b) after the
simulation annealing.
177
Mean Number of particles per mm 2
(a)
18000
16000
14000
12000
Fully annealed_2500min
2
Max Temp (450˚C)

Max Temp (420˚C)
10000
N/m m
Position 1
Position 6
8000
Position 1
Position 6
6000
4000
2000
0
Mean Area fraction %

(b)
0.8
0.7
0.6
2
0.5
Me a n N/m m
Max Temp (420˚C)
Max Temp (450˚C)
0.4
Position 1
Position 1
Position 6
0.3 Position 6
0.2
0.1
0.0
Mean Circle diameter

(c)
0.7
0.6
0.5
2
Max Temp (450˚C)

Max Temp (420˚C)
Me a n N/m m
0.4
Position 6
Position 1
Position 6
Position 1
0.3
0.2
0.1
0.0
Figure 76: Graphs comparing the second phase particles’ (a) number per mm2,
(b) mean area fraction and (c) mean circle diameter, between the extreme coil
positions, at the maximum achieved metal temperatures (Max Temp) and after the
simulation annealing (Fully annealed 2500 min). The error bars indicate (a, b) ± 1σ,
(c) 95 % CI.
178
100000
Position 1 Max Temp (420˚C)
Position 6 Max Temp (450˚C)
Position 1 Fully annealed_2500min
Position 6 Fully annealed_2500min
10000
N/mm > Dc
2
1000
100
10
0 1 2 3
Dcircle (um)
Figure 77: Logarithmic, cumulative graph of the particle size distribution of the
simulated extreme coil positions, at the maximum achieved metal temperatures
(Max Temp) and after the simulation annealing (Fully annealed 2500 min).
179
150 ˚C
300 ˚C
180
350 ˚C
Maximum metal
temperatures
181
Post simulation
annealing
~2500min
Figure 78: 3D imaging representation of grain structures of the simulated extreme

coil positions, at the selected examination intervals, viewed at x50 and x200
magnification.
182
Mean Lineal intercept length - Maximum achieved
Temperatures - Surface
40
35
30
25
Max Temp (450˚C)

Ī - (um)
Max Temp (420˚C)

20
Position 6
Position 1
15
10
Mean Lineal intercept length - Fully annealed,

2500min - Surface plane
40
35
Fully annealed – 2500min
Fully annealed – 2500min

30
25
Ī - (um )
Position 6
Position 1
20
15
10
Max Temp - Grain size Histogram Fully annealed - Grain size Histogram
Position 1 - Surface plane Position 6 - Surface plane Position 1 - Surface plane Position 6 - Surface plane
2.5 2.5
2 2
Frequency
Frequency
1.5 1.5
1 1
0.5 0.5
0 0
20 25 30 35 40 20 25 30 35 40
M e an Line al Inte rcept M e an Line al Inte rce pt
Figure 79: Graphs showing the measured mean lineal intercept length of the
simulated extreme coil positions 1 and 6, in the surface plane, at the maximum
achieved metal temperatures (Max Temp) and after the simulation annealing (Fully
annealed 2500 min). The corresponding histograms are also shown. The error bars
indicate ± 1σ.
183
Electrical conductivity of the “extreme” coil positions during simulation annealing
61.4
Electrical Conductivity / % IACS
61.2 (Post-anneal)*
(350 ˚C – 245min) (Fully annealed – 2500min)
61.0
Less in solid solution
60.8
(300 ˚C – 180min) (350 ˚C – 340min)
60.6
(Pre-anneal)*
60.4
(300 ˚C – 270min)
60.2 Position 1
Position 6
60.0 (150 ˚C – 110min)
(150 ˚C – 45min)
59.8
0 100 200 300 400 500 1000 1500 2000 2500 3000
*Production samples time / minutes
Figure 80: Graph of the changing electrical conductivity curves, for the extreme coil
positions 1 and 6, as measured at the selected examination intervals of laboratory
annealing simulation (2). The error bars indicate ± 1σ.
Laboratory annealling simulation (2): Extreme coil positions -

