Aggerbeck, M. - Optical - Appearance of Aluminium, PHD Th. (Tech Univ. Denmark, 2010) PDF

Technical University of Denmark
Department of Management Engineering
Department of Mechanical Engineering

Optical Appearance of Aluminium
Aluminiums optiske fremtoning
Handed in: 2010-09-10
By:
Martin Aggerbeck, s042362
Supervisors:
Torben Lenau, DTU-MAN
Rajan Ambat, DTU-MEK
In collaboration with:
Danish Technological Institute
Bang & Olufsen
DTU Fotonik

Martin Aggerbeck DTU MAN & MEK 2010-09-10
1 Acknowledgements
This is the thesis of the Design and Innovation master program at the Technical University of
Denmark. The Design and Innovation program is run by DTU-MAN and this project has
been produced in close collaboration with DTU-MEK, where most of the work has been
carried out due to the nature of the project. This thesis counts for 30 ECTS points for the
period from 1st of March to 10th of September 2010.
First of all I would like to thank my supervisor at DTU-MEK, Rajan Ambat for believing in
me and getting me into this project and for his help, support and encouragement throughout
the project. And a big thank to my supervisor at DTU-MAN, Torben Lenau for his huge
support throughout the project even though I left another project with Torben Lenau to
make this project.
Thanks to the Danish Agency for Science, Technology and Innovation for their economical
support of the project.
A big thank to my industrial contacts Kristian Rechendorff and Klaus Pagh Almtoft from the
Tribology Centre at Danish Technological Institute and Ib Kongstad and Flemming Jensen
from Bang & Olufsen, they have been very kind and keen to participate and skilled when
answering technical questions and joining discussions.
I have been several times at DTU Risø at the Department of Photonics Engineering where I
have been met with great hospitality and a lot of help from Jørgen Schou and Stela Canulescu,
thanks to them both.
A special thank to Ph.D.-student Juliano Soyama at DTU-MEK, with whom I have had a
weekly meeting for discussing each other’s project.
A big thanks to all the people, that have helped me with equipment, discussions, setting up
experiments and so much more: Manthana Jariyaboon, Helle B. Brandt, Steffen Munch, Laila
Leth, Flemming B. Grumsen from DTU-MEK and Christian Ravn from IPU. Also Lars
Pedersen and John Troelsen at the workshop at DTU who are always helpful and extremely
efficient.
Thanks to Søren Bredmose Simonsen, Ph.d. student at Haldor Topsøe and again Kristian
Rechendorff from Danish Technological Institute, who has proofread this thesis.
Finally thanks to Per Møller who is always ready for a discussion and throwing twenty ideas at
the table at the same time.
Technical University of Denmark, 2010-09-10.

Supervisors:
Torben Lenau, DTU-MAN, Section for Innovation and Sustainability
Rajan Ambat, DTU-MEK, Section for Materials and Surface Engineering
__________________
Martin Aggerbeck
1
2 Resumé (Danish)
Tre aluminium handelslegeringer (1050, 5754 og 6082), med forskellige
overfladebehandlinger (kombinationer af ætsning og polering) er blevet undersøgt med
LOM, GDOES og fotospektrometri, for at belyse, hvordan og hvorfor
legeringssammensætning og overfladebehandling påvirker aluminiumemners optiske
fremtoning. Der er fundet frem til at refleksionsfarven er legeringsafhængig og at
refleksionsintensiteten både er afhængig af overfladebehandling og legeringens renhed.
Undersøgelser har vist at et emne med høj overfladeruhed efter væskepolering bliver sort
under anodiseringsprocessen. Indledende forsøg med PVD film af Al og Ti på støbt Al er
udført for at undersøge sammenhængen mellem Ti-koncentrationen og emnernes optiske
fremtoning. Opståede problemer under anodiseringen startede undersøgelser af filmen med
LOM, SEM og XRD. Få fotospektrometrimålinger er udført på de u-anodiserede PVD film.
Igangværende forsøg af et vandmærke under det anodiserede lag og et mokumé gane-produkt
er blevet opstartet.
3 Abstract
Three commercial aluminium alloys (1050, 5754 and 6082), with different surface
treatments (combinations of etching and polishing) has been investigated by LOM, GDOES
and photospectrometry, to study how and why alloy composition and surface treatment
affects the optical appearance of an Al specimen. It is found that reflection colour is alloy
dependent and reflection intensity depends on both surface treatment and alloy purity.
Studies have shown that a specimen with high surface roughness caused by water polishing
turns black during anodising. Introductory experiments have been made with PVD coatings
of Al and Ti on cast Al to investigate, the connection between Ti-concentration and optical
appearance. Problems occurring when anodising the coatings have initiated examinations of
the coatings by LOM, SEM and XRD. A few photospectrometry measurements have been
done on the non-anodised PVD coatings. Ongoing experiments of a watermark under the
anodised layer and a mokumé gane product have been initiated.
2
4 Abbreviations
The following abbreviations is used throughout this thesis:
AFM Atomic Force Microscopy

BEI Backscatter Electron Imaging
CRT Cathode Ray Tube
DC-diode Direct Current two-electrode
EDS Energy Dispersive X-ray Spectroscopy
LOM Light Optical Microscope
PVD Physical Vapour Deposition
RFGDOES Radio Frequency Glow Discharge
Sometimes just GDOES Optical Emission Spectroscopy
SDOM Standard Deviation Of Mean
SEI Secondary Electron Imaging
SEM Scanning Electron Microscope
TEM Transmission Electron Microscope
XRD X-Ray Diffraction
Table 4.1: Overview of abbreviations.
3
Table of Contents
1 Acknowledgements ......................................................... 1
2 Resumé (Danish) ............................................................. 2
3 Abstract ........................................................................ 2
4 Abbreviations ................................................................ 3
5 Introduction ................................................................... 6
6 Theory .......................................................................... 8
6.1 Optics ........................................................................................................ 8
6.2 Materials ................................................................................................... 9
6.2.1 Aluminium ........................................................................................... 9
6.2.2 Recycled cast aluminium ..................................................................... 13
6.3 Surface modification processes for aluminium ............................................. 14
6.3.1 Polishing by buffing and water polishing ............................................. 14
6.3.2 The anodising process ........................................................................ 15
6.3.3 Physical Vapour Deposition (PVD)....................................................... 19
6.4 Characterisation techniques ....................................................................... 25
6.4.1 Scanning Electron Microscope (SEM) .................................................. 25
6.4.2 (Radio Frequency) Glow Discharge Optical Emission Spectroscopy
((RF)GDOES) ................................................................................................. 27
6.4.3 XRD................................................................................................... 27
6.4.4 Spectrophotometer measurements....................................................... 28
7 Materials and preparation techniques .............................. 29

7.1 Materials used.......................................................................................... 29
7.1.1 Used Al alloys ................................................................................... 29
7.1.2 Titanium grade 1 ............................................................................... 30
7.2 Surface finishing treatments on commercial alloys ....................................... 30
7.2.1 Polishing using a buffing wheel ........................................................... 31
7.2.2 Anodising treatment ........................................................................... 32
7.2.3 Naming of commercial alloy specimens ............................................... 33
7.3 Synthesis of aluminium based plasma coatings............................................ 34
8 Characterization techniques ........................................... 36

8.1.1 Optical microscopy and SEM .............................................................. 36
8.1.2 GDOES ............................................................................................. 37
8.1.3 XRD................................................................................................... 38
8.1.4 Photospectrometry ............................................................................. 39
8.1.5 Measurement errors on photospectrometry ......................................... 42
9 Results and discussion ................................................... 43

9.1 The effect of alloy and treatment on optical properties ................................ 43
9.1.1 Anisotropy in optical measurements on a surface ................................. 43
4
9.1.2 Presentation of the anodised specimens............................................... 44

9.1.3 LOM examination of the anodised specimens ...................................... 45
9.1.4 Element enrichment in the surface........................................................ 46
9.1.5 Alloy / treatment for anodised specimens ............................................ 48
9.1.6 Full, diffuse and specular reflection ..................................................... 51
9.1.7 Visual effect of anodising.................................................................... 56
9.1.8 Summary on alloy and treatment affect on optical properties................ 60
9.2 Water polished specimens ......................................................................... 62
9.2.1 Black anodising.................................................................................. 63
9.2.2 The etching experiment on water polished specimen ............................ 65
9.2.3 Summary on water polishing part ........................................................ 70
9.3 The effect of Ti-concentration on optical properties in aluminium coating ....... 70
9.3.1 Examination of the PVD coating .......................................................... 71
9.3.2 Visual impact of titanium concentration on full reflection ....................... 74
9.3.3 Full vs. diffuse reflection...................................................................... 76
9.3.4 Change of substrate material .............................................................. 78
9.3.5 Anodising the PVD coatings ................................................................ 78
9.3.6 Reason for bad anodising................................................................... 80
9.3.7 Summary on PVD part ........................................................................ 83
9.4 Watermark under the anodised layer ......................................................... 84
9.5 Mokumé gane .......................................................................................... 85
10 Conclusion ................................................................. 87

11 Future Work ............................................................... 88
12 References ................................................................. 89
5
5 Introduction
Aluminium is a key part of the green technology of the future. The possibility of
manufacturing low weight products and thereby increasing the energy efficiency, e.g. in the
transport sector is very important. Moreover aluminium is very easy and cheap to recycle,
however, the recycled (secondary) aluminium contains a high amount of impurities, making it
less efficient to use than the newly extracted (primary) aluminium. Inter-metallic particles of
impurity elements are formed during casting and thermo-mechanical treatment in the
secondary aluminium. This is the source of problems and secondary aluminium is therefore
more obvious for casting than as wrought aluminium, since cast aluminium is not as
vulnerable to impurities.
For many products, when one uses aluminium for designing (e.g. Bang & Olufsen), the use of
the casting process is important because complicated shapes can be easily fabricated.
However, the cast components have a more inhomogeneous microstructure compared to the
components fabricated by a machining process from thermo-mechanically treated aluminium
(sheets, bars, etc.). Additionally, the cast components have a number of defects especially the
porosity is important. Due to these facts and the chemical composition of the cast aluminium,
problems occur with surface modification especially anodising for decorative application.
Unfortunately, cast aluminium turns black and contagious when anodised caused by the
silicon added for easing the casting process.
The problems can hopefully be solved by coating the cast components by an aluminium
coating, either commercially pure or added alloying elements. The physical vapour deposition
(PVD) process can make the coating, which then can be anodised, so that the adverse effect of
the cast components can be overcome. The coating can be used for acquiring both good
decorative optical and / or corrosional properties. However, in order to achieve this, the
microstructure and composition of the coating should be controlled; PVD parameters should
be adjusted properly, and the coating microstructure needs to be investigated in detail.
Furthermore, the used plasma technique also allows the introduction of additional alloying
elements, which are not possible to alloy with aluminium by a melting process. Thereby the
optical and corrosional properties of the coating can be varied. The present work focuses on
the optical properties of aluminium specimens as a function of chemical composition and
surface treatment.
This project is a part of the work carried out under the innovation consortium project, IdeAl
surfaces, started in March 2010. The consortium consists of six industrial partners and five
knowledge institutes in Denmark, Belgium, Germany and Italy and is partly founded by the
Danish Agency for Science Technology and Innovation.
The overall objective with IdeAl is to develop a generic technology platform based on
aluminium based coatings deposited on a variety of materials by PVD or laser cladding in
combination with the anodising process. The aim is to produce coatings with good decorative,
optical properties, and with satisfactory corrosion wear resistance.
6
The IdeAl project has two focuses:

1. Environmentally friendly corrosion protection of aluminium parts, among other
things by avoiding the use of chromium and increasing the possibility of using
recycled aluminium.
2. Design of durable optical effects using aluminium based plasma coatings on a wide
variety of substrate materials, e.g. recycled aluminium, steel and other metals,
polymers, composites and ceramics.
The goal for this report is to investigate to which extent alloy composition and surface
treatments affect the optical appearance of aluminium, and gaining experience with analyses
methods of the structure of a PVD coating and its optical properties.
The findings in this project will be further exploited and strengthened during the Ph.D.
program stating in October, hopefully developing new ways to decorate aluminium surfaces.
This thesis is divided into two major parts:
1. Alloy composition and surface finishing’s effect on optical properties of anodised
specimens (sections 9.1 + 9.2)
This part should give fundamental contribution for a future standard method of analysing
optical properties of aluminium specimens.
2. The effect of titanium concentration in aluminium coating on optical properties
(section 9.3)
This part should give experience with the use of varying compositions with the PVD process
and how the change of concentration of only one element affects the optical properties of the
specimen.
Two minor parts in the ends of the report presents ongoing experiments making a watermark
beneath the anodised layer and a remote control decorated by the mokumé gane technique.
The work on this project has been conducted in collaboration with Danish Technological
Institute (hereafter TI), DTU Department of Photonics Engineering and Bang & Olufsen
(hereafter B&O).
This project is partly based on experience from a master thesis from 2008, Anodisering af
aluminium med optimerede egenskaber (Anodising of aluminium with optimized properties) by
H. Tobias Holt and Rasmus Hauberg Møller [1] and a Ph.D. thesis from 2009 Advanced
Anodizing Technology by Naja Tabrizian-Ghalehno [2].
7
6 Theory
6.1 Optics
Optics is a huge scientific field. Here, only the relevant topics will be briefly described.
Light can be viewed as a beam, as an electromagnetic wave or as particles. Light interacts with
surfaces and generates various visual effects, which are determined by the interaction of the
light waves with the material. This causes effects such as scattering, reflection, refraction,
interference, absorption and diffraction depending on the nature of the surface and the
material. In this project the focus is on the interaction of the visible spectrum of light with the
surface causing various visual effects. The visible spectrum of light is not distinct but varies
from person to person and therefore from source to source [3] [4]. The visual spectrum is
approximately from 400 nm (violet) to 750 nm (red).
When a beam of light is hitting a surface the reflection can be described as a function of [5]
[6]:
• Specular reflection: The direct reflection, where the incident angle equals the
reflected angle, e.g. a mirror.
• Diffuse reflection: The light scattered in the surface topography, e.g. a piece of paper.
• Ambient reflection: The light scattered from the surroundings without the current
light source taken into account.
Diffuse reflection comes as a result of the surface roughness reflecting the light in all
directions in a specular way, but in such small areas, that it is not perceived as specular
reflections but as a diffusing surface. Diffusivity therefore increases with surface roughness
with magnitude comparable to the wavelength of light. In Figure 6.1 is illustrated specular and
diffuse reflection, where the blue arrows are the incoming rays of light, and the red arrows are
the reflected rays of light.
Figure 6.1: Illustration of specular and diffuse reflection (source: http://www.physicsclassroom.com).
From Figure 6.1 it is seen that the diffusivity of a material is increased by the surface
roughness.
8
6.2 Materials
The IdeAl consortium, and therefore this project, focuses on lightweight application of
aluminium and aluminium based coatings. Both wrought and cast aluminium is also used as
underlying substrate for the aluminium coatings. Also other metals, ceramics, polymers and
composites are to be used as substrate in the long term.
6.2.1 Aluminium
Aluminium is extracted from bauxite1 and it requires several steps and a big amount of energy
in formation of alumina (Al2O3) (extracted aluminium is called primary aluminium). On the
other hand it only takes about 5 % of the energy for extracting new aluminium to recycle used
aluminium (called secondary aluminium) [7].
Aluminium has become remarkably popular and it is the most used non-ferrous metal with an
annual consumption of 25 million tons [7]. The success is primarily due to the big diversity of
semi products and functionality in castings and extrusions [8] and due to the relationship
between density and Youngs modulus, which is as high as the one for stainless steel, while at
the same time aluminium structures turns out to be up to 50 % lighter than equivalent
structures made of stainless steel [7]. Aluminium is the lightest of all common metals (2700
kg/m3) making it excellent for e.g. the transport industry improving the fuel consumption
significantly.
When pure aluminium is exposed to atmospheric air a thin passivating oxide layer of alumina
(Al2O3) is formed on the surface. After creating the layer all over the specimen the process will
stop. Alumina is very hard and highly resistant to corrosion in atmospheric and wet
environments and therefore the alumina is effectively protecting the underlying aluminium.
The natural oxide film is 1-3 nm [8] and can therefore easily wear off, but a thicker layer of
alumina can be created in a controlled way by the anodising process which is described in
details on page 15.
1
Bauxite is a form of rock and consists of several minerals including Al(OH3), -AlO(OH),
AlO(OH) and iron and titanium oxides [6]
9
Aluminium has a high reflectivity, which does not vary significantly with wavelength in the
visible spectrum of light. Therefore aluminium is often used in mirrors, reflector screen,
optical equipments and the like [4]. The optical spectrum of the reflected light from
aluminium is presented in Figure 6.2 along with silver, platinum, gold and iridium.
Figure 6.2: Representation of the reflectivity as function of wavelength

