Tomasz Liskiewicz* and Amal Al-Borno
Charter Coating Service (2000) Ltd., No. 6, 4604 13th Street NE, Calgary, AB, T2E 6P1...
Functional surfaces for corrosion protection:
• What are available classes of anti-corrosion coatings?
• What are current ...
Outline
Background
• Surface Engineering
• Coating selection
• Corrosion resistant coatings
Where are we coming from?
• Bi...
What is Surface Engineering?
→ Engineer’s perspective
“… makes possible the design and manufacture of engineering
componen...
5
Surface functionalization
Design Improvements
• Longer service life
• Ability to tolerate greater loads
• Ease and low c...
6
Surface engineering technology
Image cortesy: Linköping University
7
Role of corrosion resistant coating
Exposure time
Freeenergychange,Go,k-calmole
0
-81
 FeOOH line
Uncoated
steel
Coate...
8
Anti-corrosion coating: idealized scenario
9
Anti-corrosion coating: real-life scenario
substrate
coating
substrate
coating
substrate
coating
Barrier coating insulat...
Where are we coming from ?
11
Coatings for decoration & identification
15000 BC
Roman Era
• First known cave painting from
natural iron oxides (Franc...
12
First protective coatings
6000 BC
Middle
Ages
• Chinese lacquer
• First protective coating developed in
Egypt – pitches...
13
Emergence of paint & varnish industry
18th
Century
20th
Century
• Watin first described the paint and
varnish industry ...
14
Historical trends
• Occurrence over time - books
• paint phrase search
• Source: Google Ngram Viewer
• Shows how the ph...
15
Historical trends
• Occurrence over time - books
• coating phrase search
• Source: Google Ngram Viewer
• Shows how the ...
16
Historical trends
• Occurrence over time - books
• coating & corrosion phrase search
• Source: Google Ngram Viewer
• Sh...
17
Historical trends
• Occurrence over time - books
• thermal spray phrase search
• Source: Google Ngram Viewer
• Shows ho...
18
Historical trends
• Occurrence over time - books
• Physical vapor deposition & physical vapour deposition
phrases searc...
Where are we now ?
20
Coating vs surface modification
substrate
surface
modification
coating
21
Classes of anti-corrosion coatings
ORGANIC INORGANIC CONVERSION METALLIC
Coal tars
Phenolics
Vinyls
Acrylics
Epoxy
Alky...
Coating thickness (µm)
Substratetemperature(°C)
1,000
0
200
400
600
800
0.1 100101 1,000 10,000
Physical Vapour
Deposition...
23
Design criteria: coating thickness
Chemical
Vapor
Deposition
Physical Vapor Deposition
Thermal Spray
Organic Coating
Particle velocity on impact, m/s
Particletemperature,oC
1000
2000
3000
200 400 600 800 1000
Flame &
arc spray
Plasma spray...
25
Design criteria
What conditions am I designing for?
• Environment
• Chemical vs mechanical damage
• Geometrical limitat...
26
Methodology for coating selection
2 Component
specification
1 Application and
design study
3 Functional
corrosion
requi...
27
Current trends
Search popularity over time - web
• Phrase: corrosion (worldwide search popularity)
• Source: Google Tre...
28
Current trends
corrosion (Brazil)
Search popularity over time - web
• Phrase: corrosion (search popularity limited to B...
29
Current trends
Search popularity over time - web
• Phrase: corrosion (search popularity limited to Brazil)
• Source: Go...
30
Current trends
smart coating (worldwide)
not enough data
Search popularity over time - web
• Phrase: smart coating (wor...
31
Current trends
nano coating (worldwide)
Search popularity over time - web
• Phrase: nano coating (worldwide search popu...
32
Current trends
zinc coating (worldwide)
Search popularity over time - web
• Phrase: zinc coating (worldwide search popu...
33
Current trends
Search popularity over time - web
• Phrase: zinc coating (worldwide search popularity)
• Source: Google ...
34
Current trends
functional coating (worldwide)
Search popularity over time - web
• Phrase: functional coating (worldwide...
35
Patents
0
500
1000
1500
2000
2500
1900 1910 1920 1930 1940 1950 1960 1970 1980 1990 2000 2010
Granted patents over time...
Sustainedplasmadensity/10ncm-3
ILangmuir
TMaiman,1sTLaser
Tesla–arcgeneration
Crookes–plasmaphysics
JJThomson
BBerghaus,pl...