Microhardness
60
Position 1
Position 6
55
50
Microhardness / HV
45
40
35
30
25
20
Post simulation
150˚C 300˚C 350˚C Max Temp annealing
Figure 81: Graph of the microhardness values of the extreme coil positions 1 and 6
at the selected examination intervals. The error bars indicate ± 1σ.
184
(a) Ultimate tensile strength
50
220
As rolled Baked UTS strength drop
Drop in UTS after baking / MPa

40
200
180 30
UTS / MPa
160
20
140
10
120
100 0
Sample 5 Sample 6 Sample 9 Sample 10 Sample 11
(b) Yield strength

50
220
Drop in Yield strength after baking / MPa

As rolled Baked Yield strength drop
40
200
180 30
YS / MPa
160
20
140
10
120
100 0
185
(c) Elongation
3,5 3,5
As rolled Baked Drop in elongation
3 3
Drop in elongation after baking / %

2,5 2,5
Elongation / %
2 2
1,5 1,5
1 1
0,5 0,5
0 0
(d) Modulus
80
As rolled Baked
70
60
Modulus / GPa
50
40
30
20
10
0
Figure 82: Graphs of the mechanical properties testing, as rolled and baked (after
heat treatment). The graphs show the results of (a) ultimate tensile strength,
(b) yield strength, (c) % elongation and (d) modulus. The error bars, where
available, indicate ± 1σ.
186
Figure 83: Representative backscattered electron micrographs of the second phase
particles population, size and distribution, after final cold rolling, at 0.3 mm gauge, in
the longitudinal plane, viewed at x1000 magnification. Sample 5 (S5: outer-coil,
IA-1), sample 6 (S6: inner-coil, IA-1), sample 9 (S9: inner-coil, IA-3), sample 10
(S10: inner-coil, IA-3) and sample 11 (S11: inner-coil, non-annealed).
187
(a) (N) - Mean number of particles per m m 2
18000
16000
14000
12000
10000
Annealed / IA-1 (O)
Annealed / IA-1 (I)
Annealed / IA-3 (I)
Non-Annealed (I)
Annealed / IA-2 (I)
8000
6000
4000
2000
0
S5_L S6_L S9_L S10_L S11_L
(O): Outer-coil, (I): Inner-coil
(b) (A%) - Mean Area fraction %
0,8
0,7
0,6
0,5
Annealed / IA-1 (O)
0,4
Annealed / IA-1 (I)
Annealed / IA-2 (I)

Annealed / IA-3 (I)
Non-Annealed (I)
0,3
0,2
0,1
0,0
S5_L S6_L S9_L S10_L S11_L
(c) (Dc) - Mean Circle diameter / um
0,8
0,7
0,6
0,5
Annealed / IA-1 (O)
0,4
Annealed / IA-1 (I)
Annealed / IA-2 (I)

Annealed / IA-3 (I)
Non-Annealed (I)
0,3
0,2
0,1
0,0
S5_L S6_L S9_L S10_L S11_L
Figure 84: Graphs of (a) the mean number of particles per mm2, (b) the mean area
fraction of particles and (c) the mean particle circle diameter, as measured in the
longitudinal plane of the 0.3 mm cold rolled samples. The error bars indicate (a, b) ±
1σ, (c) 95 % CI.
188
S5_L - Annealed / IA-1 (O) S6_L - Annealed / IA-1 (I) S9_L - Annealed / IA-3 (I)
S10_L - Annealed / IA-2 (I) S11_L - Non annealed (I)
10000
1000
N/mm > Dc
2
100
10
0,5 1 1,5 2 2,5 3
Dcircle (um)
Figure 85: Logarithmic, cumulative graph of the particle size distribution, in the
longitudinal plane of the 0.3 mm cold rolled samples.
(a) (N) - Mean number of particles per mm 2
18000
16000
14000
12000 0.3 mm gauge / No-anneal (I)
10000
0.3 mm gauge (O)
8000
0.3 mm gauge (I)
Post tandem (O)
Post anneal (O)

Post Tandem (I)
Post anneal (I)
6000
4000
2000
0
S1_L S2_L S3_L S4_L S5_L S6_L S11_L
189
(b) (A%) - Mean Area fraction %
0,8
0,7
0,6
0.3 mm gauge / No-anneal (I)

