Functional surfaces for corrosion protection – current challenges and future trends

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

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]

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

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
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
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
Coated
steel
Lifetime of coating
After: “Paint and Coatings – Applications and Corrosion Resistance”, Philip A, Schweitzer, Taylor & Francis, CRC Press, 2006

8
Anti-corrosion coating: idealized scenario

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

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
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
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
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
Historical trends
• coating phrase search
• Years 1800 – 2000

16
Historical trends
• coating & corrosion phrase search
• Shows how the phrases have occurred in a corpus of books
• Years 1800 – 2000

17
Historical trends
• thermal spray phrase search
• Years 1800 – 2000

18
Historical trends
• Physical vapor deposition & physical vapour deposition
phrases search
• Shows how the phrases have occurred in a corpus of books
• Years 1800 – 2000

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
Alkyds
Urethanes
Silicates
Ceramics
Glass
Anodizing
Phosphating
Chromate
Molybdate
Galvanizing
Vacuum vapor
deposition
Electroplating
Diffusion

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
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
HVOF spray
Cold spray
Increased adhesion & cohesion / Reduced porosity
24
Design criteria for thermal spray

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
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
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
Current trends
corrosion (Brazil)
• Phrase: corrosion (search popularity limited to Brazil)
• Years 2004 - 2014

29
Current trends
• Phrase: corrosion (search popularity limited to Brazil)
• Years 2004 - 2014

30
Current trends
smart coating (worldwide)
not enough data
• Phrase: smart coating (worldwide search popularity)
• Years 2004 - 2014

31
Current trends
nano coating (worldwide)
• Phrase: nano coating (worldwide search popularity)
• Years 2004 - 2014

32
Current trends
zinc coating (worldwide)
• Phrase: zinc coating (worldwide search popularity)
• Years 2004 - 2014

33
Current trends
• Phrase: zinc coating (worldwide search popularity)
• Years 2004 - 2014

34
Current trends
functional coating (worldwide)
• Phrase: functional coating (worldwide search popularity)
• Years 2004 - 2014

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

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
• 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

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 of service…

42
Industry specific challenges

• 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

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

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

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 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
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
• 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
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
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
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
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

PVD: technology for functional surfaces
• Full scale industrial components and R&D samples
• Fully automated
• Repeatable coating composition
55

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 picked up by water droplets
• Replicated by nano-patterned surfaces
• Challenge: volumetric effect
• Commercial self-cleaning glass

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
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
Innovation happens every day
http://news.illinois.edu/news/14/0508plastic_ScottWhite_JeffryMoore_NancySottos.html, accessed on May 19th 2014

61
Innovation happens every day
http://http://www.nanowerk.com/nanotechnology-news/newsid=35422.php , accessed on May 19th 2014

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

“YOU NEVER CHANGE THINGS BY
FIGHTING THE EXISTING REALITY.
TO CHANGE SOMETHING, BUILD
A NEW MODEL THAT MAKES THE
EXISTING MODEL OBSOLETE.”
- BUCKMINSTER FULLER

tliskiewicz@chartercoating.com
@tomliskiewicz

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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