37
• Anti-corrosion coatings not limited to one class of coatings
• Number of sector specific (traditional) technologies
•...
)
Where are we going ?
Industry challenges
39
Where are we going?
Technology trends
Emerging technologies
Where are we going ?
Industry challenges
Industry aiming for ZERO defects & ZERO failures
41
Major challenge
“zero”
BUT 85% of coatings
fail in the first
3 years o...
42
Industry specific challenges
• Early failure detection
• Performance prediction
• New chemistry coatings with higher Tg
• Retain adhesion
• Resist cath...
Specific challenge: DLC for internal bores
• Drawback of PVD technology: line-of-sight deposition
• PECVD equipment handle...
Specific challenge: DLC for internal bores
• D. Lusk, M. Gore, W. Boardman, T. Casserly, K. Boinapally, M. Oppus, D. Upadh...
Where are we going ?
Technology trends
47
"When I was a student at MIT, we all shared one computer and
it took up a whole building. The computer in your cell pho...
48
Exponential growth
Source:SingularityisNear,http://www.singularity.com/charts/page17.html
49
Nanotechnology
Source:SingularityisNear,http://www.singularity.com/charts/page17.html
50
Internet of things
• It was only 70 years after the invention of the aeroplane that
100 million people travelled by air...
51
TRIZ
• TRIZ: Theory of Inventive Problems Solving
• Teoriya Resheniya Izobreatatelskikh Zadach
• TRIZ message: Innovati...
52
TRIZ
Genrich Altshuller
• Using the knowledge and experience of former inventors
• 2m patents studied by Altshuller’s t...
53
TRIZ trends - generic
• Number of generic trends that systems tend to evolve along
• To determine the evolutionary stat...
54
TRIZ trend – surface related
• Unique & straightforward repeatable pattern
• Indication of the most likely successful f...
PVD: technology for functional surfaces
• Full scale industrial components and R&D samples
• Fully automated
• Repeatable ...
Where are we going?
Emerging technologies
Glimpse into the future
57
Self-cleaning surfaces
• Inspired by Lotus leaf surface
• Hierarchical structure
• Super-hydrophobic effect
• Dirt pick...
58
Self-healing materials
Arteria Solutions:
• Start-up company at the Leeds University
• Self-healing nano-coating
• Insi...
59
Programmable materials
• Prototype of a selective vibration-damping material
• Piezoelectric discs which can be simulat...
60
Innovation happens every day
http://news.illinois.edu/news/14/0508plastic_ScottWhite_JeffryMoore_NancySottos.html, acce...
61
Innovation happens every day
http://http://www.nanowerk.com/nanotechnology-news/newsid=35422.php , accessed on May 19th...
62
• Exciting journey from where we were to where we are going
• We have a privilege of living in a fantastic time of
tech...
“YOU NEVER CHANGE THINGS BY
FIGHTING THE EXISTING REALITY.
TO CHANGE SOMETHING, BUILD
A NEW MODEL THAT MAKES THE
EXISTING ...
tliskiewicz@chartercoating.com
@tomliskiewicz
IMAGE CREDITS
Slide 2: Image 1 - source: Wikimedia Commons (http://commons.wikimedia.org/wiki/File:Bhimbetka_Cave_Painting...
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Functional surfaces for corrosion protection – current challenges and future trends

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Originally presented as a keynote paper during Intercorr 2014 conference in Fortaleza, Brazil, on May 21st, 2014.