0,5
0,4
0.3 mm gauge (O)
0.3 mm gauge (I)

Post tandem (O)
Post anneal (O)

0,3 Post Tandem (I)
Post anneal (I)

0,2
0,1
0,0
(c) (Dc) - Mean Circle diameter / um
0,8
0,7
0,6
0.3 mm gauge / No-anneal (I)

0,5
0,4
0.3 mm gauge (O)
0.3 mm gauge (I)

Post tandem (O)
Post anneal (O)

Post Tandem (I)
0,3
Post anneal (I)
0,2
0,1
0,0
Figure 86: Graphs of (a) the mean number of particles per mm2, (b) the mean area
fraction of particles and (c) the mean particle circle diameter, as measured in the
longitudinal plane, before annealing (blue columns), after annealing (green columns)
and after final cold rolling at 0.3 mm gauge (orange columns), also comparing to the
non-annealed 0.3 mm gauge sample (grey column). The error bars indicate (a, c) ±
1σ, (b) 95 % CI.
190
S2_L - Pre anneal S4_L - Post anneal (I)
S6_L - 0.3 mm gauge (I) S11_L - 0.3 mm gauge, No anneal (I)
10000
1000
N/mm > Dc
2
100
10
0,5 1 1,5 2 2,5 3
Dcircle (um) (I): Inner-coil
Figure 87: Logarithmic cumulative graph of the particle size distribution, in the
longitudinal plane, at the inner-coil position, before and after annealing, after final
cold rolling (at 0.3 mm gauge) and also comparing to the non-annealed 0.3 mm
gauge sample.
191
(a) Surface plane
S5 S6 S9
S10 S11
(b)
Longitudinal
S5
S6
S9
S10
S11
192
(c)
Transverse
S5
S6
S9
S10
S11
Figure 88: Representative micrographs of the 0.3 mm gauge grain structures in

(a) the surface, (b) the longitudinal and (c) the transverse planes, viewed at x50
magnification. Sample 5 (S5: outer-coil, IA-1), sample 6 (S6: inner-coil, IA-1),
sample 9 (S9: inner-coil, IA-3), sample 10 (S10: inner-coil, IA-3) and sample 11
(S11: inner-coil, non-annealed).
193
Figure 89: 3D imaging representation of the 0.3 mm cold rolled sheet samples’
grain structures, viewed at x200 magnification.
Figure 90: 3D imaging representation of the grain structure evolution, through

inter-annealing (IA) and final cold rolling (CR), viewed at x200 magnification.
194
55
50
-2
Current density / Adm
45
40 Q
-2
S5: 1019.7 Cdm
-2
S6: 1016.5 Cdm
-2
35 S9: 1014.5 Cdm
-2
S10: 1018.6 Cdm
-2
S11: 1027.4 Cdm
30
0 5 10 15 20 25
time / s
Figure 91: Graph of the measured current densities against time, after laboratory
AC-electrograining, also showing the calculated charge densities. Sample 5 (S5:
outer-coil, IA-1), sample 6 (S6: inner-coil, IA-1), sample 9 (S9: inner-coil, IA-3),
sample 10 (S10: inner-coil, IA-3) and sample 11 (S11: inner-coil, non-annealed).
195
(x500)
(x1000)
Figure 92: Representative secondary electron micrographs of the laboratory

AC-electrograined surfaces, at 40˚ tilt, viewed at x500 and x1000 magnification.
196
Gloss - 20˚
(a)
1,50
1,40
Gloss units / GU 1,30
1,20
1,10
1,00
S5 Annealed S6 Annealed S9 Annealed S10 Annealed S11 Non-
(IA-1) - (O) (IA-1) - (I) (IA-3) - (I) (IA-2) - (I) annealed - (I)
(b) Gloss - 60˚
10
8
Gloss units / GU
0
(c) Gloss - 85˚
30
25
Gloss units / GU
20
15
10
5
0
Figure 93: Graphs of the gloss measurements on the 0.3 mm cold rolled sheet
samples’ AC-electrograined surfaces, at (a) 20˚, (b) 60˚ and (c) 85˚. The error bars
indicate ± 1σ.
197
12
50mm
Figure 94: Graphic representation of a coil, showing the, indicated from the
mathematical annealing models, hottest (position 12) and coolest (position 7) coil
positions, during annealing. The coil positions 1 and 6 were also investigated.
Maximum achieved temperatures (coil positions:1 - 12)