(source: http://www.furuyametals.co.jp).
As seen in and Figure 6.2 aluminium has a relatively uniform reflection of the visible light
around 91-92 %. This is quite unique together with silver, which is the reason that these
materials are the ones used for making mirrors. In general metals have an area of reflection
around 40-60 %2, as seen for iridium and gold in the shorter wavelengths.
Pure aluminium is very soft and mechanically weak and therefore not useful for many
applications. This is why aluminium alloys are added various amounts of additional elements
as shown in Table 6.1. Aluminium alloys also invariably contains impurities such as Fe, Si and
Mn to a certain extent. Making extra pure aluminium is very costly, therefore some level of
impurities is accepted in all aluminium alloys. Problem can occur during surface modification
or corrosion can appear due to these impurities and their electrochemical behaviour.
2
From a discussion with Jørgen Schou, Senior Researcher at DTU Fotonik
10
Various aluminium alloys have been divided into groups according to their primary alloying
elements. In the EN 573 and EN 1780-standards the casting alloys have a group number
followed by four others while wrought alloys have the group number followed by three
numbers. A quick overview of the main groups are seen in Table 6.1:
Primary alloying
Cast alloys Wrought alloys Typical applications
element(s)
None 1xxxx 1xxx Foil, sheets, decorative
Copper (Cu) 2xxxx 2xxx Aircraft industry
Manganese (Mn) 3xxx Cans, building radiators
Silicon (Si) 4xxxx 4xxx Heat exchangers
Magnesium (Mg) 5xxxx 5xxx Cans, transportation, building
Magnesium + silicon 6xxx Transportation, building
Zinc (Zn) (+ copper) 7xxxx 7xxx Aircraft industry, radiators
Other elements 8xxx Foil and aircraft industry
Table 6.1: The main group of the aluminium alloys.
The 8xxx series contains often Fe+Si and Li.
There are different reasons for the use of different alloying elements. In the following the
effect of some of the elements is described:
Iron is mainly an unwanted but common impurity. Normally it gives grey or black stripes if
the Fe-Si ratio is greater that 7:1. The stripes are a result of inter-metallic compounds
between iron and silicon.
Silicon is both seen as impurity and alloying element. It is normally used in cast alloys to ease
the casting process. Even small amounts of silicon can give shadow formation in the surface
after anodising.
Titanium is a grain refiner. It can cause grey or black stripes as with iron.
Magnesium and manganese enhances the mechanical properties of the alloy. Magnesium does
not have a large impact on the decorative properties up to 7 % where manganese content up
to 1% will vary the surface from clear to brown to clearly spotted. 0,3-0,5% of manganese will
cause a brown colouring due to formation of MnO2. Manganese also enhance the weldability
as silicon.
Chromium content of 0,3% causes a yellowish surface.
11
From a decorative point of view the following limits are advised:
Element Advised Concentration limit
Iron (Fe) 0,5%
Silicon (Si) 2-3%
Magnesium (Mg) 7%
Manganese (Mn) 0,5-0,8%
Zinc (Zn) 6-8%
Chromium (Cr) 0,3%
Titanium (Ti) 0,3%
Copper (Cu) 1-2%

Table 6.2: Advised limits from a decorative point of view [9].
There are many applicable alloy groups for this project but here only the most relevant
wrought alloys will be described, 1000-, 5000- and 6000-alloys that is.
The 1000-series
The 1000-series consist of alloys with a purity of at least 99 % with Si and Fe as the major
impurities. These alloys are highly corrosion resistant due to the low amount of alloying
elements [7], have high heat and electrical conductivity and are very soft and thereby good
workability.
The 1000-series is mainly used for electrical and chemical fields plus decorative applications.
The 1050-alloy is generally pure with various extents and very much used for decorative and
other applications where high levels of mechanical properties are not needed. The 1050 alloy
gives a good compromise between mechanical property, ductility, and decorative appearance
[7]. Because of its purity of 99,5% it is very soft compared to the other used alloys.
The 5000-series
The main alloying element in the 5000-alloys is Mg (normally up to 5 %) added in order to
enhance the mechanical properties. Apart from Mg the 5000-series is often alloyed with Mn
(additional mechanical strength), Cr (corrosion protection) and Ti (grain refiner).
Heating can cause precipitation of Al3Mg2 intermetallic compounds, commonly called the -
phase. Precipitations happen in the grain boundaries and are anodic with respect to the grains
and therefore there is a risk of intercrystalline corrosion especially when the Mg-level is high,
under significant strain hardening, and at high service temperatures [7]. For the same reason
caution is recommended when using more than 3 % Mg if the alloy is used above 66 °C
because of the risk of stress corrosion [10].
The 5754-alloy is mainly alloyed with Mg, and with the combination of Mn or Cr the alloy is
suited in the building sector, transport and mechanical industries. [7]
12
The 6000-series
The main alloying elements in the 6000-alloys are Mg and Si. They form magnesium silicide
(Mg2Si) making very fine precipitates that increases the strength of the alloys. The 6000-
series have many very good properties e.g. mechanical, corrosional and visual. Therefore the
6000-series is widely used for extrusions around 6 million tons is used per year [7].
Due to its favourable properties, the 6000-series is used in a large variety of products in the
transport industry and other mechanically requiring applications.
The 6000-seies have a slight tendency to intercrystalline corrosion but normally not to a very
high extent. These alloys do not experience stress corrosion.
The alloy 6082 is widely used in commercial vehicles, railcars, shipbuilding, in the mechanics
industry, and as forging stock [7].
6.2.2 Recycled cast aluminium

In 2008 according to [11] the amount of recycled aluminium covers 20-30 % of the total
spend aluminium in Europe. The recycled aluminium comes mainly from the building
industry, the transport sector, mechanical and electrical engineering and household
appliances. In 2004 the amount of collected scrap was 70 % of the available resources [7].
Because of the vast amount of impurities the recycled aluminium is more or less only used for
casting [11].
About 60 % of all cast aluminium today is used in the automotive industry as engine
components [7]. Many of these alloys contain a lot of silicon and also at least 3 % copper. The
reasons for the use of silicon are to enhance the ability of filling the form and reduce the
suction of aluminium when it hardens after the casting process. As seen on Figure 6.3 the Al-
Si phase diagram has a eutectic point around 12,6 wt% of Si. Most cast alloys are around this
amount of Si creating a eutectic microstructure.
Figure 6.3: Al-Si phase diagram [1].
Copper is also added to ease the casting process.
13
The 40000-series
The 40000-series is the most commonly used of the cast aluminium alloys. The series has a
good castability due to its low eutectic point temperature (577 ºC).
The 46500-alloy contains about 2-4 % copper and is especially suitable for pressure casting
and is much used for complicated geometries. When heated, particles of CuAl2 will
precipitate along the grain boundaries, which will enhance the mechanical properties.
Unfortunately the CuAl2 particles will act cathodic to the aluminium. Therefore the material
around the precipitates will slowly corrode. Consequently, the adhesion between the grains
will slip and the material will fail [1].
6.3 Surface modification processes for aluminium

A number of surface treatment processes can be used for aluminium and its alloys; however,
only the important ones used in this project will be described in detail.
6.3.1 Polishing by buffing and water polishing

Prior to the anodising process some of the specimens may have scratches, pits and other
inhomogeneous appearances that can be removed by polishing. There are differed between
mechanical and chemical polishing, which are used for different roughness and finishing.
Polishing can e.g. give a smooth mirror like surface for shiny products or subsequent coating
process, or a uniformly rough surface making it suitable for e.g. painting.
In the present project, two types of mechanical polishing have been used, which will be
described in detail:
6.3.1.1 Wheel polishing

The wheel-polishing machine is using a cloth wheel for polishing. A wheel of round cloth-
pieces is made and sewed together. The wheel is fixed on a rotating machine so that the cloth
wheel is vertical and the machine spins usually more than 1200 rounds per minute [8]. A
polishing wax is added and the machine can now be used for polishing.
Difference in the alloy can give different results when buffing due to their alloying elements
and hardness from e.g. heat treatments. In general, harder specimens are tougher to polish
while the process heat softer specimens more. The temperature easily reaches 200 °C and may
locally rise up to 500-1000 °C [8].
The number of threads in the mop may vary, and a higher number of treads gives a harder buff.
On the wheel are cloth disc separators adjusting the buffing wheel to become a bit softer.
The process is carried out by first polishing perpendicular to the largest scratches on the
specimen. When these are removed, the specimen is turned so that the next round of polishing
is done perpendicular to the scratches just made when removing the big scratches.
Due to the heat from the polishing process Beilby [12] has suggested that the material from
the peaks of the aluminium is displaced into the valleys making an amorphous and / or very
fine crystalline layer, called the Beilby layer.
14
An illustration of the Beilby layer is seen in Figure 6.4.
Figure 6.4: The Beilby layer [12].
In Figure 6.4 it is seen that the Beilby layer is also coated by an oxide and a water vapour layer.
6.3.1.2 Water polishing

Another method is water polishing. Here the polishing machine uses high-pressure air to
shoot out water mixed with small hard alumina particles. The particles have enough energy to
remove impurities, scratches and other irregular surface features [8]. The process can be done
directly perpendicular to the specimen or fixated while shooting diagonally to get into
structures, which are not properly removed when shooting perpendicular. After the polishing
the specimen is cleaned in demineralised water.
The blasting treatment also work-hardens the surface, resulting in advantageous effects
against mechanical influences such as stress and fatigue.
6.3.2 The anodising process

Anodising is an important process for aluminium alloys for various applications spanning
from decorative, corrosion, hardening etc. and covers application sectors such as architectural,
designing, building, automotive, offshore and many more [8].
15
In Table 6.3 the suggested thickness of the anodising layer can be seen according to the use of
the final product:
Thickness Application areas

