Fe
H2O O2
x FeO · y Fe2O3 · z H2O
Chemical corrosion
What is chemical corrosion?• series of reactions at the phase border• measureable structural change• may lead to total material destruction
Contact corrosion
steel stainless steel
H2O O2
OH-
e-
Mex+
What is contact corrosion?• series of reactions at the phase border, electrochemical reaction• measurable structural change• may lead to a total destruction of the material
Photo creditU.l.:Dredge No.4, Wikimedia Commons, licensed under: CreativeCommons-Lizenz by-sa-2.0-de, URL: http://creativecommons.org/licenses/by-sa/2.0/de/legalcodeU.r.:Zeche Zollern, Dortmund, Germany , Wikimedia Commons, licensed under : CreativeCommons-Lizenz by-2.0-de, URL: http://creativecommons.org/licenses/by/2.0/de/legalcodeL.l.:Corroding iron machinery at the White Island sulphur mine, abandoned after a lahar killed all the workers in 1914 , Wikimedia Commons, licensed under : CreativeCommons-Lizenz by-sa-3.0-de, URL: http://creativecommons.org/licenses/by-sa/3.0/de/legalcodeL.r.: A rusty screw, Wikimedia Commons, licensed under : CreativeCommons-Lizenz by-2.0-de, URL: http://creativecommons.org/licenses/by/2.0/de/legalcode
Corrosion - Example
met
al
2-3
mm th
ick
laye
r (e.
g. b
ase
oil)
50-1
00 m
m a
dditi
onal
pac
kagi
ng
(e.g
. PE
-Foi
l)
activ
e pr
otec
tion
laye
r (e.
g.
addi
tives
)water
oxygen
salts
How does corrosion protection work?
External influence factors
Rust Prevention
material
surface
packaging
transport conditions
storage conditions
External influence factors
Rust Prevention
material
surface
packagingstorage conditions
transport conditions
External influence factors
materials
aluminium
steel
iron
galvanized
cast
• corrosion tendency of materials• aluminium is easiest to protect• cast is the most problematical material
External influence factors
surface
• surface condition influences the corrosion tendency• clean and dry parts a optimal• Wet parts are in constant danger of corrosion
• clean• dry+• wet• dirty• processed-
External influence factors
transport conditions
• Transport overseas has the highest demands• day/night cylces with crossing of the dew point is
demanding for the rust preventative• Regional transport and direct processing is optimal
no transport
regional transport
national transport
transport across the
Alps
overseas on deck
overseas lower deck
Photo credit1.f.l: Petrofer Chemie2.f.l.: Baureihe 185, Wikimedia Commons, licensed under: CreativeCommons-Lizenz by-sa-2.0-de, URL: http://creativecommons.org/licenses/by-sa/2.0/de/legalcode3.f.l.: Postpanamax-Containerschiff Xin Shanghai auf der Elbe bei Hamburg (2007), licensed under: CreativeCommons-Lizenz by-sa-2.0-de, URL: http://creativecommons.org/licenses/by-sa/2.0/de/legalcode4.f.l.: MD-11F, Wikimedia Commons, licensed under: CreativeCommons-Lizenz by-sa-3.0-de, URL: http://creativecommons.org/licenses/by-sa/3.0/de/legalcode
External influence factors
packaging
• storage in closed systems, even though in combination with VCI-products is optimal for dry workpieces (beware of air humidity and humid parts!)
• open systems do not provide additional corrosion protection
• closed systems• additional foil/paper• VCI products+• no packaging• open systems-
Photo creditleft: http://www.1averpacken.de/cosmoshop/pix/a/n/1346670156-4434.jpg; Effective: 21.02.2015middle: http://www.vci-korrosionsschutz.ch/VCI-Korrosionsschutz/VCI_Korrosionsschutz_files/Kiste_mit_VCI-Folie_web_medium.jpg; Effective: 21.02.2015right: http://www.muhesa.de/s/cc_images/cache_2443028916.jpg?t=1411204810; Effective: 21.02.2015
External influence factors
storage conditions
• inside storage is optimal for corrosion protection• outside storage is demanding to the rust preventative• salt containing air near shore promotes fast corrosion
inside
sheltered
outside
near shore
Picture creditleft: Gdansk Nowy Port kregi, Wikimedia Commons, licensed under: CreativeCommons-Lizenz by-sa-3.0-de, URL: http://creativecommons.org/licenses/by-sa/3.0/de/legalcoderight: Warmband im Lager, Wikimedia Commons, licensed under: CreativeCommons-Lizenz by-sa-3.0-de, URL: http://creativecommons.org/licenses/by-sa/3.0/de/legalcode
• the film type influences the protection time• higher film viscosity improves the corrosion protection• Varnish-type films show long term corrosion protection• Choice is influenced by external factors as well as further
processing
Film types
not perceptible
oily
vaselinewaxy
varnish
System overview
1 10 100 1000 10000 1000001
10
100
1000
10000
film viscosity [mm²s-1]
corr
osio
n pr
otec
tion[
d]
dipping is possible
oils forsyntheticsolutions
thixotropic oils
oils
emulsifable oils
waxes
System overview
1 10 100 1000 10000 1000001
10
100
1000
10000
film viscosity [mm²s-1]
corr
osio
n pr
otec
tion[
d]
thixotropic oils
oils forsyntheticsolutions
oils
emulsifyable oils
waxes
solving – heating –varpourising - cooling
oils + soft waxes
outside,without shelter
outside,sheltered
inside,unpacked
inside,packed
1d 1w 1m 1y 10y
emulsion
no film
risk
hard waxes
+VCI +VCI
System overview
Corrosion protection concept
optimal rust preventativematerial
surface
packaging
transport conditions
storage conditions
protection time
workflow
VCI-method• VCI- Volatile Corrosion Inhibitor. Inhibitors are substances capable of inhibiting or suppressing chemical reactions. They may be considered the opposite to catalyst, which enable or accelerate certain reactions.