minimum coil size Maximum coil size
450
440
Temperature / °C
430
420
410
400
390
10
11
12
1
9
n
n
io
io
io
io
io
io
io
io
io
io
io
io
sit
sit
sit
sit
sit
sit
sit
sit
sit
sit
sit
sit
Po
Po
Po
Po
Po
Po
Po
Po
Po
Po
Po
Po
Figure 95: Graph of the maximum achieved temperatures, as those were predicted
from the mathematical annealing model, for all the considered coil positions.
198
(a) 'minimum' coil size_1.5mm
500
450
400
350
Temperature / C
300
250
200
150
100
50
0
0 50 100 150 200 250 300 350 400 450 500
time / min
(b) 'Maximum' coil size_1.5mm

500
450
400
350
Temperature / C
300
250
200
150
100
50
0
0 50 100 150 200 250 300 350 400 450 500
tim e / m in
Figure 96: Graphs of the annealing curves at the investigated coil positions 1, 6, 7
and 12, as those derived from the mathematical annealing model, for (a) the
’minimum’ coil size and (b) the ‘maximum’ coil size. The arrows indicate the largest
temperature differences occurring at ~120 minutes.
199
(a) 'minimum' coil size 1.5 mm - ∆Τ
(∆Τ) Pos 6 - Pos 1 (∆Τ) Pos 12 - Pos 7
160
140
120
Temperature / °C
100
80
60
40
20
0
0 100 200 300 400 500
time / min
(b) 'Maximum' coil size 1.5 mm - ∆Τ

(∆Τ) Pos 6 - Pos 1 (∆Τ) Pos 12 - Pos 7
160
140
120
Temperature / °C
100
80
60
40
20
0
0 100 200 300 400 500
time / min
Figure 97: Graphs of the ∆Τ between coil positions 6 and 1 and between coil
positions 12 and 7 against time for (a) the ’minimum’ and (b) the ‘maximum’ coil
size.
200
Position 1 (IA-1)
minimum' coil size_1.5mm - A07 Maximum' coil size_1.5mm - A07
500
400
Temperature / C
˚
300
200
100
0
0 50 100 150 200 250 300 350 400 450 500
time / min
(IA-1)
Position 6
500
400
˚
Temperature / C
300
200
100
0
0 50 100 150 200 250 300 350 400 450 500
time / min
201
Position 7 (IA-1)
500
400
Temperature / C
˚
300
200
100
0
0 50 100 150 200 250 300 350 400 450 500
time / min
(IA-1)
Position 12
500
400
˚
Temperature / C
300
200
100
0
0 50 100 150 200 250 300 350 400 450 500
time / min
Figure 98: Graphs comparing the mathematical annealing model curves between
the ‘minimum’ and ‘maximum’ coil sizes, at the investigated coil positions 1, 6, 7 and
12.
202
4. General Summary and Conclusions
The aim of this research was to evaluate the influence of inter-anneal and cold
rolling processes on the critical requirements of the lithographic sheet product.
4.1 Conclusions
Due to the broad scope of this project, only one alloy type (material) was
investigated and the cold rolling process was considered as constant. The experimental
focus was on the following aspects:
• Properties evolution of industrial scale (annealed and cold rolled) samples.
• Material recrystallization kinetics.
• Mathematical model (annealing plus cooling) predictions.
• Laboratory annealing simulations.
4.1.1 Industrial scale samples

The inter-annealing (different annealing practices or annealing omission and
sampling position) and sequential cold rolling process do not influence the particle size
distribution and volume fraction significantly. Some minor differences observed in the
particle population, especially after cold rolling, are possibly due to their break-up during
rolling. The majority of the particle break-up has already occurred during prior to
annealing hot and cold rolling. The analysis was limited to particles of area:
A ≥ 0.15 um2. It was thus impossible to comment on the differences in dispersoids
or fine precipitates evolution.
The grain size, expressed with the mean lineal intercept length ( l ), remained the
same after industrial scale inter-annealing, despite the different annealing practices and
the sampling position. The grain orientation (texture) was not investigated.
The electrical conductivity (k) increased slightly after industrial scale

inter-annealing (0.7 % IACS). This increase is largely attributed to the strain hardening
(cold work) prior to annealing. This suggests little or no measurable solute change after
industrial scale inter-annealing.
The microhardness decreases 50 % in Hardness Vickers (HV) during industrial

scale inter-annealing for all samples (different annealing practices and sampling
position).
The annealing process matters greatly as regards to the tensile properties.