Surfaces exposed to an extensive form of corrosion or wear. Especially outdoor
25 μm
applications in highly corrosive environments.
Surfaces exposed to heavy or normal outdoor applications, e.g. for building
materials, vehicles, ships, etc.
20 μm Indoor surfaces exposed to chemicals or moist-containing atmosphere in
connection with production plants, process lines and equipment used in e.g. the
food industry.
Surfaces exposed to medium indoor wear, e.g. door handles or decorative
15 μm
outdoor areas.
Surfaces used indoors and outdoors in dry clean atmospheres e.g. reflectors,
10 μm
fittings, decorative plates for vehicles, and sports equipment.
5 μm Only suitable for surfaces used indoors.
Table 6.3: Overview of suitable application areas as a function of the thickness of anodised aluminium
layer [9].
The anodised alumina layer is hard, scratch and corrosion resistant and can be used for
decorative applications uncoloured and can be coloured in a wide variety of colours.
The anodising process is normally divided into the several subprocesses, as seen in Figure 6.5,
which will be gone through in the following:
Figure 6.5: Schematic anodising process.
6.3.2.1 Degreasing
During the degreasing phase oil, lubricants and other greasing agents are removed from the
surface. This can be done e.g. by immersing the specimen into a soap solution or simply using
ethanol.
6.3.2.2 Etching
The etching process is often done in sodium hydroxide at 60 °C. This removes the natural
passivating oxide and a thin layer of material from the surface as the microstructure of this
layer is different from the bulk. The etching process levels out larger surface imperfections
but it also creates a mat pattern to the surface, and is therefore not used for shiny specimens.
During this process some precipitated products of alloying elements could be formed on the
surface, e.g. for copper containing alloys, copper enrichment is possible at the surface.
As seen in Figure 6.5 the etching process is not always done but is e.g. skipped when making
shiny surfaces.
16
6.3.2.3 De-smutting
The purpose of the de-smutting phase is to remove smut (precipitates) from the etching
process sticking to the surface of the alloys. It is normally done in a solution of concentrated
nitric acid. Pure aluminium gives less smut than highly alloyed aluminium. Nitric acid also
removes any enriched copper on the surface in the case of copper containing alloys.
6.3.2.4 Anodising
The anodising creates a film of aluminium oxide (alumina) on the surface by an
electrochemical reaction. The properties of the anodised layer depend on the substrate
composition, bath chemistry, temperature etc., and varying these parameters will change the
properties of the anodised layer. Anodising is a commonly used process, normally performed
on aluminium, titanium and magnesium.
Anodising is an electrolytic process where the specimen to be anodised is coupled as anode in
a chemical bath, and potential is applied so that the metal will dissolve from the surface,
which subsequently is converted into oxide on the surface. The cathode in anodising is often
aluminium or titanium, the latter being more expensive but also much more resistant to the
electrolyte and therefore hold much longer. The electrolyte in the electrochemical cell can be
sulphuric acid, chromium acid, boric acid and oxalic acid and others, or even a combination of
two or more electrolytes [13]. Sulphuric acid is most common since it is effective and cheap.
The anodising converts the surface of the aluminium into alumina (Al2O3), which is a hard,
brittle, very corrosion resistant transparent ceramic. During this conversion the material will
expand and one third of the total anodised layer will then be above the original surface of the
specimen [14]. The converted layer consists of pores in hexagonally shaped cells with a central
pore perpendicular to the surface as illustrated in Figure 6.6.
Figure 6.6: Idealised anodising structure (source: electrochem.cwru.edu).
17
The pore diameter varies but it is typically about 15 nm and 1000 times thinner than the
thickness of the layer [7].
The process starts at the surface and runs perpendicular into the specimen. Consequently, the
surface of the anodised layer will be exposed to the anodising agent for the longest time. This
can create a powdering effect where the pores do not have vertical walls, but they are inclining
away from the centre of the pore.
At the bottom of the pores is a thin dense barrier layer, which is only 0,1-0,2% of the total film
thickness. The barrier layer is non-porous and conducts the current from the electrolyte to
the specimen bulk building further the oxygen layer [8].
The anodising process is controlled by the voltage, current density, temperature and time. The
impact of these will briefly be described [2]:
Voltage: When increasing the voltage the pore diameter is increased and thereby the number
of pores per cm2 decreases.
Current density: Low current density produces soft, porous and thin films.
Temperature: Low temperature gives less pores per cm2 but bigger pores and thicker cell
walls. The growth speed increases with the temperature.
Time: The thickness of the coating is mainly controlled by the time. This is the case until a
maximum thickness where the powdering effect will stop the layer from getting thicker. The
inclining walls of adjacent pores will simply meet and follow the pore growth downwards into
the specimen.
6.3.2.5 Colouring
The colouring process is normally done in one of the following three ways [9]:
• Absorption colouring is the cheapest, simplest and most commonly used method. In this
process the specimen is immersed into a liquid solution containing the dye that will go
into the pores of alumina. This process can be used for a wide variety of colours.
• In electrolytic colouring a metal or metallic salt is precipitated in the bottom of the
pores. The variety of colours are not as great as with dyes, but these colours are more
resistant to uv light and the colour therefore holds for a much longer time.
• Integral colouring colours the alumina instead of in the pores between the alumina. In
this process the electrolyte of the anodising process is containing one or more organic
acids that will colour the oxide layer. A big advantage is the anodising and colouring is
done at the same time in the same bath.
18
Figure 6.7 illustrates absorption colouring and integral colouring.
Figure 6.7: Colouring methods: Left: Absorption colouring (the Al2O3 is transparent).
Right: Integral colouring.
6.3.2.6 Sealing
After anodising and the possible colouring process the surface has a high capillary effect as a
result of the porous surface making it extremely susceptible to fingerprints, oil, dirt etc.
Additionally if dyes have been added into the pores, the dyes will tend to leave the pores if
these are not closed. To avoid this, the specimen is sealed normally by dipping the specimen
into hot demineralised water around 100 °C. Sealing can also be done e.g. with steam (from
water), chromate and dichromate.
During the sealing process the upper most ceramic alumina is converted together with the
water into the softer mineral called böhmite:
Al2O3 + H2O 2AlO(OH)2
During this conversion the surface will expand and close the top of the pores in the surface.
The sealing also stop particles from getting into the pores acting as corrosive particles.
During the sealing process the optical appearance can be impaired due to the closing of the
capillary pores. This is called sealing bloom. This can influence the interaction of light on the
surface. Also change in chemistry during the sealing process can affect the optical properties.
Temperature, pH, water characteristics and amount of silica in water are essential factors [2].
6.3.3 Physical Vapour Deposition (PVD)

The PVD process is used for depositing a thin film of commercially pure aluminium or
aluminium mixed with a controlled amount of other elements.
Since PVD is a plasma process the concept of plasma is described followed by an outline of
the PVD process.
19
6.3.3.1 Plasma
By raising the temperature of a gas, the electrons will be removed from their atom or
molecule. This state of matter is called an ionised gas or plasma
Plasma is consisting of three types of particles:
• Neutral particles – atoms and molecules
• Ions
• Electrons
Because of the charged particles the plasma as a whole will be electrically conducting
although the amount of ions often will constitute less than 0,1% of all the particles.
When heating creates the plasma it is called thermal ionization. In this case the plasma is
produced by electrical discharges in a vacuum chamber, this is sometimes called electrical
ionisation.
The plasma is produced in an electric field between a positive anode and a negative cathode.
Whenever an electron is removed from a neutrally charged atom/molecule, a negatively
charged electron and one positively charged ion is formed. The electron will be accelerated
towards the anode and on its way it is likely to hit one or more electrons making more charged
particles – again hitting other electrons – thereby maintaining the plasma.
The initial electron will hit electrons that will hit a whole subsequence of electrons. For this
to happen the initial electron most have a lot of energy. Apart from hitting electrons freeing
from their atoms, energy is also absorbed by excitation of electrons that during decaying emits
a photon. This energy is wasted according to the maintenance of the plasma.
The initial electron is generated when positively charged ions bump into the target material of
the cathode.
In Figure 6.8 the voltage drop between the anode and cathode can be seen.
Figure 6.8: Voltage drop over anode/cathode region [1]. Left: Before plasma is ignited. Right: Plasma is
switched on. Note that the gradient is mainly close to the electrodes.
Normally Vp is 10-30 V and V0 is 300-500 V.
Notice that the actual potential of most of the plasma (Vp) is higher than the potential of the
anode due to the fact that the electrons have a high velocity compared to the other particles.
The electrons will therefore more often leave the plasma than the ions.
20
6.3.3.2 The PVD process

In this project the focus has been primarily on the non-reactive PVD processes. The non-
reactive PVD-process is subdivided into thermal evaporation processes where the target is
heated to evaporation, and the sputtering process, which is the focus of the following part.
The sputtering process is using an ionized gas, usually Ar, hammering into the target, which is
then atomized, i.e. sublimated. Because of the low pressure inside the chamber the atomized
target material cover everything inside the chamber including the chamber walls, the holders,
and the substrates as seen in Figure 6.9. The PVD process is a line-of-sight process meaning
that only surfaces in straight line-of-sight from the target will be coated.
Figure 6.9: Everything in the chamber is coated during the process.

Notice the Ar inlet in the top of the chamber.
A BIAS voltage can be coupled to the specimen holder making the specimens slightly
negatively charged e.g. 40 or 80 V. The negative charge attracts the Ar-ions, which thereby
slightly sputter the surface of the specimens.
21
The amount of target atoms that is atomized is depending on the sputtering yield (also called
sputtering coefficient) of the target material (Figure 6.10). The sputtering yield is defined as
“the number of atoms that is removed from the target per incoming ion”.
Figure 6.10: Sputter yield / coefficient as a function of atomic number [9].
In Figure 6.10 it is seen that it is easy to sputter e.g. gold and silver but hard to sputter silicon
and titanium.
6.3.3.3 Magnetron sputtering

Magnetron sputtering is basically the simple sputtering configuration with additional
magnetic fields. The extra magnetic field is close to the target (cathode) and is perpendicular
to the electric field imposed by the electrodes as illustrated in Figure 6.11.
Figure 6.11: The principle of magnetron sputtering [15].
This forces the particles to circulate through the magnetic field instead of following the
magnetic field in a straight line to the substrate (anode). Because of elongated path the
number of collisions is raised and the plasma can be maintained at a lower pressure. A
conventional DC-diode sputter operates at 0,5 - 10 Pa where as a magnetron sputtering
process can operate at 10-3 – 1 Pa. The reduced pressure leads to less contamination of the
process e.g. from the Ar gas. The lower pressure is also raising the mean free path of the target
particles, which is the average path the particles can move before they collide with a particle
from the gas. The longer mean free path, the higher the energy of the target particle when it
reaches the substrate and the better quality is the final coating at the substrate.
22
When comparing magnetron sputtering, to conventional sputtering the former process raises
the deposition rate and the ionisation efficiencies in the plasma and lowers the substrate
heating effects [16].
The non-reactive sputtering process can be combined with a reactive gas (typically oxygen or
nitrogen) in the chamber, turning it into a reactive sputtering process. This is e.g. used to make
coatings of: TiN, TiO2, TiAlN and CrN.
One of the problems with magnetron sputtering is the low usage of the target, which for at
standard cathode is generally less than 30 % [15]. Inserting an extra magnet in the centre of
the cathode and unbalancing the magnets to one another have improved the utilization
significantly. In Figure 6.12 the type 1 has a stronger centre magnet while type 2 has a stronger
ring of magnets in the perimeter of the cathode.
Figure 6.12: Schematic representation of the plasma confinement observed in conventional and
unbalanced magnetrons [16]. Type 1: Stronger centre magnet.
Type 2: Stronger ring of magnets in the perimeter.
The type 2 unbalanced magnetron sputtering is the most used and gives plasma that is not
strongly confined to the target region but is also flowing towards the substrate.
6.3.3.4 Coating structure model

There are important considerations to be done according to the microstructure of the
deposited thin film when coating with PVD. It is important to know the crystal structure and
whether the coating is tightly closed or if it contains small pores. For making an overview of
the structure of thin PVD coatings Thornton [17] made a structure model (Figure 6.13).
23
This model has been developed from experiments with OFHC (Oxygen Free High thermal
Conductive) copper [17]:
Figure 6.13: The Thornton structure model [17].
The Thornton structure model is divided into three main zones and a transition zone:
Temperature range,
Name Structure
suggested in [17]
Zone 1 Porous structure T/TM

Densely packed
Zone T 0,3

fibrous grains
Tight columnar
Zone 2 0,5

structure
Zone 3 Equiaxial structure

Table 6.4: Structure zones in the Thornton model.
TM is the melting temperature of the coating material.
In several cases the Thornton model has not been completely satisfying thus others have made
structure models e.g. Messier and Kelly & Arnell [16]. There have been discussions on
whether the y-axis should describe the Ar pressure or if other values (if necessary combined)
would be more appropriate and if this actually should be four dimensional or even more.
In relation to the structure model, the most important to this project, is being aware of the
different structure zones.
24
6.4 Characterisation techniques

The characterisation have primarily been carried out by four characterisation techniques:
scanning electron microscope (SEM), radio frequency glow discharge optical emission
spectroscopy (RFGDOES), normally called G-DOES, X-Ray Diffraction (XRD) and photo
spectrometry. In this section these four methods will briefly by described.
6.4.1 Scanning Electron Microscope (SEM)

For many tasks in material technology a light optical microscope (LOM) can be used, but
sometimes it is necessary with a higher magnification. In this case a scanning electron
microscope (SEM) is used. If even higher magnification is needed a transmission electron
microscope (TEM) should be used. Here follows a description of the SEM with the most
relevant features and detectors.
In Figure 6.14 is a schematic overview of a SEM.
Figure 6.14: Schematic overview of the component in a SEM [source: Wikipedia.org].
The source to the electrons is the electron gun, which is basically a heated filament of tungsten
or LaB6, which emits electrons (a field emission electron gun can also be used). The electrons
are attracted by an anode ring and are hereby accelerated towards the specimen. The lenses
focus the beam via electromagnets. The electron beam goes through the deflection coils that
control the direction of the beam and can thereby make the electron beam sweep over the
specimen surface like the electron beam of an old CRT (cathode ray tube) television screen.
A vacuum pump is connected to the microscope chamber to avoid the electrons of the beam
from collisions with the particles in the air. The magnitude of the vacuum is among other
factors dependant on the filament type and the sample type, but is in general the interval of
10-4-10-2 Pa for W and LaB6 filaments.
25
When the beam hits the sample two different kinds of electrons will be scattered from the
surface of the sample with energies as seen in Figure 6.15.
Figure 6.15: Energy distribution of scattered electrons.

Area A: Secondary electrons. Area B: Back scattered electrons [18].
The electrons in area A with low energy (< 50 eV) are generally the secondary electrons (the
beam is the primary electrons) and the electrons in area B with high energy (as high as the
incident beam) are called the backscattered electrons.
The secondary electrons are electrons being removed from its atom by a primary electron. An
electrical field of +400 V attracts the electrons to the secondary electron detector (Figure 6.14).
The brightness of the image from this detector depends on the number of secondary electrons
reaching the detector. The signal from the secondary electrons origins from only a few
nanometres into the sample surface. Because of the narrow beam it will have a large depth of
field compared to e.g. a LOM. Due to these abilities the secondary electron images (SEI) is
excellent for images of topology in a specimen surface.
The backscattered electrons are the primary electrons scattered back after a collision with an
atom in the sample. A donut-shaped backscatter electron detector is situated over the sample
around the incoming beam, since this is where the backscattered electron signal has the
highest intensity. Heavy elements in the sample will scatter electrons back more strongly than
light elements, and therefore heavier elements will appear brighter on the backscatter image.
The picture, are a result of the mean value of the elements in one spot, meaning that e.g. Al
will appear brighter (heavier) than Al2O3 since the mean weight of pure Al is higher than the
mean weight of Al and O (with and without the ratios considered). The signal of the
backscattered electrons can origin from a depth of up to 100 nm into the sample, and thereby
much deeper than the secondary electrons [18]. Due to the mentioned abilities the
backscatter electron images (BEI) are normally used for studying the surface for differences
in elements, e.g. whether a particle in the surface is a different material than the substrate.
Apart from the secondary and the backscatter electron detectors an X-ray detector is often
used. After emitting a secondary electron, the atom is left in an exitet state with a hole in one
of its shells. An electron from an outer shell fills the hole, and this can generate a characteristic
X-ray with an energy corresponding to the atomic energy shell. The energy / wavelength of
the emitted electromagnetic wave is registered by the X-ray detector. All elements have its
own characteristic X-rays and by e.g. energy dispersive X-ray spectroscopy (EDS or EDX) it is
possible to quantify the amount of the elements in a given area of the sample. By this
technique the EDS can be used to examine the composition of an area of a specimen.
26
6.4.2 (Radio Frequency) Glow Discharge Optical Emission

Spectroscopy ((RF)GDOES)
GDOES is used to make a depth profiling of elements in a material by sputtering into the
surface while detecting optical discharge emissions.
An argon gas is ionized and accelerated into a vacuum chamber and hammer into the
specimen, by which the atoms in the surface are removed from the surface into the chamber
(Figure 6.16). Additionally the atoms are exited and therefore emitting characteristic
wavelengths like in an EDS-analysis. The GDOES is slowly sputtering from the surface into
the specimen and thereby the GDOES can be used both for substrate analysis, to get a picture
of the element distribution from the surface and into the specimen.
Figure 6.16: Schematic overview of the GDOES chamber (Source: The graphical abstract of [19]).
After an experiment it is possible to quantify the result, so that it is possible to calculate the
weight percentage of each element.
By initial experiments with a given material it is possible to know the depth of the crater as a
function of the time.
6.4.3 XRD
X-ray diffraction (XRD) uses X-ray waves, which are sent towards a material. It is mainly the
electrons of the material that reflect the X-ray beam, and the beam is thereby diffracted [20].
The diffraction pattern is specified by the wavelength of the beam, , the spacing between the
lattice planes, d, and the incident angle, . The interference from the diffraction is completely
constructive when Bragg’s law is fulfilled [3]:
27
2d sin = n where is the incident angle to the surface, n is an integer and is the
wavelength of the incoming beam. A schematic illustration of Bragg’s law is presented in
Figure 6.17
Figure 6.17: Schematic illustration of Bragg's law (source: commons.wikimedia.org).
XRD can be used for several purposes e.g. identifying crystallographic phases and lattice types
and parameters.
6.4.4 Spectrophotometer measurements