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  • Surface properties can be manipulated in order to realize certain advantages in the technological competition:
  • Functional surfaces for corrosion protection – current challenges and future trends

    1. 1. Tomasz Liskiewicz* and Amal Al-Borno Charter Coating Service (2000) Ltd., No. 6, 4604 13th Street NE, Calgary, AB, T2E 6P1, Canada * tliskiewicz@chartercoating.com I N T E R C O R R 2 0 1 4 , F o r t a l e za / C E , B ra z i l , M ay 1 9 - 2 3 , 2 0 1 4 Functional surfaces for corrosion protection – current challenges and future trends
    2. 2. Functional surfaces for corrosion protection: • What are available classes of anti-corrosion coatings? • What are current technology trends? • What might be future technology trends? • How to stay ahead of the game in anti-corrosion business? What I want to achieve with this talk 2 Where are we now? Where are we going to?Where are we coming from? [* Credits to Creative Commons images used in the presentation given in the final slide]
    3. 3. Outline Background • Surface Engineering • Coating selection • Corrosion resistant coatings Where are we coming from? • Bit of history - from painting caves to painting bridges Where are we now? • Coating vs surface modification • Comparison of some coating technologies • Coating design – fit for purpose • Market & patent analysis Where are we going? • Industry challenges • Technology trends • Early ideas / novel technologies Summary 3
    4. 4. What is Surface Engineering? → Engineer’s perspective “… makes possible the design and manufacture of engineering components with combination of bulk and surface properties unobtainable in a single monolithic material” Bell, 1985 Surface engineering 4 Manipulation of properties Tailored performance Surface functionalization
    5. 5. 5 Surface functionalization Design Improvements • Longer service life • Ability to tolerate greater loads • Ease and low cost of maintenance • Improved response in kinetic systems • Lower energy consumption • Resistance to corrosion • Possibility of designing to close tolerances • Environmental gains and conservation of resources • Use of lower-cost base materials
    6. 6. 6 Surface engineering technology Image cortesy: Linköping University
    7. 7. 7 Role of corrosion resistant coating Exposure time Freeenergychange,Go,k-calmole 0 -81  FeOOH line Uncoated steel Coated steel Lifetime of coating After: “Paint and Coatings – Applications and Corrosion Resistance”, Philip A, Schweitzer, Taylor & Francis, CRC Press, 2006
    8. 8. 8 Anti-corrosion coating: idealized scenario
    9. 9. 9 Anti-corrosion coating: real-life scenario substrate coating substrate coating substrate coating Barrier coating insulates substrate from the corrosive atmosphere Barrier integrity broken: moisture and corrosive species pass through Corrosion and barrier coating undercutting atmosphere, mechanical damage
    10. 10. Where are we coming from ?
    11. 11. 11 Coatings for decoration & identification 15000 BC Roman Era • First known cave painting from natural iron oxides (France & Spain) • Egypt: first synthetic pigment – Egyptian Blue; Vehicles used: egg white, gelatins, beeswax • Asia: fired pigments and organic pigments; similar vehicles as in Egypt • American Indians: variety of organic materials used for pigments – charcoal, graphite, lignite, calcined deer bones; vehicle – salmon eggs • Romans: same essential materials as Egypt with more artificial colors
    12. 12. 12 First protective coatings 6000 BC Middle Ages • Chinese lacquer • First protective coating developed in Egypt – pitches and balsams to coat boats • Varnish developed in Egypt from Gum Arabic • Lacquer also used in Japan and Korea • Romans use pitch and wax on ship bottoms • Sap used to waterproof drinking vessels in Japan • Considerable use of paint to protect wood in Middle Ages
    13. 13. 13 Emergence of paint & varnish industry 18th Century 20th Century • Watin first described the paint and varnish industry (1773) • First varnish factory in England (1790) • First reference to use of zinc as a protective coating (1840) • First prepared paint on the market (1867) • First protective coating system: red lead-graphite linseed oil paint (1800- 1900) • New era in the coating industry with increased emphasis on science and chemistry (early 20th century)
    14. 14. 14 Historical trends • Occurrence over time - books • paint phrase search • Source: Google Ngram Viewer • Shows how the phrase has occurred in a corpus of books • Years 1800 – 2000
    15. 15. 15 Historical trends • Occurrence over time - books • coating phrase search • Source: Google Ngram Viewer • Shows how the phrase has occurred in a corpus of books • Years 1800 – 2000
    16. 16. 16 Historical trends • Occurrence over time - books • coating & corrosion phrase search • Source: Google Ngram Viewer • Shows how the phrases have occurred in a corpus of books • Years 1800 – 2000
    17. 17. 17 Historical trends • Occurrence over time - books • thermal spray phrase search • Source: Google Ngram Viewer • Shows how the phrase has occurred in a corpus of books • Years 1800 – 2000
    18. 18. 18 Historical trends • Occurrence over time - books • Physical vapor deposition & physical vapour deposition phrases search • Source: Google Ngram Viewer • Shows how the phrases have occurred in a corpus of books • Years 1800 – 2000
    19. 19. Where are we now ?