Annealing omission is not ideal for the on-press material performance. The tensile
203
properties measured on 0.3 mm industrial scale, cold rolled samples were not influenced
by sampling position and longer or hotter annealing practices (either in the as rolled or
baked condition). However, the non-annealed sample displayed a much greater
decrease compared with the annealed samples in both yield strength and elongation
after baking.
The electrochemical roughening behaviour of all 0.3 mm gauge samples was not
influenced by the sampling position nor the annealing practices (longer, hotter or none).
The measured current and charge densities for all samples were the same. SEM
investigation of the surface graining topographies did not reveal any significant
differences. The surface reactivity was not influenced greatly by the inter-annealing
process, however, gloss measurements revealed a less uniform graining result deriving
from annealing omission, compared with the annealed samples, which grained
uniformly.
4.1.2 Material recrystallization kinetics

From the isochronal experiment, it was derived that the material’s “critical
recrystallization temperature” (TREX), for a 30 minute dwell, was TREX ≈ 310°C . At
this temperature, the onset of recrystallization was observed after just 5 minutes,
with full recrystallization after 45 minutes. The microhardness did not change once
the grain structure was fully recrystallized.
The recrystallization kinetics broadly follows the JMAK equation.

Microhardness is not an appropriate method for calculating the fraction recrystallized
of highly deformed (non-recovered) sheet because Hardness Vickers cannot
distinguish between recovery and recrystallization.
4.1.3 Mathematical model predictions

The mathematical model predicted significant differences in heating rate,
temperature and time at temperature within a coil during both annealing plus
cooling.
These differences were greater between the coil-interior and top-of-coil

positions, during annealing, especially in larger (≥ 1850 mm) coils. During both
annealing plus cooling, the time above TREX ≈ 310°C is approximately the same for
the coil-interior and top-of-coil positions. However, the coil’s top-of-coil position
experiences higher temperatures (> 400 ˚C) for longer time periods (up to
200 minutes, depending on the OD and coil width position) compared with the
204
coil-interior. The reason for this is that large coils, of OD ≥ 1850 mm, are very near
the furnace air exhaust, where the hot air velocity is great. These top-of-coil areas
are likely to develop “hot spots” i.e. microstructural heterogeneity.
Due to the difficulty of transferring the heat through the coil wrappings to the
coil’s interior, the targeted annealing temperatures and times are not equally and
uniformly achieved within a coil.
The above mathematical model predictions have not yet been industrially
verified. Until such an instrumented annealing cycle is performed, the above results
and conclusions remain unsupported.
4.1.4 Laboratory annealing simulations
Two simulations of a typical annealing practice (IA-1) were performed in a

laboratory furnace. The first one simulated two typical (average) interior coil
positions [positions 2 and 5 - laboratory annealing simulation (1)] and the second
simulated two extreme coil positions [positions 1 and 6 - laboratory annealing
simulation (2)].
4.1.4.1 Laboratory annealing simulation (1) – typical coil position
The onset of recrystallization during IA-1 was noted between 250 and
300 °C, corresponding to between 190 and 280 minute s from annealing initiation. At
350 ˚C the structure is fully recrystallized, after 345 minutes. However, the metal
continues to heat up to a maximum of 420 °C over a total period of 495 minutes.
Once the grain structure is fully recrystallized, the average grain size does
not change significantly i.e. there is no grain growth.
The microhardness evolution during annealing (IA-1) and cooling displays