A spectrophotometer is used for measuring the intensity of light in the visible and near visible
area as a function of wavelength. The results from a spectrophotometer is giving a relative
value of the intensity over the visible spectrum, thus it is possible to derive the general
intensity and the colour of the light from the graph. Spectrophotometers can be used for all
types of sources, e.g. measuring directly into a light source, transmission through e.g. a liquid or
a reflection on a material surface, which will be additionally elaborated here.
When measuring the reflection of a material, it is often preferred to use an integrating sphere.
An integrating sphere is a hollow sphere covered on the inside with a white layer, with a highly
diffusing and powerful reflection. With this equipment it is possible to get a complete
measurement of both the specular and the diffuse reflection of the current surface. Since an
integrating sphere diffuses completely the incident light the result is the same no matter
where a beam of light of a given intensity and colour enters the integrating sphere. [21]
28
7 Materials and preparation techniques

In the following chapter the used materials and the preparation techniques employed in the
present project is described.
7.1 Materials used

The primary materials for the project have been commercial aluminium alloys and aluminium
based plasma coatings.
7.1.1 Used Al alloys

During the project, four wrought alloys were used and one cast alloy. The details of these
materials are given below:
7.1.1.1 Alloy 1050

The 1050 alloy has the following composition:
Alloy Mg Si Fe Cu Mn Zn Ti V
1050 0,05 0,25 0,4 0,05 0,05 0,05 0,03 0,05
Table 7.1: The composition of the 1050-alloy [22].
Specimens of 50*50*1 mm has been cut out of a sheet of 1050 alloy supplied by LMG
(Lemvigh-Müller) in Denmark.
7.1.1.2 Alloy 5754

The 5754-alloy has the following composition:
Alloy Mg Si Fe Cu Mn Zn Ti Cr
5754 2,6-3,6 0,4 0,4 0,1 0,5 0,2 0,15 0,3
Specimens of 50*50*1 mm has been cut out of a 5754 alloy sheet by an unknown supplier.
7.1.1.3 Alloy 6082

Alloy Mg Si Fe Cu Mn Zn Ti Cr
6082 0,6-1,2 0,7-1,3 0,5 0,1 0,4-1,0 0,2 0,1 0,25
Specimens of 50*50*1 mm has been cut out of a 6082 alloy sheet supplied by LMG.
29
7.1.1.4 Alloy 6401

Alloy Mg Si Fe Cu Mn Zn Ti
6401 0,35-0,7 0,35-0,7 0,04 0,05-0,2 0,03 0,04 0,01
Specimens of 75*40*5,5 mm in alloy 6401 ALMINOX alloy were delivered from B&O
supplied by WkW-Erbslöh Automotive, Velbert, Germany. ALMINOX is a special flawless
alloy that is only produced by Erbslöh [24].
The specimens were polished by buffing on one side before sent to TI.
7.1.1.5 Alloy 46500

The cast 46500 alloy has the following composition:
Alloy Mg Si Fe Cu Mn Zn Ti Pb Sn Ni
46500 0,15-0,55 8,0-11,0 0,6-1,2 2,0-4,0 0,55 3,0 0,2 0,35 0,25 0,55
The main alloying elements in the 46500-alloy are Si and Cu.

Specimens of 75x25x4 mm in alloy 46500-alloy was delivered from B&O supplied from PDC
Teknik, Denmark. The specimens were polished on one side before sent to TI.
7.1.2 Titanium grade 1

Titanium grade 1 has the following composition:
Alloy C Fe H N O Ti
Ti Grade 1 0,1 0,2 0,015 0,03 0,18 99,5
Table 7.6: The composition of the titanium grade 1 [26].
The grade 1 titanium is a commercially pure alloy.

The titanium is used as cathodes in the PVD process. With varying power on the two
cathodes it is possible to vary the amount of Ti in the PVD coating. It this way a series of
specimens with different amounts of Ti has been produced to investigate how this changes
the optical properties of the coating.
7.2 Surface finishing treatments on commercial alloys

Here is the summary of various surface treatments employed throughout the project for
investigating the effect of surface finishing on optical properties before and after anodising
on the commercial 1050, 5754 and 6082 alloys.
30
7.2.1 Polishing using a buffing wheel

The buffing is done on a Polette 6NE from REF-Motor A/S at DTU (Figure 7.1). The
machine runs 3000 rounds per minute and uses a standard 150 mm cloth disc.
Figure 7.1: The used buffing machine.
As polishing agent is used a wax block, which is designated as coarse grained. The actual
polishing agent is unknown.
The polishing was examined and accepted based on visual inspection.
To transport heat away from the specimen, a small aluminium block was cut with a recess in
order to hold the specimens while polishing. By using the block the chance of generating the
previously described Beilby layer was reduced.
7.2.1.1 The water polishing machine

Water polishing was done on a Vapormate 3 delivered by ABS-Hesø I/S at DTU (Figure 7.2).
Figure 7.2: The used water polishing machined.
31
The top of the machine was opened and the specimen was placed on a cloth on the floor of
the chamber. The jet of water and particles was forcefully applied perpendicular to the
specimen surface and generally done in easy motions while ensuring that the whole specimen
is being polished more or less equally.
7.2.2 Anodising treatment

The anodising of the required aluminium specimens is carried out using a sulphuric acid bath.
The specimen is mounted on a titanium holder and a steel cylinder is used as the other
electrode. The experiment has been done in standard beakers with the following details:
• Degreasing with ethanol
• 4 minutes etching in a 60 g/L Alficlean solution at 60-62 ºC. Alficlean is a NaOH-
based cleaning and mild etching agent used at B&O
• 2 minutes rinsing in a beaker with demineralised water
• 2 minutes in a 55 ml/L HNO3 (from 65 % HNO3)
• 2 minutes rinsing in a beaker with demineralised water
• 30 minutes anodising in 100 ml/L H2SO4, at 21 ºC with 14 V with agitation
• 2 minutes rinsing in a beaker with demineralised water.
• 30 seconds rinsing with demineralised tap water
• 1 minutes blow drying at low level
• 1 minutes blow drying at high level
• Keep in dessicator
The anodising was done in a double-sided glass connected to a silicon oil cooler to maintain
the temperature. The temperature was continuously monitored to maintain the temperature
at a stable level. In general the cooling pump was set at 18,5 ºC as soon as the anodising
process was started to maintain the sulphuric acid at 21ºC. See Figure 7.3 for a graphical
overview of the anodising setup.
32
Figure 7.3: Graphical overview of the anodising setup.
7.2.3 Naming of commercial alloy specimens

Three different alloys has been used with two different polishing methods (or without
polishing), been etched (or not) and been anodised (or not). The naming of the specimens is
following this template:
Index Surface Not

Alloy Etching?
number treatment anodised?
xx n/B/W yyyy E %
Table 7.7: Template for naming the specimens.
Here xx is the sequential number given to the specimen. The n/B/W means that the specimen
has received “no polishing”, Buffing or Water polishing. The alloy is written in the place of
yyyy. If the specimen has been etched the letter E is written after the alloy. If the specimen has
not been anodised, there is a % at the end. Not etched and not anodised specimens do not
have the given mark.
Example:
27B1050E is specimen number 27 that has been polished with the buffing machine, it is the
1050 alloy and it has been etched and anodised.
The specimens are presented continuously in the results and discussion section due to the
high amount of specimens.
33
7.3 Synthesis of aluminium based plasma coatings
7.3.1.1 The PVD machine

The PVD process was done at the Tribology Centre at TI in Århus on a CemeCon 800/8,
which is shown in Figure 7.4.
Figure 7.4: The CemeCon 800/8 PVD machine at TI in Århus.
The specimens are cleaned before coating. This is done by 30 seconds in an ultra sonic bath at
40 ºC with acetone, followed by cleaning in ethanol, and blow-drying with clean air.
The specimens are mounted in the chamber along with two different sized pins, a small sheet
of glass and silicium. These are used for following tests of the coating and stored for later
references.
For the Ti-experiments two targets are used, where the left is an aluminium 1050 target. The
right target is either a pure titanium target or a Ti target with Al1050-pins drilled into it to
lower the surface area of Ti. The latter is used for getting an even lower amount of Ti in the
coating.
34
The standard process has been a coating with pure 1050-alloy. Meaning that two 1050-
targets were used both with 1000 W.
Left target Right target Starting Substrate Cathode

Heat Argon flow
power power pressure bias power voltage
1000 W 1000 W 0W 6 mPa 200 ml/min - 40 V ≈ - 500 V

Table 7.8: Standard setup for the PVD-process.
When a Ti-containing target replaces the right target, it is set at a cathode power between
100-300 W and then the left target power is raised to 2 kW to maintain the expected coating
thickness.
6401 targets have also been used with 1000 W as cathode power.
35
8 Characterization techniques
8.1.1 Optical microscopy and SEM
For the study of microstructure there were used a LOM Olympus GX41 (with Altra 20 Soft
Imagining System for connecting to the computer) and the JSM-5900 SEM from JEOL
(Figure 8.1) was used both at DTU.
Figure 8.1: The JSM-5900 SEM at DTU.
SEM pictures are taken with an acceleration voltage of 10 kV and a spot size of 35-40. EDS
analysis are done at 15 kV and calibrated with a nickel specimen.
36
8.1.2 GDOES
For an elemental analysis across the thickness of the anodised layer (depth profiling), Glow
Discharge Optical Emission Spectroscopy (GDOES) was used. The equipment used was the
GD Profiler 2 from Horiba Jobin Yvon as seen in Figure 8.2.
Figure 8.2: The GD Profiler 2 at DTU.
The examinations were done on a hard coatings 0-program, which is specified in Table 8.1.
Program name Pressure Power Pulse? Module Phase
Hard coatings 0 650 Pa 35 W No 7,6 V 3,8 V

Table 8.1: Setup details on the GDOES.
The examinations were done throughout the thickness of the anodised layer but in this report
mainly the first 200 nm will be in focus.
The measurements have been quantified according to weight percentage in the Quantum
XP2 program from HORIBA Jobin-Yvon. However the machine was not calibrated for Mg
and Zn, and therefore the results does not include these elements.
The thickness of the GDOES measurements is based on a value calculated in [2], where
comparisons with SEM pictures and other measurements concluded that the GDOES
sputtering removes approximately 37 nm/s when sputtering alumina.
37
8.1.3 XRD
For XRD measurements the D8Discover from Bruker AXS has been used (Figure 8.3).
Figure 8.3: The XRD setup. On the right is the X-ray source, in the middle is the specimens sticked to
the holder and to the left is the detector.
A continuous measurement has been done moving 0.03 degrees every nine seconds. The
turning of the specimen and the detector has been done with a two-to-one rate, meaning that
the detector turns twice as fast as the specimens. This is called a locked couple scan. The
generator has been set to 40 kV and 40 mA.
The measurements have been analysed in the EVA-software from Bruker.
38
8.1.4 Photospectrometry
The optical measurements on the specimens have been measured at DTU Fotonik at Risø
using the equipment seen in Figure 8.4.
Figure 8.4: The photospectrometry setup. On the picture is shown the lamp (blue box), the integrating
sphere (grey box) and the photospectrometer (black box).
A Mikropack HL-2000 white halogen light source (Mikropack GmbH, Germany) is

connected via an optical fibre to the top of a small aluminium cup. The cup is coated inside
with a white hemisphere called an integrating sphere. The optical fibre lights from the top of
the integrating sphere and down through a hole in the bottom of the cup (10 mm in
diameter). In one side of the cup, there is an optical fibre connecting to a photospectrometer
(Avantes, AvaSpec-2048), which is connected to a PC via USB. The PC has the AvaSoft 7.4
software installed.
Prior to measurements the program is calibrated, to make a black reference the lamp shutter
is closed and the cup is placed on a black piece of paper. The shutter is opened, and with a
special white calibration specimen the white reference is recorded in the program as the 100
% reflection spectrum. By this calibration the following measurement is done with respect to
the calibration spectrum, thus the spectrum of the lamp is taken into account in the spectrum
of the reflection curves.
As previously described, the reflection of a material can be described as a result of specular,
diffuse and ambient reflections. Since the aluminium cup is shutting of the surroundings, the
reflection is here only from diffuse and specular reflections in the material.
Before each measurement the specimen is visually examined to make sure that the area of
measurement is not contaminated.
Each specimen is measured two times, preferably on both sides unless the one side is not of
satisfying surface quality. The two measurements are plotted in the same figure and the
39
difference is estimated to validate the measurement error. An example of a validation plot can
be seen on Figure 8.5.
Validation graph example
27B1050E
71 Measurement on one
side of the specimen
70
69
Reflection [%]
Used mean graph
68
Measurement on the other
side of the specimen
67
66
65
400 500 600 700

Wavelength [nm]
Figure 8.5: Example for a validation graph.
Figure 8.5 shows two measurements for the specimen 27B1050E (alloy 1050 specimen, which
has been polished by buffing, etched and anodised), which have been measured on each side of
the specimen. By examination of the graphs, the measurements are determined to vary half a
percentage point. These measurements are therefore accepted as representative for the
specimen and the measurement error is estimated to be ± 0,5 %-point. The mean graph is also
plotted on the figure and this is the graph used for representing the measurements on
specimen 27B1050E on the following made figures.
Notice in Figure 8.5 that there is a bump around 640 nm. This is caused by the equipment and
not by the specimen. This has been tested on several other specimens than the ones for this
project.
In general for all the specimens, the characteristic3 (colour) of the two graphs from the
measurements are the same, but with varying intensity. The difference in intensity is in general
under two percent, and the ones with a higher variation are supplemented with additional
measurements. An average of the measurements is calculated and used for plotting.
By replacing a small part of the integrating sphere with a black part, the specular reflection
can be removed from the reflection graphs measuring only the diffuse reflection. By
subtracting the diffuse reflection from the full reflection (diffuse and specular) the
contribution from the specular reflection can be calculated.
3
By characteristic is meant the course or shape of the graphs
40
To check the setup, measurements were done on a mirror specimen found in the lab and on a
water polished alloy 1050 specimen, which were neither etched nor anodised (50W1050%.)
A picture of the water polished specimen and a mirror can be seen in Figure 8.6.
Figure 8.6: Diffuse (50W1050%) and specular (a mirror, not the used one) reflecting specimens.
The mirror has a high specular reflection and little diffuse reflection, while it is the opposite
for the water blasted specimen.
In Figure 8.7 the thick graphs are for the full reflections (diffuse + specular reflection), while
the thin graphs are only the diffuse reflection. Thus the specular reflection is the distance
between the thin and the thick graph.
On Figure 8.7 the black graphs are for the mirror where the full reflection is varying from 35%
to 45%, while the diffuse reflection is about 10%.
The measurements for the diffuse specimen (red graphs) are on top of each other around 35
%, showing that the specimen does not have any specific specular reflection but is totally
diffuse (the thin one is not obvious to find, but is easiest to see at the shorter wavelengths).
41
Full (thick) vs. diffuse (thin) reflection

50 Specular and diffuse reflecting specimen
Specular reflecting specimen (mirror)
40
Diffuse specimen (50W1050%)
30
Reflection [%]
20
10
0
400 500 600 700
Wavelenght [nm]
Figure 8.7: Full and diffuse reflection for a mirror and the water blasted specimen 50W1050%.
Figure 8.7 shows that the setup is working as expected.