    20. 20. 20 Coating vs surface modification substrate surface modification coating
    21. 21. 21 Classes of anti-corrosion coatings ORGANIC INORGANIC CONVERSION METALLIC Coal tars Phenolics Vinyls Acrylics Epoxy Alkyds Urethanes Silicates Ceramics Glass Anodizing Phosphating Chromate Molybdate Galvanizing Vacuum vapor deposition Electroplating Diffusion
    22. 22. Coating thickness (µm) Substratetemperature(°C) 1,000 0 200 400 600 800 0.1 100101 1,000 10,000 Physical Vapour Deposition (PVD) Thermal Spray Welding Roll Cladding Chemical Vapour Deposition (CVD) Electroplating 0-1-10 100,000 Thermo- chemical Diffusion Ion Implant. Anodising / PEO Cold spray 22 Design criteria: process temperature
    23. 23. 23 Design criteria: coating thickness Chemical Vapor Deposition Physical Vapor Deposition Thermal Spray Organic Coating
    24. 24. Particle velocity on impact, m/s Particletemperature,oC 1000 2000 3000 200 400 600 800 1000 Flame & arc spray Plasma spray HVOF spray Cold spray Increased adhesion & cohesion / Reduced porosity 24 Design criteria for thermal spray
    25. 25. 25 Design criteria What conditions am I designing for? • Environment • Chemical vs mechanical damage • Geometrical limitations? Other factors? • Short series vs mass production • Geographical technology limitations Tailored surface functionality – coating specification Feasible solution
    26. 26. 26 Methodology for coating selection 2 Component specification 1 Application and design study 3 Functional corrosion requirements 4 Functional coating requirements 5 Non-functional requirements 6 Economic and procurement requirements 7 Coating process characteristics 8 Coating material characteristics 9 Specific coating material and process characteristics SOLUTION What is needed? What is possible? After:“CoatingsTribology”,KennethHolmbergandAllanMatthews,Elsevier,2009.
    27. 27. 27 Current trends Search popularity over time - web • Phrase: corrosion (worldwide search popularity) • Source: Google Trends • Searches done relative to the total number of searches done on Google over time • Years 2004 - 2014 corrosion (worldwide)
    28. 28. 28 Current trends corrosion (Brazil) Search popularity over time - web • Phrase: corrosion (search popularity limited to Brazil) • Source: Google Trends • Searches done relative to the total number of searches done on Google over time • Years 2004 - 2014
    29. 29. 29 Current trends Search popularity over time - web • Phrase: corrosion (search popularity limited to Brazil) • Source: Google Trends • Searches done relative to the total number of searches done on Google over time • Years 2004 - 2014
    30. 30. 30 Current trends smart coating (worldwide) not enough data Search popularity over time - web • Phrase: smart coating (worldwide search popularity) • Source: Google Trends • Searches done relative to the total number of searches done on Google over time • Years 2004 - 2014
    31. 31. 31 Current trends nano coating (worldwide) Search popularity over time - web • Phrase: nano coating (worldwide search popularity) • Source: Google Trends • Searches done relative to the total number of searches done on Google over time • Years 2004 - 2014
    32. 32. 32 Current trends zinc coating (worldwide) Search popularity over time - web • Phrase: zinc coating (worldwide search popularity) • Source: Google Trends • Searches done relative to the total number of searches done on Google over time • Years 2004 - 2014
    33. 33. 33 Current trends Search popularity over time - web • Phrase: zinc coating (worldwide search popularity) • Source: Google Trends • Searches done relative to the total number of searches done on Google over time • Years 2004 - 2014
    34. 34. 34 Current trends functional coating (worldwide) Search popularity over time - web • Phrase: functional coating (worldwide search popularity) • Source: Google Trends • Searches done relative to the total number of searches done on Google over time • Years 2004 - 2014
    35. 35. 35 Patents 0 500 1000 1500 2000 2500 1900 1910 1920 1930 1940 1950 1960 1970 1980 1990 2000 2010 Granted patents over time (worldwide) • Phrase: corrosion (in the patent title) • Source: Espacenet – European Patent Office
    36. 36. Sustainedplasmadensity/10ncm-3 ILangmuir TMaiman,1sTLaser Tesla–arcgeneration Crookes–plasmaphysics JJThomson BBerghaus,plasmaSEapplications V.Petrov,Arcdischarge DMattox,IonPlating Penning-Trap/SimpleMagnetron BWindow,UnbalancedMS WSproul,ClosedFieldMS Lasersteeredarc 1800 1900 1920 1940 1960 1980 2000 2020 PVDworldwidepatentssubmittedperyear 150 100 50 200 250 n=15 n=10 n=5 n=20 n=25 TriodeIonPlating/Mag.sputtering HIPIMSTechnology JThornton,RotatingMScathode 36 Evolution of plasma based technology
    37. 37. 37 • Anti-corrosion coatings not limited to one class of coatings • Number of sector specific (traditional) technologies • Incremental improvements across all classes of coatings • Coating choice often a result of historical or geographical factors • Potential coating solutions to be identified through coating design / selection methodology • Coating selection informed by what is needed but also by what is possible • Various trends analyses can be used to characterize current state of technology Summary – where are we now
    38. 38. ) Where are we going ?