two regions:
i. A rapid decrease due to recovery and recrystallization.
ii. A steady region once the structure is fully recrystallized.
4.1.4.2 Laboratory annealing simulation (2) – extreme coil positions
The particle size analysis did not measure significant differences between
the extreme coil positions. This suggests particle homogeneity within the coil despite
205
all time-temperature differences. However, due to the analysis limitations (for
particles of A ≥ 0.15 um2), no conclusion could be derived for the differences in
dispersoids and fine precipitates.
The top-of-coil recrystallized faster compared with the coil-interior. The faster
heating rate of the top-of-coil position is an accelerating factor for recrystallization.
The grain size was similar between the extreme coil positions after
laboratory annealing plus cooling. This suggests that the longer dwell of the
top-of-coil position at higher temperatures does not result in grain growth.
The time-temperature differences experienced by the extreme coil positions

have a significant influence on the respective electrical conductivities (k) during
annealing. The electrical conductivity of each position follows the respective heating
rate, thus, increases as fast as the position is heated. Nonetheless, after laboratory
annealing plus cooling, the k difference between those two positions is relatively
small (0.2 % IACS). This suggests that the solute content is generally similar within
a coil after annealing, despite the time-temperature differences experienced.
There was no difference measured in Hardness Vickers between the

extreme coil positions.
4.2 General Summary
From the above conclusions it is understood that the inter-annealing process

alters the material’s grain structure, conductivity and microhardness but not its coarse
constituents second phase particles or its solute content (measurably). The tensile
properties are formulated by the cold rolling process, which was considered as constant
for this experimental series, but influenced only from annealing omission, not by the
different annealing practices or the sampling position. The electrochemical roughening
behaviour is similarly influenced only by annealing omission.
The material’s critical recrystallization temperature is TREX ≈ 310°C (for a
30 minute dwell) and is fully recrystallized by 350 ˚C, after 345 minutes from
annealing initiation. Despite the model’s predictions of significant time-temperature
differences within a coil, no significant homogeneity differences were measured from
laboratory simulations. The different rates of heating within a coil do not impose
significant differences on the material’s coarse constituents second phase particles,
solute content, grain structure and microhardness, after annealing plus cooling.
206
From the Literature it is anticipated that the most likely requirements to be
influenced during the inter-annealing and cold rolling processes, are those related to
microstructure. A high enough annealing temperature helps retain as much of the
additional elements in solid solution. A rapid cooling (forced) also enhances this effect.
The microstructure evolution is also closely associated with the tensile properties
(strength related requirements). Moreover, the coil homogeneity and surface uniformity
are features dependent on microstructure, which subsequently influence greatly the
electrochemical roughening behaviour. The other critical product requirements of
flatness, lack of surface defects and anodizing quality are much less anticipated to be
influenced.
This research has shown that inter-annealing is an important process step which
aids the control of the final tensile properties and enhances the uniformity of the
AC-electrograining result.
207
5. Suggestions for Future Work
The following list describes suggestions for further work related to the
research undertaken in this project.
• The cold rolling process was not thoroughly investigated but considered as
constant for this experimental series. Amongst the parameters that would be
interesting to measure and monitor in order to assess the influence of this
process to the critical product requirements, are:
o The cold reduction (stress, strain and strain rate),
o the number of passes to final gauge (intermediate gauges),
o the temperature escalation during process (time at temperature after

coiling) and
o the coiling tension.
• The analysis limitations did not enable the characterization of the

dispersoids and evolution of fine precipitates during annealing. These
microstructural features are extremely important for the property evolution of
the final product. The use of specialized methodology, such as TEM
analysis, would be an interesting topic of further investigation.
• The solute content was measured using eddy currents. However, literature
indicates more suitable ways of accurate solute content measurement, such
as the thermoelectric power (TEP). This should be extremely useful in order
to assess the influence of annealing to the solute content, especially since
the solute differences are expected to be subtle due to the alloy type.
• Evaluation of the resultant AC-electrograined topography is not always

straightforward. The effect of inter-annealing and cold rolling on the
electrochemical roughening behaviour could be also measured with 3D
topographic techniques (uniformity of roughness) and sophisticated imaging
analysis (statistical analysis of pit size, number and density).
• The grain orientation (texture) was not investigated in this experimental