Adjacent averaging in the Avasoft program has been used for smoothing the graphs.
8.1.5 Measurement errors on photospectrometry

From the validation plots a measurement error has been specified so that the difference
between the validation graphs is the measurement error in the photospectrometry
measurements. The measurement errors are presented in Table 8.2:
Specimens Measurement error
Anodised specimens ± 0,5 % points
Non-anodised specimens ± 2,0 % points
PVD coated specimens ± 0,5 % points

Table 8.2: Measurement errors for photospectrometry experiments.
Notice that the measurement errors stated in Table 8.2 is only for the intensity, not for the
characteristic (colour), which has an insignificant measurement error.
42
9 Results and discussion

This section is divided into three major parts about the effect of alloy composition and
treatment on optical properties (9.1), water polished specimens (9.2) and 9.3 concerning the
effect of titanium concentration in a PVD coating (9.3). In the end, two minor sections dicuss
the possibility of making a watermark underneath the anodised layer (9.4) and the use of
mokumé gane (9.5), which both are in progress.
9.1 The effect of alloy and treatment on optical properties

This section is divided into several subsections. The first subsections only focus on anodised
specimens being polished by buffing and non-polished specimens.
9.1.1 Anisotropy in optical measurements on a surface

On a rolled sheet, the grains of the specimens will not be equiaxial but visibly elongated along
the direction of the rolling. To test whether the grain orientation affects the optical
appearance, introductory measurements were made in the same spot with varying angle
according to the rolling direction. In Figure 9.1 the measurements of angle dependency on
specimen 22n5754E (alloy 5754, not polished, etched and anodised) is presented. On the x-
axis is the wavelength from 400-750 nm. On the y-axis is the reflection intensity, which is a
percentage of the reflection from the calibration specimen.
65 Angle dependency on sample 22n5754E
0 and 180 degrees follow the rolling direction
0 degrees
180 degrees
90 degrees
60
Reflection [%]
45 degrees
55
400 500 600 700

Wavelength[nm]
Figure 9.1: Angle dependency for the reflection on specimen 22n5754E.
43
In Figure 9.1 it is observed that there might be only a slight angle dependency on the specimen
with the used equipment. The reflection is highest for 0 and 180 degrees (following the grains
elongated axis) and lowest for 90 degrees (perpendicular to the elongated axis). The
difference in the measurements is up to two percent for the non-polished specimens.
When polishing, the elongated grains are not visible anymore and the angle dependency is
removed.
9.1.2 Presentation of the anodised specimens

The anodised specimens are presented in Table 9.1.
Anodised specimens
Alloy 1050 Alloy 5754 Alloy 6082
No polishing, with etching 36n1050E 22n5754E 23n6082E
Buffing, no etching 24B1050 25B5754 26B6082
Buffing, with etching 27B1050E 28B5754E 29B6082E

Table 9.1: Overview of the used anodised specimens.
The relationship between the surface treatment of different alloys and the optical effects is
investigated. Therefore as seen in Table 9.1, the specimens number 36+22-29 are variations
of the alloys 1050, 5754 and 6082 plus no polishing and buffing with and without etching.
44
9.1.3 LOM examination of the anodised specimens

The surface conditions of the anodised specimens have been examined with a LOM (Figure
9.2).

Figure 9.2: Surface conditions of the nine anodised specimens –the scale bar in the picture is 100 m.
Figure 9.2 shows clearly that the non-polished specimens have significant impressions from
the rolling process, which are removed during the polishing process. The structure of the
1050-alloy is smoother than the 5754- and 6082-alloys that contain holes and pores in the
surface both with and without both buffing and etching. The surface of 5754 and 6082 alloys
seems to be similar.
45
9.1.4 Element enrichment in the surface

Tabrizian-Ghalehno [2] suggest that the different colours of different aluminium alloys
could be due to enriched concentration of alloying elements (nanometer scale) in the surface
of the specimens. This enrichment was detected to peak around 30 nm from the surface.
With the performed optical measurements, it is now possible to correlate these with the
element concentration by using GDOES. An example of the GDOES measurements is seen in
Figure 9.3.
15
26B6082
10 Mn
Wt%
5 Si H
Ti+Cu
0
0 50 100 150 200
Depth (nm)
Figure 9.3: GDOES measurement for an alloy 6082 specimen, which has been polished and not etched
before anodising.
Figure 9.3 presents the amount of elements in wt% as a function of the depth under the
specimen surface. This figure is representative for the GDOES measurements for the 5754
and the 6082 alloys (see appendix).
As presented in Figure 9.3 has the same enrichment as proved in [2], although it does not peak
exactly at 30 nm.
As presented in Figure 9.4 the 1050 alloy has the same tendency of element concentration in
the surface as the other alloys. However, the non-etched specimen has as high concentration
as the other alloys, whereas this is much lower for the etched specimens.
46
Alloy 1050 for 0-200 nm

15 36n1050E
N
10 O Al
Wt%
S
5
H
Si Mn
Ti
0
0 50 100 150 200
15 24B1050
O
10 Mn
N
Wt%
5 H
Si
Ti+Cu Fe+Cr
0
0 50 100 150 200
15 27B1050E
10 N
Wt%
5 S
Si
Mn H
0 Ti Cu
0 50 100 150 200

Depth (nm)
Figure 9.4: GDOES measurements for the 1050 alloy specimens.
47
9.1.5 Alloy / treatment for anodised specimens

In Figure 9.5 the photospectrometry measurements are shown in three plots4 where the top
plot is only with alloy 1050, the middle is with alloy 5754 and bottom is with alloy 6082. In
each of the plots the black graph is the specimen that has not been polishing and etched. The
red graph is for buffing and no etching and the blue is for buffing followed by etching.
In Figure 9.5 the middle and the bottom plots are quite similar, with the red and blue graph
with the same intensity, and the black graph about five percent points below the others. In
the top plot, the red graph is the one with the lowest reflectivity and still with blue a little
above the black graph. From this finding it can be deduced that alloys 5754 and 6082 visually
react in the same way after the performed treatments, while 1050 does not. This is discussed
in the end of this section. Additionally it is found that the etching does not affect the
reflection intensity of 5754 and 6082 alloys, since the red and blue graphs has the same
intensity in the middle and lower plot, however, the etching increase the reflection intensity
of the 1050-alloy.
If looking at the characteristic (intensity vs. wave length reflected) of the graphs, the colour of
the surface deduced from the graph is the same for the same alloy with no dependency to the
treatment. Meaning that, the colour of the specimens is alloy-dependent, while the intensity
of the reflection is treatment-dependent.
In Figure 9.6 the same nine graphs have been plotted, but this time sorted so that graphs in the
same plot have received the same treatment. Thus, here the variation in a plot is the alloy.
In these plots it is observed that the top plot (no polishing, with etching) and the lowest plot
(buffing, with etching) are similar. The reflection of 1050 has higher intensity than the other
two, which has the same intensity. The middle graph is standing out since 1050 has the same
intensity as the other alloys in the interval around 600-650 nm.
When looking at the characteristic (colour) of the graphs 1050 is having relatively higher
intensity in the shorter wavelengths and lower intensity in the longer wavelengths. This
applies for all three plots. Visually this means that 1050 will appear more bluish (or perceived
as a cleaner white/grey) than the other alloys. This is also the case when looking at the
specimens with the eye.
Additionally, 5754 has higher intensity in both short and long wavelengths compared to 6082.
This could in principle give 5754 and 6082 slightly different tints, although this is not seen
with the eye.
As seen in Figure 6.2 (page 10) aluminium has a high reflectivity compared to other metals.
From this it can be expected that the intensity of the reflection in aluminium alloys will be
reduced with the amount of alloying elements. Therefore 1050 would be expected to have the
highest reflectivity of the three alloys, which is seen for the etched specimens. However, this
correlation is not present for the not-etched specimens, where they have the same reflectivity.
4
Notice that the word plot is consistently used for a drawn co-ordinate system with graphs.
Meaning that the word graph is used for a single graph on a plot.
48
When looking at the GDOES measurements for alloy 1050 (Figure 9.4), the concentration of
the alloying elements is much higher for the non-etched specimen, and therefore this can be
the reason for the lower reflection.
Sorted by alloy
Alloy 1050
Buffing, etching
70
Reflection [%]
No polishing, etching
65 Buffing, no etching
400 500 600 700

Alloy 5754 Buffing, no etching
65 Buffing, etching
Reflection [%]
60
55
400 500 600 700

65 Buffing, etching
Reflection [%]
60
55
400 500 600 700

Wavelength [nm]
Figure 9.5: Photo spectrometric plots for alloy 1050, 5754 and 6082 with three different pre treatments
before anodising.
49
Sorted by treatment
70 No polishing, with etching

1050
65
Reflection [%]
5754
60
6082
55
400 500 600 700

Buffing, no etching
5754
Reflection [%]
65
6082
1050
60
400 500 600 700

Buffing, with etching
70 1050
Reflection [%]
6082
65 5754
60
400 500 600 700

Wavelength [nm]
Figure 9.6: Photo spectrometric plots for three different treatments before anodising.
50
9.1.6 Full, diffuse and specular reflection

As described, measurements can be made, with only the diffuse reflection. This has been done
to get an overview of how big a contribution is made from the diffuse and the specular
reflection, and how this varies with alloy and pre treatment followed by anodising.
The measurements of the full (or total) and only the diffuse reflections are presented in
Figure 9.7 and Figure 9.8. In the same plot, two graphs of the same colour represent the same
alloy and pre-treatment. The thick graphs are the full reflection (diffuse + specular), the thin
graphs are for the diffuse reflection. The distance between these two graphs is the specular
reflection.
In Figure 9.7 it is observed that the black graphs on all the plots has the smallest distance to
each other, especially for 5754 and 6082 alloys. This means that the non-polished specimens
are relatively more diffuse reflecting than the polished specimens. Since the buffing is done to
obtain a more shiny surface, this is as expected.
The graph for buffing, no etching (red) has the greatest distance for alloy 1050, meaning that
this specimen has the highest specular reflection. However, the etching of the polished
specimens does not have an influence on the reflection type of the 5754 and 6082 alloys. This
might be because the etching agent in these experiments (Alficlean) is mild, compared to the
caustic etching where large amounts of material are removed from the surface.
In the middle and the lower plot the graphs are looking more or less the same, thus again 5754
and 6082 act very much the same to the treatments. This corresponds with the LOM
investigations presented in Figure 9.2.
When looking at Figure 9.8 the etched specimens (top and bottom plots) are comparable,
whereas the non-etched 1050-alloy specimen (middle plot) is standing out once more with
the lowest diffuse reflection.
When looking at each single pair of graphs (same colour, thick and thin in the same plot), it is
clear that the characteristic of the reflection is changed, meaning that the colour of the
reflection is different for diffuse and specular reflection. The distance between the graphs is
increasing with the wavelength, meaning that the characteristic (colour) of the graphs changes
when comparing the full and the diffuse reflection.
To make this fact clear, Figure 9.9 shows the specular reflection of the specimens where the
diffuse graph has been subtracted from the full reflection graph. Here the specular reflection
is more reddish compared to the diffuse reflections in Figure 9.7. Additionally the graphs
show that the characteristics of the graphs are the same for the polished specimens, but
compared to the non-polished specimens they are different. This means that the colour of the
specular reflection of these specimens vary with the surface treatment, and not with the alloy
as for the full reflection.
51
The difference in colour between the diffuse and the specular reflection could be due to the
surface structure of the specimens. As earlier mentioned the buffing gives a roughness around
1 μm, which is close in magnitude to the light, thus this can affect the light reflection. It could
also be due to scattering of the light caused by the alumina. Scattering will affect the blue light
the most leaving more red lights in the specular reflection.
Whether this is a general property for materials or it is a special property for these specimens
(or for anodised aluminium) has not been investigated further.
52
Full (thick) vs diffuse reflection

Alloy 1050
70 Buffing, etching
Reflection [%]
65
no polishing, etching
60
50
400 500 600 700

70
65
Reflection [%]
Buffing, etching
60
55
50
400 500 600 700
70 Alloy 6082 Buffing, no etching
65
Reflection [%]
Buffing, etching
60
55
50
400 500 600 700
Wavelenght [nm]
Figure 9.7: Measurements on full (thick) and only diffuse (thin) reflection, sorted by alloys.
53
Full (thick) vs. diffuse (thin) reflection

Sorted by treatment
70 No polishing, etching
1050
65
Reflection [%]
5754
60 6082
55
50
400 500 600 700
6082
1050
65
Reflection [%]
5754
60
55
50
400 500 600 700
Buffing, etching
1050
70
6082
Reflection [%]
65
5754
60
55
50
400 500 600 700
Wavelenght [nm]
Figure 9.8: Measurements of full and only diffuse reflection, sorted by treatment.
54
Specular reflection
Sorted by treatment
1050
Reflection [%]
5
5754
6082
0
400 500 600 700
1050
Reflection [%]
10 5754
6082
5
0
400 500 600 700
Buffing, etching
10 1050
Reflection [%]
5754
6082
5
0
400 500 600 700
Wavelenght [nm]
Figure 9.9: Only the specular reflection, sorted by treatment

(calculated as full minus diffuse reflection).
55
9.1.7 Visual effect of anodising

Another set of specimens was prepared with the same treatment but without anodising
(Table 9.2):
Not anodised specimens
No polishing, with etching 41n1050E% 42n5754E% 43n6082E%
Buffing, no etching 44B1050% 45B5754% 46B6082%
Buffing, with etching 47B1050E% 48B5754E% 49B6082E%