    39. 39. Industry challenges 39 Where are we going? Technology trends Emerging technologies
    40. 40. Where are we going ? Industry challenges
    41. 41. Industry aiming for ZERO defects & ZERO failures 41 Major challenge “zero” BUT 85% of coatings fail in the first 3 years of service…
    42. 42. 42 Industry specific challenges
    43. 43. • Early failure detection • Performance prediction • New chemistry coatings with higher Tg • Retain adhesion • Resist cathodic disbondment 43 Oil & gas sector challenges Changing environment • Increasing depths (onshore and offshore) • High temperature (enhanced oil recovery, SAGD) • Pipelines to carry viscous media (oil sands) • High abrasion Requirements
    44. 44. Specific challenge: DLC for internal bores • Drawback of PVD technology: line-of-sight deposition • PECVD equipment handles situation better but struggles with large length:diameter situations Proprietary technology developed around 2005 to address tubular components W.J. Boardman, A.W. Tudhope, R.D. Mercado, Method and system for coating internal surfaces of prefabricated process piping in the field, United States Patent 7300684. 44
    45. 45. Specific challenge: DLC for internal bores • D. Lusk, M. Gore, W. Boardman, T. Casserly, K. Boinapally, M. Oppus, D. Upadhyaya, A. Tudhope, M. Gupta, Y. Cao, S. Lapp, Thick DLC films deposited by PECVD on the internal surface of cylindrical substrates, Diamond and Related Materials, 17 (2008), pp. 1613-1621. • W. Boardman, K. Boinapally, T. Casserly, M. Gupta, C. Dornfest, D. Upadhyaya, Y. Cao, M. Oppus, Corrosion and Mechanical Properties of Diamond-like Carbon Films Deposited Inside Carbon Steel Pipes, NACE Corrosion, 2008, Paper 08032, pp. 1-11. • M. Gore, W. Boardman, Emergence of Diamond-like Carbon Technology: One Step Closer to OCTG Corrosion Prevention, SPE International Conference on Oilfield Corrosion, 2010, Paper 131120, pp.1-9. • Plasma generated within the pipe itself • coating deposited on the internal wall of the pipe • multilayer Si-DLC coating up to 50 microns thick was generated • internal bores and enclosures up to 3 meters and aspect ratio of 1:40 (length:diameter) • BUT technology implementation proved to be challenging 45
    46. 46. Where are we going ? Technology trends
    47. 47. 47 "When I was a student at MIT, we all shared one computer and it took up a whole building. The computer in your cell phone today is a million times cheaper and a thousand times more powerful. What now fits in your pocket 25 years from now will fit into a blood cell and will again be millions of times more cost effective." -- Ray Kurzweil Accelerating intelligence • The Singularity Is Near, book, 2005 • Singularity University, CA, USA • Transcendent Man, movie, 2007 • Transcendence, movie, 2014
    48. 48. 48 Exponential growth Source:SingularityisNear,http://www.singularity.com/charts/page17.html
    49. 49. 49 Nanotechnology Source:SingularityisNear,http://www.singularity.com/charts/page17.html
    50. 50. 50 Internet of things • It was only 70 years after the invention of the aeroplane that 100 million people travelled by air • It took 50 years after the invention of the telephone for 100 million people to use this form of communication • The 100-million user mark was achieved by PCs after 14 years • The Internet made 100 million users after just 7 years The cycles of adoption of Internet related technologies are even shorter: Facebook acquired 100 million users in 2 years
    51. 51. 51 TRIZ • TRIZ: Theory of Inventive Problems Solving • Teoriya Resheniya Izobreatatelskikh Zadach • TRIZ message: Innovation Can Be Codified There are universal principles of invention that are the basis for creative innovations that advance technology If these principles are identified and codified, they can be taught to people to make the process of invention more predictable