• The VCI method is an active corrosion protection.
• Volatile corrosion inhibitors are among the most efficient and cost-effective classes of means used to protect metals from atmospheric corrosion.
Mode of actiondue to is evaporation properties, the VCI substance (applied onto paper) passes relatively continuously into the gas phase an is deposited as a film onto the item to be protected (metal surfaces).
• independently of ordinary temperatures or humidity levels
• The mode of action wrapped in VCI paper.
Mode of action• wrapped in VCI paper.
• Metallic surfaces must be clean
• The VCI paper should be no further than 30 cm away from the item to be protected.
• Approximately 40 g of active substances por m3
• Airtight heat sealing is not required
• The mode of action dictates how VCI materials are used. At item to be protected is, wrapped in VCI paper.
PetroCo
r P1
PetroCo
r P1
PetroCo
r P1
Mode of action
German Technical Regulations for Hazardous Substances, TRGS 615 “Restrictions on the use of corrosion protection agents which may give rise to N-nitrosamines during use”
Comparison of advantages and disadvantages of the VCI methodFunctional advantages:
• Since the gas also penetrates holes and cavities.
• slight film-formation on the workpiece
• Corrosion inhibition can be controlled by the concentration of the emulsion
• The wrapping need not be provide with an airtight heat seal.
Comparison of advantages and disadvantages of the VCI method
Disadvantages:
• PetroCor P1 is only suitable for steels and stainless steel.
PetroCor
Product Suggested for Suitable for
PetroCor P1 Kraft paperHot-rolled, Cold rolled steel, coils or
plates, their cutting and punching parts, electrical steel, Carbon steel, stainless
steel, cast iron, galvanized steel
PETROCOR P1 is a solvent-free water-miscible rust preventive to finish special paper (VCI-paper: volatile corrosion inhibitor), which is used to protect steel and alloys. Mode of operation• low vaporization of contents and change into the gaseous phase• set up of protection atmosphere• performance of a protecting and active film Advantages• efficient inhibition of electrochemical corrosion reactions as a result of an active film• high affinity to steel although it is wet (migration)• protection of hollows and drill holes as a result of inhibitors out of the gaseous phase
Titan Paper Mill• Paper Mill in Russia.• Creping paper for steel covering during for metallurgy industry.• Technology that they are using was developed by themselves.• They use ready kraft-paper, wetting it and then drying with Yankee and crepping it.• They use urotropin (C6H12N4) and sodium nitrit.• Customers for this paper is big metal plants witch produce metals mostly in sheets.• Yankee temperature app. 80°C• In ready paper they have around 5g of active ingredients per sq m of paper
Titan Paper Mill
• It’s needed to protect metal for the transportation period including transportation via ocean (few months)
• Wild range of temperature -40 +50 C. And paper itself can be kept few months before use.
• Humidity
• They have plan to produce 500t such paper per month.
outside storage
Inside storageoutside storage
sheltered storagePetrofer plant Hildesheim
Test-field
sample holder
Testfield
Test Methods: CH-Test
Condensation atmosphere with constant humidity (CH) according to DIN EN ISO 6270-2
Air temperature: 40±3°CAir humidity: ~100%
• continuous condensation on the specimen• no defined cycle-time
Suitable for: All types of rust preventives, cleaners, coolants…
Test Methods: AHT-Test
Condensation Climate with alternating humidty and air temperature (AHT) according to
DIN EN ISO 6270-2
DIN EN ISO 6270-2 Petroferfor 8 hours
Air temperature: 40±3°C 40°CHumidity: ~100% ~100%
for 16 hoursAir temperature: 18-28°C 23°CHumidity: <100% ~60%
• 100% condensation of the specimen for 8h; <100% condensation for 16h• cycle time: 24h
Suitable for: All types of rust preventives, cleaners, coolants…
Test Methods: AHT-Test
For different concentration of PetroCor P1 are given in combination in 5 cycles. • The concentration of the product:
• 5% Petrocor P1 in tap water. 1,0-1,5 g/m2
• 10% Petrocor P1 in tap water. 2,5-3,0 g/m2
Note: the individually packed parts (steel sheets) must be wrapped in plastic to avoid the loss of the vapor-phase to the outside.