Table 9.2: Overview of the used not anodised specimens.
This was to investigate how the anodising is affecting the optical properties of aluminium in
general. And hopefully thereby to explore which part of the reflection is from the alumina and
which is from the substrate.
The results of the anodised and non-anodised specimens are plotted together (Figure 9.11
and Figure 9.12). Graphs with the same colour (on the same plot) are the same alloy and same
pre-treatment. The thick graphs are for the anodised specimens and the thin graphs are for
the non-anodised specimens.
In figure Figure 9.11 the results are presented in the same way as Figure 9.5, sorted by alloy.
In the top plot (1050-alloy) the no polishing, etching-specimen (black) falls in intensity after
anodising. The polishing, etching-specimen (blue) rise in intensity after anodising. And the
polishing, no etching-specimen (red) is both falling and rising varying with wavelength.
In the middle plot (5754-alloy) the two polished specimens rise in intensity after anodising.
The non-polished both rising and falling varying with the wavelength.
In the bottom plot (6082-alloy) the polished, no etching (red) graph has the same intensity, the
blue is rising and the black falls significantly.
The results do not seem to have any clear patterns as an effect of the treatment.
When looking at each single pair of graphs (same colour, thick and thin in the same plot), it is
clear that the characteristic (colour) of the reflection is changed, when anodising the
specimens. The thin graphs (except the blue in the bottom plot) for the specimens before
anodising is compared to their thick counterpart, and they all have relatively less intensity in
the shorter wavelengths and relatively higher intensity in the longer wavelengths. This means
that the specimens will look more red and less blue before the anodising compared to after.
Since the only difference from the previous measurements is the added layer of alumina, this
layer is expected to absorb more red than blue light. However, the explanation for this is not
clear, which needs more detailed experiments. Notice that in the previous example the overall
intensity of the reflection has not been taken into account, it is only relative to the
measurement for the same specimen with and without anodising.
56
The findings described above is clearly seen with the eye as observed in Figure 9.10 where two
6082-alloy specimens have been compared. It is seen that the unanodised specimen to the left
has a much more warm and reddish tint, than the anodised specimen to the right.
Figure 9.10: Alloy 6082 with etching, before anodising (left) and after anodising (right).
As mentioned the specimen of alloy 6082 with polishing and etching (blue in bottom graph)
does not follow this pattern, but the other way around. Additionally, the specimen of alloy
6082 with polishing and no etching (red) does not have the same significant change as the
other graphs. Consequently, this can be alloy dependent, and if that is the case, it is probably
due to higher amount of silicon or lower amount of magnesium since this is where the 6082-
alloy is clearly different from the 5754-alloy.
From Figure 9.12 an extra point must be added. The alloy 1050 has the highest reflection for
all the specimens before the anodising, no matter the pre treatment. In both the top and the
middle plot the 6082 alloy specimens has the highest reflection compared to 5754-alloy,
which is not the case in the bottom one. Additionally the 6082-alloy in the bottom graph has
a much different characteristic compared to the other alloys with the same treatment.
The alloy 6082 specimen, that has been polished and etched seems to be abnormal and
another specimen should be prepared to validate these measurements. This is supported by
the fact than on no other plot is observed an effect of the etching on alloy 6082.
57
Anodised (thick) vs. not anodised (thin)

Sorted by alloy
Alloy 1050
75
Reflection [%]
Polishing, etching
70
65
Polishing, no etching
60
400 500 600 700
70 Alloy 5754
65
Reflection [%]
60 no polishing, etching
55 Polishing, etching
50
400 500 600 700
70 Alloy 6082
65
Reflection [%]
Polishing, etching
60
55
50
400 500 600 700
Wavelength[nm]
Figure 9.11: Reflection curves for anodised and not anodised specimens, sorted by alloy.
58
Anodised (thick) vs. not anodised (thin)

Sorted by treatment
Reflection [%] 75
70 1050
65
5754
60 6082
55
50
400 500 600 700
70 Polishing, no etching 6082 5754
Reflection [%]
65
1050
60
55
50
400 500 600 700

Polishing, etching
70 1050
Reflection [%]
65 6082
5754
60
55
50
400 500 600 700

Wavelength[nm]
Figure 9.12: Reflection curves for anodised and not anodised specimens sorted by treatment.
59
9.1.8 Summary on alloy and treatment affect on optical properties

LOM investigation of the anodised specimens showed that non-polished specimens have
significant impressions from the rolling process, and that the structure of the 1050-alloy is
finer than the 5754- and 6082-alloys that contains holes and pores in the surface.
GDOES analysis showed an enrichment of alloying elements within the first 50 nm of the
surface of the anodised specimens.
The 1050-alloy has the highest reflectivity compared to 5754 and 6082 due to its higher
purity. Colour is alloy dependent, while intensity is treatment dependent. This might be due
to the fact that the surface treatment determines the roughness, therefore diffused reflection
and in turn the intensity. Etching with Alficlean increases reflectivity of 1050 compared to
the other alloys, probably due to the fact that the low levels of intermetallics are removed, and
thereby giving a higher reflectivity. However, this is not easy for other alloys due to the higher
density of distributed intermetallic particles. More detailed work on correlation with
microstructure and roughness before and after etching is needed to understand the exact
reason. It is interesting to see that in all cases, the more complex alloys 5754 and 6082 act
similar to the treatments, including that they are not affected by etching with Alficlean.
Buffing increases the specular reflection for all the alloys.
The specular reflection is reddish for all the specimens the colour varies with the surface
treatment, and not with the alloy as for the full reflection. It is suggested that alumina scatters
the blue light causing the specular reflection to be reddish. It has not been checked whether a
reddish specular reflection is a common property for specular reflecting materials.
Specimens will look more reddish and less bluish before anodising compared to after. Since
the alumina layer is the only difference, it must be the source of the change, e.g. because the
alumina absorbs more red than blue light.
60
In Table 9.3 is presented an overview:
Alloy 1050 5754 6082
Standard reflection
Highest Same as 6082 Same as 5754
(anodised), intensity
Standard reflection
Bluish white Reddish white Reddish white
(anodised), colour
Etching effect Higher intensity None None
Buffing effect, total Higher intensity

Higher intensity Higher intensity
reflection when etched
Buffing effect, specular

Higher intensity Higher intensity Higher intensity
reflection
Specular colour vs. diffuse

More reddish5 More reddish5 More reddish5
colour
Anodising effect, intensity Unknown Unknown Unknown
Anodising effect, colour More blue More blue Slightly more blue
Intensity before anodising Highest Medium Lowest
Intensity change when Enrichments Enrichments

element enrichment in Lowered present for all present for all
specimen surface measurements measurements
Colour effect of element Enrichments Enrichments

enrichment in specimen None present for all present for all
surface measurements measurements
Table 9.3: Summary of findings on optical variations.
It was planned to compare the results with SEM pictures, and specimens were put into the
SEM, unfortunately, these specimens charged too much for taking pictures. The specimens
must be carbon coating and taken into the SEM again. Unfortunately, the charging was
discovered too late and therefore this has not been done.
5
The effect is amplified when buffing
61
9.2 Water polished specimens

To investigate the effect when making an extra rough surface, water polishing was used. In
Table 9.4 the anodised specimens are presented and in Table 9.5 the not-anodised specimens
are presented.
Anodised specimens
Water polishing, no etching 30W1050 (31W5754) (32W6082)
Water polishing, with etching 33W1050E 34W5754E 35W6082E

Table 9.4: Water polished specimens that have been anodised.
The parenthesis around specimen 31+32 mean, that these are not made.
Not anodised specimens
Water polishing, no etching 50W1050% 51W5754% 52W6082%
Water polishing, with etching (53W1050E%) (54W5754E%) (55W6082E%)

Table 9.5: Water polished specimens that have not been anodised.
The parenthesis around specimens 53-55 means that these are not made.
62
9.2.1 Black anodising

In Figure 9.13 is seen a picture of two specimens, both are water polished, the one to the left is
not anodised, while the specimen to the right is anodised.
Figure 9.13: Water polished specimens. Left: 50W1050% without both etching and anodising. Right:
33W1050E, which has been etched and anodised.
Surprisingly, the specimen turns black when anodising. To make sure, that this phenomenon
is not alloy or etching dependent, all three alloys were water polished with the same result.
Also a specimen without etching before anodised gave the same result.
All three alloys have been measured in the GDOES with results looking much like the
previously shown in Figure 9.3 (shown in appendix).
SEM pictures have been taken of a water polished specimen without anodising (Figure 9.14)
and a specimen after anodising (Figure 9.15).
63
Figure 9.14: SEM picture of water polished, etched but not anodised specimen.
Figure 9.15: SEM pictures of water polished, etched and anodised specimen.
The pictures show a very chaotic structure with small structures of material everywhere.
There do not seem to be a big difference in the microstructure of the specimens, although it is
important to remember that the anodised specimen is having the previously described porous
anodised structure. As opposed to the non-polished and buffed specimens where the pores
are unidirectional perpendicular to the surface, here the pores will possibly go in all directions,
going into the surface, out from the surface and parallel to the surface. This might trap the
light inside the specimen surface structure instead of being reflected back. This phenomenon
is also known from zinc powder, which appears black even though it is actually light grey. On
the other hand, the pores are about 15 nm wide and they do therefore not affect the light.
64
The reason to the black anodising might be due to the formation of the highly deformed layer
on the surface due to the blasting, which responds to the anodising treatment in a different
way compared to the bulk material. The deformed layer on the surface usually will have a
nanocrystalline structure with high shear deformation and fractured making it highly reactive
during the anodising process. The disappearance of the black colour by simply etching the
specimen in NaOH (explained below) proves that the blackening effect is possibly due to the
formation of the highly deformed layer.
9.2.2 The etching experiment on water polished specimen

At B&O 6% NaOH is used as etching agent to avoid the black colour after e.g. shot peening6
and before anodising.
A specimen (alloy 5754) was water polished and afterwards dipped into a bath at 60 degrees
6% NaOH instead of the Alficlean. The specimen was dipped in a way, so that the top cm of
the specimen was not etched. After five seconds of etching, the specimen was raised one cm
etc. This was done so that the same specimen was etched for 0, 5, 10, 20 and 30 seconds. The
names of the regions is seen in Table 9.6:
Time of etching 0 seconds 5 seconds 10 seconds 20 seconds 30 seconds
Name Etching0 Etching5 Etching10 Etching20 Etching30

Table 9.6: Naming of specimen areas for the etching experiment.
6
Shot peening is much like water polishing, shooting round hard particles at a specimen. Shot
peening is normally for modifying the mechanical properties by plastically deforming the
surface material.
65
As expected based on experience from B&O the specimen went from black to light grey after
anodising, which is seen in Figure 9.16.
Figure 9.16: Etching experiment. The left side has been carbon coated for the SEM.
As observed in Figure 9.16 only five seconds of etching have a big impact on the appearance
after anodising. Hereafter the specimen is slowly turning lighter. This is also supported by
photospectrometry measurements, which is presented in Figure 9.17.
The etching experiment
30 sec
50 20 sec
10 sec
40 5 sec
Reflection [%]
30
20
0 sec
10
400 500 600 700
Wavelength[nm]
Figure 9.17: The etching experiment.
Even though it is hard to see in the picture (Figure 9.16), it is shown in Figure 9.17 that the
intensity increases with the amount of etching.
66
SEM pictures were taken of the specimen, where Figure 9.18 is of etching0, Figure 9.19 is of
etching5 and Figure 9.20 is of etching30 (etchng10 and etching20 can be seen in appendix). It
is seen for etching0, etching5 and etching30 that the structure starts chaotic but is etched
more and more homogenous by the NaOH giving round craters in the surface as seen in
etching30.
Figure 9.18: SEM of etching0.
67
Figure 9.19: SEM of Etching5.
Figure 9.20: SEM of etching30.
68
In the visual appearance in Figure 9.16 the biggest change is from etching0 to etching5, and
when examining the SEM pictures of these, it is discovered that the biggest folds and
corrugations of the structure is etched away in the first five seconds.
GDOES were used to investigate whether an extremely high enrichment of alloying elements
is present in the surface after water polishing (Figure 9.21). The etching0 is seen in the top left
corner, followed by 5 and 10 seconds of etching going right. The etching 20 and etching 30 is
in the lower row.
Etching experiment -zoom

Etching0 Etching5 Etching10
S
N
5 5 5
Wt%
Wt%
Wt%
H
H
H
Cu Cu Si
Mn Mn Ti
Cu Ti
Si Mn
Ti Si Fe+Cr
0 0 0
0 50 100 150 200 0 50 100 150 200 0 50 100 150 200
Depth (nm) Depth (nm) Depth (nm)
Etching20 Etching30
N
N
5 5
Wt%
Wt%
Si Si
Cu
Mn Mn
Ti
0 0
0 50 100 150 200 0 50 100 150 200
Depth (nm) Depth (nm)
Figure 9.21: GDOES measurements on etching experiment.
From Figure 9.21 it is found that the enrichment in the surfaces is similar for all the
specimens. However, when correlating the measurements, it is experienced that the amount
of enrichment of elements peak somewhere between etching5 and etching20. Notice that Cu
is higher at etching5 than etching10, meaning that Cu peaks before the other elements. This
might be due to the fact that Cu has a quite high sputter coefficient as seen in Figure 6.10
(page 22).
As already mentioned, the rolling process enriches the alloying elements in the surface. When
etching, the aluminium is etched more than the other elements, and therefore a ditch will
appear around these non-aluminium-particles, which consequently will be dug free over time.
When sputtering it will be “easier” to sputter particles if they have already been partly dug
free. This progress occurs until a point, where the particles are etched completely free and the
particles leaves the surface during the etching process prior to the sputtering. This is the
69
evolution that can be followed on the GDOES graphs. This finding is probably most
interesting from an academic point of view.
9.2.3 Summary on water polishing part

When water polished specimens are anodised (no matter of alloy and etching in Alficlean),
they turn black. This effect would be nice to control as long as UV-light and wear does not
affect the colour in an unfortunate way.
The black anodising can be turned grey by just five seconds of etching from a rough etching
agent as 6 % NaOH, and the specimen is turning brighter with the time of etching, at least in
the first 30 seconds.
When etching, the structure goes from extremely chaotic and rough to more homogeneous
and slowly the roughness is also evened out.
9.3 The effect of Ti-concentration on optical properties in

aluminium coating
Notice that all measurements in the following sections have been performed on non-anodised
specimens.
In Table 9.7 an overview of the PVD specimens is presented:
PVD specimens
Specimen TI batch Layer Also steel

Composition Right target
name name thickness substrate?
Pure1050 b2165 Pure 1050 22 – 28 μm 1000 W (as left)
Pure6401 b2164 Pure 6401 22 – 28 μm 1000 W (as left)
AlTi3 b2194 3,0 ± 0,1 wt% Ti 24 μm Mixed, 100 W Yes
AlTi4 b2178 4,3 ± 0,1 wt% Ti 7 μm Pure Ti, 100 W
AlTi5 b2188 5,4 ± 0,1 wt% Ti 16 μm Pure Ti, 100 W Yes
AlTi9 b2179 9,3 ± 0,1 wt% Ti 6 μm Pure Ti, 200 W