    52. 52. 52 TRIZ Genrich Altshuller • Using the knowledge and experience of former inventors • 2m patents studied by Altshuller’s team • 5m (?) patents studied up to date • Problems and solutions were repeated across industries • Patterns of technical evolution were repeated across industries • Innovations used scientific effects outside the field where they were developed
    53. 53. 53 TRIZ trends - generic • Number of generic trends that systems tend to evolve along • To determine the evolutionary state of existing system • To predict where the system will evolve in the future Immobile system Joint Multiple joints Completely elastic Liquid/ gas Field TRIZ for Engineers: Enabling Inventive Problem Solving, Karen Gadd, Wiley, 2011
    54. 54. 54 TRIZ trend – surface related • Unique & straightforward repeatable pattern • Indication of the most likely successful future direction • Assessment and development of intellectual property TRIZ for Engineers: Enabling Inventive Problem Solving, Karen Gadd, Wiley, 2011
    55. 55. PVD: technology for functional surfaces • Full scale industrial components and R&D samples • Fully automated • Repeatable coating composition 55
    56. 56. Where are we going? Emerging technologies Glimpse into the future
    57. 57. 57 Self-cleaning surfaces • Inspired by Lotus leaf surface • Hierarchical structure • Super-hydrophobic effect • Dirt picked up by water droplets • Replicated by nano-patterned surfaces • Challenge: volumetric effect • Commercial self-cleaning glass
    58. 58. 58 Self-healing materials Arteria Solutions: • Start-up company at the Leeds University • Self-healing nano-coating • Inside of pipes in oil extraction systems • Reduce corrosion and build-up of mineral scaling • Inspired by nature • Many concepts including encapsulated healing agents and pressurised vascular networks
    59. 59. 59 Programmable materials • Prototype of a selective vibration-damping material • Piezoelectric discs which can be simulated electronically to change their thickness • Instant adaptation to environment • Can modify the propagation of mechanical waves through the structures • Vehicles, aircraft, microscopes, microphones… • Idea from Empa and ETH Zurich Image courtesy: Empa
    60. 60. 60 Innovation happens every day http://news.illinois.edu/news/14/0508plastic_ScottWhite_JeffryMoore_NancySottos.html, accessed on May 19th 2014
    61. 61. 61 Innovation happens every day http://http://www.nanowerk.com/nanotechnology-news/newsid=35422.php , accessed on May 19th 2014
    62. 62. 62 • Exciting journey from where we were to where we are going • We have a privilege of living in a fantastic time of technological development • Technological changes become faster and more dramatic • To stay ahead of the game – need to ask question How technology trends affect my work • Looking for inspiration in other sectors • Anti-corrosion coatings not limited to one class of coatings From passive coating to functional responsive surface Summary
    63. 63. “YOU NEVER CHANGE THINGS BY FIGHTING THE EXISTING REALITY. TO CHANGE SOMETHING, BUILD A NEW MODEL THAT MAKES THE EXISTING MODEL OBSOLETE.” - BUCKMINSTER FULLER
    64. 64. tliskiewicz@chartercoating.com @tomliskiewicz