Test Methods: Test panelsQ
We are using test panel from Q-LAB, the so called Q-PANELs.
MaterialSAE 1008/1010ASTM A1008ISO 3574 Type CR1Roughness: 25-65 micro-inchesSurface finish: dull matte
Compositionmax. 0.60% Manganesemax. 0.15% Carbonmax. 0.030% Phosphorusmax. 0.035% Sulfur
Test Methods: PETROFER-Test
for this Test is not required a climatic chamber.
• Procedure for each cycle (cycle time: 24hours):• Air temperature: 20+3°C • Humidity: ~100% For different concentration of Petrocor P1 are given in combination in 5 cycles. The concentration of the product: • 2,5% Petrocor P1 in tap water 0,3-0,5 g/m2
• 5% Petrocor P1 in tap water 1,0-1,5 g/m2
• 10% Petrocor P1 in tap water 2,5-3,0 g/m2
Test Methods: PETROFER-Test
The individually packed parts (steel sheets) must be wrapped in plastic to avoid the loss of the vapor-phase to the outside.
Reference Sample 2,5% PETROCOR P1 5% PETROCOR Titan-Paper
All results have been favorable as with our normalized steel sheets, as with the Titan-Paper steel sheets.
Test Methods: NSS-TestNeutral salt spray test (NSS) according to DIN EN ISO 9227
Air temperature: 35±2°CSaline concentration: 5%Collection amount: 187,5±62,5mL/(h·m2)
• hourly check of the specimen
Not suitable for water-miscible products!
Test Methods: Indoor StorageTests for indoor storage are performed in our test field. The climate is harder than for „real“ indoor tests.There is
…no humidity control… no temperature control
So the test panels have more or less the conditions of an outdoor storage but without factors like wind, rain and spray water.
Test Methods: Chip-Filter-TestDIN 51360/2: Evaluation of rustpreventive properties of water-miscible coolants
Realization: 2g sieved grey cast 25 chips on filter2g emulsion for wettingafter 2h removal of chips, rinsing of the emulsionevaluation after drying
26.11.2015 – International Training: Rusty Winter, Hildesheim
Introduction to the Global Application Center (GAC)
The idea behind the GAC
problem
• customer has a problematic process• customer has to fulfill certain specifications and
no possibility to test it
trial
• customer sends parts to Petrofer, different products/processes are tested
• customer visits Petrofer to accompany the trials
solution
• customer gets results with product recommendation
• customer buys product based on trials
• VSC 450, 480 l
• Number: 1
• Actual use: Neutral salt spray test (DIN EN ISO 9227)
• Applicability: – Salt spray tests (DIN EN ISO 9227 - DIN 50021)– Condense climate tests (DIN EN ISO 6270-2 - DIN 50017;
EN ISO 9688 - DIN 50018)– Normal climate tests (DIN 50 014, Abs. 5 Room temperatur)
Salt spray chamber
• VC3 4034, 335 l
• Number: 2
• Actual use: Condense climate tests (DIN EN ISO 6270-2)
• Applicability:– Freely adjustable from -42°C to 180°C– From 10-95°C a relative humidity of 10- 98% is adjustable
Climate chambers
• Rumed 4101 350 l
• Number: 1
• Actual use: Condensation climates
• Applicability:– -30°C to +80°C– 10% to 95% relative humidity– Freely adjustable
Rumed climate chamber
• Number: 1
• Actual use: Condensation climates, Vapor phase corrosion tests
• Applicability:– Condensation climates– Vapor phase corrosion tests
Condensation climate chamber
outside storage
Inside storageoutside storage
sheltered storagePetrofer plant Hildesheim
Test-field
sample holder
Testfield
Thanks for your attention.
Rafael del Corral SánchezGruppe Papierchemikalien / Group Paperchemicals /Grupo Químicos para el Papel
31106 Hildesheim | Römerring 12–16 | P.O. Box 10 06 45 | GermanyPhone: +49 5121 7627 379 | Postfach 10 06 45Mobil: +49 151 14 05 38 55 | Email: [email protected] | Internet: www.petrofer.com
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