Table 9.7: Overview of PVD coated specimens. Notice that AlTi8 is rounded down in the specimen
name even though it mathematically should be rounded up. SDOM (Standard Deviation Of Mean) is
given as error on compositions based on six measurements, three in two different sites.
All thickness measurements have been done at TI by cross section pictures on a SEM or by a
coating thickness test. The composition is measured with EDS in the SEM at DTU. Notice
that the rest of the composition is Al1050, not chemically pure Al.
70
Some coatings are only done on cast aluminium and some are both done on cast aluminium-
and steel-substrates as marked in Table 9.7.
9.3.1 Examination of the PVD coating

The PVD coatings have been examined with a LOM, with a representative example in Figure
9.22.
Figure 9.22: Representative LOM cross section picture of the AlTi5 specimen.
In Figure 9.22 the top black part is the resin and the mixed lower part is the cast aluminium,
with the coating as the light clean part between these. As mentioned this picture is
representative for the specimens, however, some specimens turned out to have quite large
particles underneath the coating and some are even cracking the coating as seen in Figure 9.23.
Figure 9.23: Example of particles underneath and penetrating the coating. Specimen: AlTi7.
71
In general the coatings covers the substrate sufficiently, but some places as seen in Figure 9.23
the coatings does not have as good adhesion to the substrate as e.g. in Figure 9.22. Some
representative LOM pictures can be seen in the appendix.
A SEM picture of the AlTi4 is presented in Figure 9.24.
Figure 9.24: SEM picture of cross-section of AlTi4. Taken at Århus University.
In Figure 9.24 the columnar structure described in the Thornton model (page 23) is clearly
seen. From the image the column size is measured to be approximately 0.2 to 1.0 μm wide. It is
not possible to see whether it is a zone 1 or a zone 2 structure. There is no visible spaces
between the columns, but it is not certain whether this is due to a zone 2 structure, or whether
it is because the spaces are not discovered e.g. because they are located elsewhere or they are
smaller than what is detectable in the picture.
72
The specimens have been analysed by XRD. A representative example (AlTi3) can be seen in
Figure 9.25. The other analyzed specimens gave similar results.
Figure 9.25: XRD measurements for AlTi3. Green lines are for Al and blue lines are for Si.
From Figure 9.25 it is seen that most of the peaks are from Al and Si. The Al can both be from
the coating and from the substrate of cast aluminium. On contrary the Si must be signals from
the substrate.
Around 2 = 35º there is a peak calculated to be a beta peak of the strong peak at around 2 =
38º. There are two unidentified peaks in this graph, which tend to be present in the other
graphs as well. There is an extra unidentified peak for AlTi4, and only for this. All XRD
measurements can be seen in appendix including two plots for steel substrates. The steel
substrates do not seem to affect the tendencies of the measurements.
Both unidentified peaks are present in the 1050-alloy measurements, meaning that the
titanium does not cause these. The peak at 2 = 37º is present for the steel substrate as well,
which support the fact that that this is originating from the coating.
The XRD measurements show that α-Al and Si phase is found, and one or more unidentified
phases. From these measurements no definitive conclusions can be made.
73
9.3.2 Visual impact of titanium concentration on full reflection

To find out how the Ti-concentration is affecting the optical properties of the coating, the
titanium specimens were measured with the photospectrometer at Risø. The results can be
seen in Figure 9.26 with the clean 1050-alloy as reference.
AlTi coatings on casted Al
pure 1050
85
AlTi5
Reflection [%]
AlTi4
AlTi8
80 AlTi9
75
400 500 600 700
Wavelength[nm]
Figure 9.26: Photospectrometry of AlTi coatings if different concentrations.
In Figure 9.26 the clean 1050 have the highest intensity followed by AlTi5, AlTi4 and
AlTi8+AlTi9 together. Although the AlTi5 is higher than the AlTi4, it is a trend that the
intensity of the reflection falls with the amount of Ti in the coating.
74
The intensity of the graphs in Figure 9.26 has been collected and normalised to 0% at 575 nm
to compare the colour of the specimens to find out whether there is a colour change with the
amount of Ti (Figure 9.27).
1 Comparing colours of the AlTi specimens
-1
AlTi4
AlTi5
Reflection [%]
-2
pure 1050 AlTi8
AlTi9 AlTi9
-3
AlTi8 pure 1050
AlTi5
-4
AlTi4
-5
400 500 600 700
Wavelength[nm]
Figure 9.27: Comparing colours of AlTi. The graphs has been normalised to 0 % at 575 nm.
In Figure 9.27 clean 1050 is in the middle of all the measurements. This is both for the longer
and the shorter wavelengths. The other four measurements are switching places, so that the
AlTi4 is highest in the shorter wavelengths and lowest in the longer wavelengths. AlTi8 is the
other way around. The AlTi4 specimen is then the most bluish specimen and AlTi8 is most
reddish. It is hard to make a clear conclusion from Figure 9.27 other than it seems that Ti is
changing the colour of the reflection before anodising, but this seems to be quite little, and it
is not visible by the eye.
75
9.3.3 Full vs. diffuse reflection

The full reflection (thick graphs) and the diffuse reflection (thin graphs) have been compared
for samples AlTi5 and AlTi8 in Figure 9.28.
Full (thick) vs diffuse (thin) reflection
90
85
AlTi5
Reflection [%]
80
AlTi8
75
70
400 500 600 700
Wavelenght [nm]
Figure 9.28: Photospectrometry for full (thick) and diffuse (thin) reflection on the AlTi5 and AlTi8
specimen.
As previously seen AlTi5’s full reflection is of higher intensity than the one for AlTi8. The
same turns out to be the case for the diffuse reflection. Additionally, the diffuse reflection is
“on level” at the shorter wavelengths but has got lower intensity in the longer wavelengths,
meaning the specular reflection is reddish compared to the diffuse reflection in Figure 9.28.
This is the same tendency as the previously comparisons of the full and diffuse reflections in
section 9.1.6 for the other specimens.
When looking at the specular reflection for the same two specimens in Figure 9.29 it is
observed that the specular reflection is bigger for the AlTi8 than the AlTi5.
76
Specular reflection for AlTi5 and AlTi8
5
Reflection [%]
AlTi8
AlTi5
0
400 500 600 700
Wavelenght [nm]
Figure 9.29: Specular reflection for AlTi5 and AlTi8.
In Figure 9.29 it is also found that AlTi8 has the most reddish specular reflection.
This is verified when looking with the eye (Figure 9.30):
Figure 9.30: Picture of AlTi5 (left) and AlTi8 (right).
77
At Figure 9.30 the lamp reflection is both sharper and slightly more reddish on the AlTi8 to
the right. Although this is much more clear with the eye, than on this picture.
These are the only AlTi-specimens measured for only the diffuse reflection. Figure 9.29
indicates that the specular reflection is increasing with the amount of titanium but
measurements of more specimens needs to be made.
Additionally this shows that while the specular reflection is increased the diffuse reflection is
decreased with the concentration of Ti. This might be due to the effect on the surface
roughness of the coating, which should be investigated further.
9.3.4 Change of substrate material

To check whether the substrate material has an effect on the reflection curve for the coating,
a few measurements were made with coatings on cast aluminium and steel (Figure 9.31).
Test on different substrates
AlTi5
Casted Al
85 Steel Casted Al
Reflection [%]
Steel
80
400 500 600 700

Wavelenght [nm]
Figure 9.31: Photospectrometry on steel and cast Al specimens with the same AlTi5-coating.
Figure 9.31 shows two measurements on a cast aluminium substrate and two measurements
on a steel substrate. As expected, Figure 9.31 indicates that there is no difference in the
reflections.
Notice that the coating of AlTi5 is 16 μm, so it should be expected that only the mechanical
properties of the substrate and not the optical properties should have an effect, therefore the
results of Figure 9.31 is expected.
9.3.5 Anodising the PVD coatings

B&O has anodised a layer of about 7μm on the PVD coatings. This has been done on several
specimens both with and without titanium as alloying element. Only the clean 1050-alloy has
78
been successfully anodised. Anodising of alloys 1050 and 6401 coatings are presented in
Figure 9.32. AlTi5 has also been anodised; the result is presented in Figure 9.33.
Figure 9.32: Anodised coatings on cast aluminium substrates. Top: Alloy 1050. Bottom: Alloy 6401.
Figure 9.33: Anodised AlTi5 specimen on cast aluminium substrate.
In Figure 9.32 it is observed that the 1050 coated specimen has been successfully polished and
anodised giving a glossy appearance. The 6401-alloy is normally used to make a highly glossy
finishing, but here it is quite matt. An example of a normal 6401-alloy specimen, which has
been polished is presented in Figure 9.34.
Figure 9.34: Regular 6401 specimen polished and anodised at B&O.
79
The same is observed on the AlTi5 specimen in Figure 9.33. A closer examination with the eye
shows small pores in the coatings of all the three specimens.
It is not expected that the anodising should be better than achieved on the AlTi5 specimen,
but the anodising of the 6401 coating is not expected and implies that the coating is not
satisfactory prior to the anodising.
Due to this problem, no more AlTi specimens have been anodised, instead time has been
spend on understanding the reason for the bad anodising of the 6401 coating.
9.3.6 Reason for bad anodising

The bad anodising can be the result of two reasons:
• A porous coating is created during the PVD, making it possible for the anodising
electrolyte to reach the substrate.
• Elements in the coating are located or making inter metallic particles in an
unfavourable way.
These two possibilities will be discussed in the following:
9.3.6.1 Electrolyte reaches the substrate

If there is a passage through the coating, the sulphuric acid will get in contact with the
substrate material. When the substrate material is cast aluminium, the silicon might darken
the surface as described for cast aluminium specimens. If the substrate is e.g. steel, the
sulphuric acid will corrode the steel instead and probably not leave a good result.
The open structure of the coating can either be due to larger pores, cracks or particles as seen
in LOM photo in Figure 9.23 (page 71) or because of minor pores between the grains in the
surface structure. B&O examined cross sections with LOM of the coatings after the anodising
and found no large pores or cracks. A representative picture can be seen in Figure 9.35.
Figure 9.35: LOM of specimen AlTi5. This picture is taken after the anodising.
The anodising layer is almost impossible to see, but is marked with the upper red line.
80
Figure 9.35 presents the anodised layer (very dark, 3 μm thick) and the rest of the coating,
which is measured to be 10 μm thick.
Since no big flaws in the surface was found, a Thornton zone 1 structure (page 23) should be
expected, if contact with the substrate is causing the problem. On the other hand, if it then
will be possible to obtain a zone 2-structure all over the coating, the coating will be closed and
the substrate material will not be in contact with the sulphuric acid.
9.3.6.2 Particles in the coating

If the structure is closed then the problem is in the coating. This will be inter-metallic
particles gathered in the columnar structure, mainly in the grain boundaries. This will
interfere with the anodising process and might make the anodising bad. Particles in the
coating should be present in the XRD measurements, which have neither been validated nor
discarded.
The possibility of a surface structure that is very chaotic giving a black anodising as seen with
the water polished experiments was investigated. SEM investigations of alloy 1050 and alloy
6401 and some of the AlTi specimens (top view) have been made, and they look identical.
Figure 9.36 presents the structure of the surface of a 6401-alloy specimen before anodising.
The same structure is seen for all the specimens (including 1050) making it less plausible that
the surface structure is causing a black anodising, since the 1050-alloy can be anodised.
Figure 9.36: SEM picture of 6401-alloy specimen before anodising.
The problem with the bad anodising has not yet been solved, although new tests have been
initiated.
81
9.3.6.3 Tests on PVD coatings

To find out what is actually causing the problem, a new specimen is being made with 6401-
alloy for both the substrate and the coating. In this way, if the anodising turns out bad then
the problem is caused by particles or bad structures in the coating. If the anodising turns good,
then the problem is due to contact with the substrate and thereby a non-closed coating.
After this result an experimental series will be started testing by varying heat power, specimen
bias voltage and target power. Until now 6401 substrate has been coated with 6401-alloy as
coating with the following PVD settings:
Specimen name Heat power Specimen bias voltage Target power
B2187
0W - 40 V 1000 W
(standard)
B2203 500 W - 40 V 1000 W
B2204 1500 W - 40 V 1000 W
B2205 0W - 80 V 1000 W
B2206 0W - 40 V 2000 W
Table 9.8: Overview of experimental series for avoiding bad anodising.
As seen in Table 9.8 the heat power, bias voltage and target power has been changed from the
“standard” program (b2187). Since this series is made on 6401 as substrate, this can mainly be
used if the testing on the standard program turns bad, meaning that the problem is caused by
particles in the coating.
82
9.3.7 Summary on PVD part

The total reflection intensity depends negatively on the Ti concentration. The colour does
only depend slightly on the Ti concentration, but the dependency is not obvious.
Measurements show that a higher Ti-concentration increase the specular reflection, meaning
that the roughness is less with higher Ti-concentration.
Substrate does not affect the optical properties due to the thickness of the coating.
It would have been more interesting to make measurements after anodising, but due to the
bad anodising of the 6401-coating, the main priority was to get better in controlling the PVD
coating. The bad anodising can be due to:
• Electrolyte reaches the substrate
• Particles in the coating
LOM pictures show in general good adhesion but somewhere it is wrecked by particles placed
under the coating.
SEM pictures reveal the expected columnar structure, although it is not possible to register
pores for the electrolyte to reach the substrate.
XRD measurements prove that an aluminium phase and silicon phase are present, including
one or more unidentified phases.
It has not been concluded, which of these reasons is causing the bad anodising, but further
tests has been initiated.
83
9.4 Watermark under the anodised layer

Since the PVD coating growth morphology is affected mainly by the surface morphology of
the substrate, a memory effect is observed where the tiny details of the surface morphology of
the substrate will be transferred to the coating. This means that even a tiny scratch on the
surface will be preserved through the coating and therefore the scratch can be observed on the
coating surface unlike in the case of electroplating where the scratch will be covered with
metal deposition. This was also reported in [1] where a specimen of cast aluminium was
polished and coated with 30 μm of 1050 aluminium. Now the polishing marks could not be
seen but after the anodising process the polishing grooves were coming clear and visible. As
illustrated in Figure 9.37 the PVD layer follows the topography of the underlying specimen,
this is called the memory effect.
Figure 9.37: The memory effect. PVD layers on top of a product surface [1].
Due to the memory effect, if the specimen has a scratch, the PVD coating will follow this
scratch. As indicated in Figure 9.37 the memory effect wears off when the coating gets
thicker.
This effect can e.g. be used for writing the product company name into a product, but it can
also be used as theft protection. Today computers, phones and other equipment at big
companies e.g. DTU has been branded the company name by melting the plastic of the
product as seen in Figure 9.38.
Figure 9.38: Telephone at DTU with branded name as theft protection.
84
Instead of a theft protection in a way that actually harms the aesthetics of the product this
type of theft protection has the potential of meeting the aesthetics of the rest of the product.
At the same time the watermark is placed underneath the anodised layer and thereby it is not
possible to remove the watermark without wrecking the product.
An initial experiment has been started, where a sheet has been laser engraved with varying
laser settings. The deepest of the laser engraving has been measured to be about 22 μm. The
specimen is going to be coated with 30 μm of 1050-alloy and anodised with about 7 μm
afterwards.
9.5 Mokumé gane