series. It is anticipated from literature that texture is bound to be greatly
influenced by both inter-annealing and cold rolling processes. Further
investigations, at both anneal and 0.3 mm (cold rolled) gauges, should
provide an insight on the importance of texture development on the critical
product requirements.
208
• The mathematical model was very useful in predicting significant
time-temperature differences within a coil. However, those predictions need
to be industrially verified by an instrumented annealing cycle. An indirect
method of testing the model would be by rewinding an industrial scale
annealed coil and measuring features such as conductivity, microhardness,
mechanical properties etc. in locations of different thermal histories. Once
the model is verified it could be further used to include several scenarios,
e.g. cooling rates. Those could then be simulated in the laboratory.
• The histograms of the mean lineal intercept length ( l ) measurements on

industrially annealed samples suggest that further detailed investigation is
needed to comment on when and if grain growth occurs for this material.
• The decreased electrical conductivity value at 150 ˚C, compared with its
starting (pre-annealed) value, remains inexplicable and represents an
interesting topic of further investigation.
209
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The Influence of Inter-Anneal and Cold Rolling Processes On Key Lithographic Sheet Properties

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A Thesis submitted to The University of Manchester for the degree of

1.1 Printing History - Offset Lithographic Printing Evolution and Plate 18

1.1.2 Printing processes 19

1.1.3 Evolution of the lithographic printing process 21

1.1.4 Practice of offset lithographic printing 23

1.1.5 The lithographic printing plate 24

1.1.6 Current status of the lithographic printing business 26

1.2 Aluminium in Offset Lithographic Printing 28

1.2.1 Aluminium material 28

1.2.2 Aluminium alloys 30

1.2.3 Aluminium alloy AA1050 32

1.3 Lithographic Printing Plate - Production Stages 37

1.3.1 Aluminium substrate production stage 37

1.3.3 Printer’s stage; pre- and on-press 40

1.4 Critical Product Requirements (CPRs) 40

1.4.1 Strength related properties 41

1.4.1.1 High thermal stability 41

1.4.1.2 High reverse bending fatigue strength 42

1.4.2 Lack of surface defects 44

1.4.4 Good roughening behaviour 45

1.4.5 Anodizing quality 48

1.5.1 Pre-annealing state 48

1.5.3 Recovery, recrystallization and grain growth 51

1.5.4.1 Recovery stages 53

1.5.4.2 Factors influencing recovery 54

1.5.4.3 Recovery kinetics 55

1.5.5.1 Recrystallization stages 56

1.5.5.2 Laws of recrystallization 58

1.5.5.3 Factors influencing recrystallization 59

1.5.5.4 Recrystallization kinetics 61

1.5.5.5 Impact of recrystallization on material properties 63

1.5.6 Grain growth - coarsening 64

1.5.6.1 Factors influencing grain growth - coarsening 65

1.5.6.2 Grain growth - coarsening kinetics 66

1.5.7 Annealing summary 67

1.5.8.1 Recrystallized texture evolution theories 69

1.5.8.2 Annealing texture of AA1050 69

1.5.9 Microstructure evolution through the inter-annealing process 71

1.5.9.1 Coarse constituent particles 73

1.5.9.2 Recrystallization and precipitation during the 73

1.6 Cold Rolling Process 76

1.7 Literature Review - Figures 79

2.2.1 Particle size analysis 90

2.2.2 Grain size and structure 93

2.2.3 Tensile tests and microhardness 95

2.2.4 Mathematical (annealing) model 97

2.2.5 Laboratory simulation of annealing practice IA-1 99

2.2.6 Isothermal and isochronal annealing 100

2.2.7 Electrical conductivity 101

2.2.8 Laboratory AC-electrograining 103

2.2.9 Gloss 105

2.3 Experimental Approaches 106

2.3.1 Benchmarking of pre- and post- annealed materials 106

2.3.2 Annealing modelling and laboratory annealing simulation (1): 107

2.3.6 Annealing modelling part 2: extreme coil sizes comparison 113

2.4 Experimental Procedure - Figures 114

3. Results and Discussion 121

3.1 Benchmarking of Pre- and Post-Annealed Materials 121

3.1.1 Particle size analysis 121

3.1.2 Grain structure analysis 124

3.1.3 Microhardness 126