    65. 65. IMAGE CREDITS Slide 2: Image 1 - source: Wikimedia Commons (http://commons.wikimedia.org/wiki/File:Bhimbetka_Cave_Paintings.jpg?uselang=en-gb), creator: Ekabhishek; Image 2 - Courtesy of TWI Ltd, source: flickr.com; Image 3 - source: Wikimedia Commons (commons.wikimedia.org/wiki/File:Barnard's_Galaxy.jpg), creator: European Southern Observatory (ESO) Slide 4: source: http://commons.wikimedia.org/wiki/File:Exploring_new_continents_1200728.JPG, creator: Wars Slide 5: http://en.wikipedia.org/wiki/File:File-Water_droplet_at_DWR-coated_surface1.jpg, creator: Brocken Inaglory Slide 10: source: Wikimedia Commons (http://commons.wikimedia.org/wiki/File:Bhimbetka_Cave_Paintings.jpg?uselang=en-gb), creator: Ekabhishek Slide 11: Image 1 – source: http://en.wikipedia.org/wiki/File:AltamiraBison.jpg, creator: Rameessos; Image 2 – source: http://en.wikipedia.org/wiki/File:%C3%84gyptischer_Maler_um_1360_v._Chr._001.jpg, creator: The Yorck Project: 10.000 Meisterwerke der Malerei. DVD-ROM, 2002. ISBN 3936122202. Distributed by DIRECTMEDIA Publishing GmbH; Image 3 – source: http://en.wikipedia.org/wiki/File:Pompeii_family_feast_painting_Naples.jpg, creator: unknown Slide 12: Image 1 – source: http://en.wikipedia.org/wiki/File:20080918094303!Red_lacquer_tray_with_gold_engraving,_Song_Dynasty.jpg, creator: User:PericlesofAthens; Image 2 - http://www.wikirestauro.it, creator: Gixie; Image 3 - http://commons.wikimedia.org/wiki/File:St_Mary's_church_- _medieval_south_door_-_geograph.org.uk_-_1384477.jpg, creator: Evelyn Simak Slide 13: Image 1 – source: http://en.wikipedia.org/wiki/File:Bridgewater_foundary.gif, creator: Illegible; Image 2 – source: http://en.wikipedia.org/wiki/File:4-2-2_GNR_1001.jpg, creator: Tony Hisgett from Birmingham, UK; Image 3 – source: http://en.wikipedia.org/wiki/File:Sir_Ernest_Rutherfords_laboratory,_early_20th_century._(9660575343).jpg, creator: Science Museum London / Science and Society Picture Library Slide 19: Courtesy of TWI Ltd, source: flickr.com Slide 23: source: http://commons.wikimedia.org/wiki/File:BurjKhalifaHeight.svg, creator: Derivative works of this file: BurjKhalifaHeight-de.svg Slide 25: source: http://en.wikipedia.org/wiki/File:Steel_ruler_closeup.jpg, creator: Ejay Slide 38, 39, 40, 46, 56: source: Wikimedia Commons (commons.wikimedia.org/wiki/File:Barnard's_Galaxy.jpg), creator: European Southern Observatory (ESO) Slide 41: source: http://commons.wikimedia.org/wiki/File:Corrosion-on-ships-bow.JPG, creator: Self Slide 42: Image 1 – source: http://commons.wikimedia.org/wiki/File:2012_Mercedes-Benz_C63_AMG_Car_Review_-_Flickr_-_NRMA_New_Cars.jpg, creator: NRMA Motoring and Services from Sydney, Australia; Image 2 – source: http://en.wikipedia.org/wiki/File:West_Texas_Pumpjack.JPG, creator: Eric Kounce TexasRaiser; Image 3 - source: http://en.wikipedia.org/wiki/File:Delta_A330.jpg, creator: Gietje; Image 4 – source: http://en.wikipedia.org/wiki/File:Hip_prosthesis.jpg, creator: Nuno Nogueira; Image 5 - source: http://en.wikipedia.org/wiki/File:Salem_Nuclear_Power_Plant.jpg, creator: Peretzp, Image 6 - source: http://commons.wikimedia.org/wiki/File:Drummoyne_Iron_Cove_Bridge.JPG, creator: J Bar Slide 43: source: http://en.wikipedia.org/wiki/File:West_Texas_Pumpjack.JPG, creator: Eric Kounce TexasRaiser Slide 50: source: https://www.flickr.com/photos/_rq/2959253251/, creator: JaredZammit Slide 51: source: http://fr.wikipedia.org/?title=Wikip%C3%A9dia:Oracle/semaine_34_2009#mediaviewer/Fichier:Rubiks_cube_by_keqs.jpg, creator: Lars Karlsson (Keqs) Slide 57: Image 1 – source: http://commons.wikimedia.org/wiki/File:LotusEffekt1.jpg, creator: Ralf Pfeifer; Image 2 – source: http://en.wikipedia.org/wiki/File:Lotus3.jpg, creator: William Thielicke Slide 58: source: http://en.wikipedia.org/wiki/File:Sweet_Chestnut_Forest.jpg, creator: Yzmo Slide 63: source: https://www.flickr.com/photos/bethscupham/6597798731/, creator: Beth Scupham
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