An ancient forging method has recently been reinvented. The process is called mokumé gane
and was used for swords, jewellery and ornaments in the ancient Japan. The technique relies
on experience, but Ian Ferguson has written a partly theoretically founded book on the
subject [27].
The technique is using two different alloys alternating in thin layers on top of each other. The
alloys are selected in a way so that they react differently to a selected pigment. It is important
that the adhesion of the layers does not imply too much diffusion between the two alloys. The
material is rolled out to a plate or a sheet, which is made uneven, whereafter the sheet is
polished into an even surface again (Figure 9.39).
Figure 9.39: Mokumé gane: Alternating layers of two different alloys [27].
The polishing line is seen as a thin black line cutting through the bumps.
The required amount of polishing will vary in different parts of the specimen. Thereby it will
vary which alloy is at the surface in different areas of the specimen. After anodising, colouring
and sealing, the specimen will vary in appearance in different areas as seen in Figure 9.40.
85
Figure 9.40: Aluminium bowl produced with the mokumé gane technique [27].
As seen in Figure 9.40 it is possible to use the mokumé gane technique on aluminium. The
mokumé gane gives the product a more alive and sort of pottery look.
An experiment has been started, where the mokumé gane technique is going to be used. A
remote control from B&O has been drilled for recesses with about 200 μm. In these recesses
TI has started to coat different layers of aluminium alloys for about 20μm at the time.
Afterwards B&O will anodise and colour it, hopefully, making it into the first mokumé gane
remote control. Until now there has not been done any considerations on which alloys to use,
but it has to be alloys that react differently to dyes.
Even though two remote controls have received the same treatment, this technique is so
sensitive, that the products appearance will vary as known from pottery. Now the customer
can choose which remote control he likes the most.
86
10 Conclusion
1. The experimental technique for determining the optical properties of the surfaces has
been tested on various surfaces and standardized for the investigation. The technique
seems to be very much useful for establishing the optical properties of the surfaces with
and without anodising.
2. The optical properties of the surface depend on the surface finishing and the alloy
composition. The intensity of reflection is most dependent on the surface finishing due to
the big change in diffused reflection as a function of roughness (at least for rolled sheets),
while the colour of the reflection depends most on alloy composition.
3. Anodising of the sample also shows an effect on the optical properties turning the
specular reflection reddish and the diffuse reflection bluish, which might be due to
scattering of the light by the aluminium oxide layer. It has not been possible to conclude
how the total reflection intensity is affected by anodising.
4. GDOES depth profiling of the anodised layer show enrichment of alloying elements in
the surface, which might be affecting the intensity of the reflection of pure alloys as 1050.
5. For the PVD coated specimens, increased quantity of Ti in the coating decreases the
overall reflection intensity, while the specular reflection is increased. Additionally it is
shown that increased aluminium purity increases the reflection intensity.
6. X-ray diffraction of the PVD coated samples showed that the Ti in the coating present as
elemental Ti without any second phase formation, since unidentified phases are also
found for the clean 1050 coating. There might still be phases, which are too small to be
detected by the XRD.
7. Water-polished specimens have a very rough surface structure making it totally matt.
Surprisingly, when anodising a water-polished specimen turns black, which can be avoided
by etching the specimen before anodising. An explanation of the phenomenon has not
been within the scope of this project.
87
11 Future Work
1. The described bad anodising of the PVD coatings is an essential problem for the further
movement of the IdeAl project. As described a series of specimens have been made to find
the reason for the bad anodising and to investigate how to avoid it.
2. More detailed investigation on the relation between optical appearance, surface finishing,
chemical composition, and microstructure of the alloy. This will be carried out by
preparing binary and ternary alloy systems with different alloying elements in PVD
coatings.
3. Effect of heat treatment and phase formation in the coating on change in optical
properties of the anodised layer in presence of various alloying elements in the coating.
4. Variation of refractive index of the anodised layer for the similar alloys with and without
surface treatment to understand the role of undissolved particles in the anodised layer on
optical appearance.
5. Standardised experiments using coloured anodised layers containing particles with

known size, to understand the scattering effect as a function of particle size.
6. More detailed electron microscopic investigation of the microstructure of the alloys /

coatings and surface roughness by AFM to be correlated with optical appearance.
7. Investigations of laser cladded coatings and their influence on optical properties in detail.
88
12 References
[1] H. T. Holt and R. H. Møller, Anodisering af aluminium med optimerede
egenskaber. Master thesis, DTU MEK: , 2008.
[2] N. Trabrizian-Ghalehno, Advanced Anodizing Technology. Ph.D., DTU-MEK: ,
2009.
[3] E. Hecht, Optics, 4th ed., Addison Wesley, 2001.
[4] R. J. D. Tilley, Colour and the Optical Properties of Materials: An Exploration of
the Relationship Between Light, the Optical Properties of Materials and Colour.
Wiley-Blackwell, 1999.
[5] Course: 02569, Light and Materials, “N02-b-Phong-2008.”
[6] “Wikipedia.” [Online]. Available: http://www.wikipedia.org/. [Accessed: 10-Aug-
2010].
[7] C. Vargel, Corrosion of Aluminium, 1st ed. Elsevier Science, 2004.
[8] S. Wernick, R. Pinner, and P. G. Sheasby, The Surface Treatment and Finishing of
Aluminium and Its Alloy, Volume 1, 6th ed. ASM International, 2001.
[9] P. Møller and L. P. Nielsen, Advanced Surface Technology, Part 1, 1st ed. Møller
& Nielsen, 2010.
[10] “Aluminum Metallurgy.” [Online]. Available:
http://www.secowarwick.com/pressrel/articles/aluminummetallurgy.htm.
[Accessed: 08-Aug-2010].
[11] H. Dam, L. Gerward, O. Leistiko, T. Lindemark, A. Nielsen, and O. T. Sørensen,
Materialebogen, 1st ed. Nyt Teknisk Forlag, 2008.
[12] J. Stokes, Theory and Application of the High Velocity Oxy-Fuel (HVOF) Thermal
Spray Process. Dublin City University, 2008.
[13] SkanAluminium, Aluminium Overfladebehandling. Oslo: Skanaluminium, 1972.
[14] U. J. Andersen, Anodisering af aluminium. Danish Technological Institute,
Kemiteknik, 1980.
[15] G. Bräuer, B. Szyszka, M. Vergöhl, and R. Bandorf, “Magnetron sputtering -
Milestones of 30 years,” Vacuum, vol. 84, no. 12, pp. 1354-1359, Jun. 2010.
[16] P. J. Kelly and R. D. Arnell, “Magnetron sputtering: a review of recent
developments and applications,” Vacuum, vol. 56, no. 3, pp. 159-172, Mar. 2000.
[17] J. A. Thornton, “Influence of substrate temperature and deposition rate on structure
of thick sputtered Cu coatings,” Journal of Vacuum Science and Technology, vol.
12, no. 4, pp. 830-835, Jul. 1975.
[18] J. , “Invitation to the SEM World,” JEOL, 2006.
89
[19] T. Nelis, M. Aeberhard, M. Hohl, L. Rohr, and J. Michler, “Characterisation of a

pulsed rf-glow discharge in view of its use in OES,” Journal of Analytical Atomic
Spectrometry, vol. 21, no. 2, p. 112, 2006.
[20] P. Møller, Overfladeteknologi, 1st ed. Kbh.: Nyt Teknisk Forlag, 1998.
[21] “Encyclopedia of Laser Physics and Technology - integrating spheres, Ulbricht
sphere.” [Online]. Available: http://www.rp-
photonics.com/integrating_spheres.html. [Accessed: 10-Aug-2010].
[22] J. R. Davis, Aluminum and Aluminum Alloys (Asm Specialty Handbook),
Illustrated edition. ASM International, 1993.
[23] “6401.” [Online]. Available: http://www.euralliage.com/6401.htm. [Accessed: 31-
Aug-2010].
[24] “ALMINOX - WKW.automotive - wkw.de.” [Online]. Available:
http://www.wkw.de/en/competence/material/alminox.html. [Accessed: 01-Sep-
2010].
[25] “Indian & U K Standard ( Chemical Composition of Aluminium Alloys.” [Online].
Available: http://www.docstoc.com/docs/39173549/Indian-and-U-K--Standard-(-
Chemical-Composition-of-Aluminium-Alloys. [Accessed: 20-Aug-2010].
[26] “ASM Material Data Sheet.” [Online]. Available:
http://asm.matweb.com/search/SpecificMaterial.asp?bassnum=MTU010.
[Accessed: 03-Sep-2010].
[27] I. Ferguson, Mokume Gane. Krause Publications, 2004.
90

Appendix, contents

1. GDOES measurement for non-polished and buffed specimens Pages: B-D
2. GDOES measurements for water polished specimens Pages: E-H
3. SEM pictures of etching10 and etching20 Pages: I-J
4. LOM pictures of the AlTi specimens Pages: K-Q
5. XRD measurements of PVD coatings Pages: R - W

" ! #!

1.
GDOES measurements for non-
polished and buffed specimens

" ! #!

15
22n5754E S
Al
O
10
Wt%
Mn
5
H
Ti Si
0
0 50 100 150 200
15
25B5754 S
10
N
Wt%
Mn
5
H
Si
Cu+Ti Fe+Cr
0
0 50 100 150 200
15
28B5754E
Mn
10
Wt%
5 H
Ti+Cu
Si
0
0 50 100 150 200
Depth (nm)

! "


15
23n6082E
N
10
Wt%
Mn
5 H
Si
Ti+Cu+Cr
0
0 50 100 150 200
15
26B6082
10 Mn
Wt%
5 Si H
Ti+Cu
0
0 50 100 150 200
15 29B6082E
10 Mn
Wt%
Si N
5 H
Ti Cu
0
0 50 100 150 200
Depth (nm)

! "

2.
GDOES measurements for water
polished specimens

" ! #!

30 33W1050E -Full analysis
20
Wt%
10 Precipitate
H
0
0 5000 10000 15000 20000
15 33W1050E -zoom
10
wt%
H
Mn
Si
0
0 50 100 150 200
Depth(nm)

" ! #!

30 34W5754E -full analysis
O
20
Wt%
10 S
C Mn
N
0
0 5000 10000 15000 20000
20
34W5754E -zoom
15 C
S
wt%
10
Mn
N
Si Cu+Cr
Ti
0
0 50 100 150 200
Depth [nm]

" ! #!

35W6082E -full analysis

30
20
Wt%
10 S
Mn
N Si
0
0 5000 10000 15000 20000
15
35W6082E -zoom
C
Al
10
Mn
wt%
N
Si
Ti Cr
0
0 50 100 150 200
Depth [nm]

" ! #!

3.
SEM pictures of etching10 and
etching20

" ! #!

! "

4.
LOM pictures of the AlTi-specimens

" ! #!

! "

! "

! "

" ! #!

" ! #!

" ! #!

5.
XRD measurements of PVD-
coatings

" ! #!

! "

! "

" ! #!

" ! #!

Aggerbeck, M. - Optical - Appearance of Aluminium, PHD Th. (Tech Univ. Denmark, 2010) PDF

Hochgeladen von

Dokumentinformationen

Originaltitel

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Aggerbeck, M. - Optical - Appearance of Aluminium, PHD Th. (Tech Univ. Denmark, 2010) PDF

Hochgeladen von

Copyright:

Verfügbare Formate

Handed in: 2010-09-10

Technical University of Denmark, 2010-09-10.

AFM Atomic Force Microscopy

7 Materials and preparation techniques .............................. 29

8 Characterization techniques ........................................... 36

9 Results and discussion ................................................... 43

9.1.2 Presentation of the anodised specimens............................................... 44

10 Conclusion ................................................................. 87

The IdeAl project has two focuses:

Figure 6.1: Illustration of specular and diffuse reflection (source: http://www.physicsclassroom.com).

Figure 6.2: Representation of the reflectivity as function of wavelength

From a decorative point of view the following limits are advised:

Element Advised Concentration limit

Iron (Fe) 0,5%

Silicon (Si) 2-3%

Manganese (Mn) 0,5-0,8%

Zinc (Zn) 6-8%

Chromium (Cr) 0,3%

Titanium (Ti) 0,3%

Copper (Cu) 1-2%

6.2.2 Recycled cast aluminium

Figure 6.3: Al-Si phase diagram [1].

Copper is also added to ease the casting process.

6.3 Surface modification processes for aluminium

6.3.1 Polishing by buffing and water polishing

6.3.1.1 Wheel polishing

An illustration of the Beilby layer is seen in Figure 6.4.

Figure 6.4: The Beilby layer [12].

6.3.1.2 Water polishing

6.3.2 The anodising process

Thickness Application areas

Figure 6.5: Schematic anodising process.

Figure 6.6: Idealised anodising structure (source: electrochem.cwru.edu).

Figure 6.7 illustrates absorption colouring and integral colouring.

Al2O3 + H2O 2AlO(OH)2

6.3.3 Physical Vapour Deposition (PVD)

6.3.3.2 The PVD process

Figure 6.9: Everything in the chamber is coated during the process.

Figure 6.10: Sputter yield / coefficient as a function of atomic number [9].

6.3.3.3 Magnetron sputtering

Figure 6.11: The principle of magnetron sputtering [15].

6.3.3.4 Coating structure model

Figure 6.13: The Thornton structure model [17].

6.4 Characterisation techniques

6.4.1 Scanning Electron Microscope (SEM)

Figure 6.14: Schematic overview of the component in a SEM [source: Wikipedia.org].

Figure 6.15: Energy distribution of scattered electrons.

6.4.2 (Radio Frequency) Glow Discharge Optical Emission

Figure 6.17: Schematic illustration of Bragg's law (source: commons.wikimedia.org).

6.4.4 Spectrophotometer measurements

7 Materials and preparation techniques

7.1 Materials used

7.1.1 Used Al alloys

7.1.1.1 Alloy 1050

7.1.1.2 Alloy 5754

7.1.1.3 Alloy 6082

7.1.1.4 Alloy 6401

7.1.1.5 Alloy 46500

The main alloying elements in the 46500-alloy are Si and Cu.

7.1.2 Titanium grade 1

The grade 1 titanium is a commercially pure alloy.

7.2 Surface finishing treatments on commercial alloys

7.2.1 Polishing using a buffing wheel