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Avesta Pickling Handbook PDF
Avesta Pickling Handbook PDF
PICKLING HANDBOOK
Surface treatment of stainless steels
AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
1
INDEX
2 AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
Before
3
After
AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
Foreword
This manual is intended to increase awareness and understanding of the need to treat
stainless steel surfaces. In particular, it aims to:
• Explain why, after welding and processing, stainless steel structures need cleaning in
order to preserve their corrosion resistance.
In this manual, Avesta Finishing Chemicals presents practical methods for pickling and
cleaning stainless steels. Appropriate safety procedures when handling the products
concerned are also set out.
Avesta Finishing Chemicals is a leading producer of superior pickling products for stain-
less steels and special alloys. The company is also part of the Böhler Welding Group, one
of the world’s largest manufacturers of welding consumables.
4 AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
1.
Figure 1: Before and after Figure 2: Treated and untreated stainless steel tanks
pickling
A good stainless steel surface is clean, smooth and fault- When manufacturing to surface quality specifications,
less. The importance of this is obvious when stainless the impact of defects and, ultimately, the cost of removal
steel is used in, for example, façades or applications with must be borne in mind.
stringent hygiene requirements. However, a fine surface
finish is also crucial to corrosion resistance. The cost of treating/cleaning is small compared to the
initial capital expenditure on a piece of equipment. It is
Stainless steel is protected from corrosion by its passive also small compared to the continuing operational cost
layer – a thin, impervious, invisible, surface layer that is of not cleaning.
primarily chromium oxide. The oxygen content of the
atmosphere or of aerated aqueous solutions is normally There are two main elements in the economics of
sufficient to create and maintain (“self-heal”) this passive post-fabrication cleaning – the cost of cleaning and the
layer. Unfortunately, surface defects and imperfections benefits that cleaning brings as regards long-term per-
introduced during manufacturing may drastically dis- formance. Fabrication can reduce the overall corrosion
turb this “self-healing” process and reduce resistance to performance of a stainless steel to below its “normal”
several types of local corrosion. Thus, as regards hygiene level. Furthermore, in real conditions, it is difficult, if not
and corrosion, a final cleaning process is often required impossible, to complete the fabrication of a significant
to restore an acceptable surface quality. facility or piece of equipment without some surface
contamination.
The extent of, and methods for, post-fabrication treat-
ment are determined by a number of factors. These Because they generally have relatively poor corrosion
include: the corrosivity of the environment (e.g. marine); performance, areas that have not been cleaned after
the corrosion resistance of the steel grade; hygiene re- fabrication are essentially the weak link in the chain.
quirements (e.g. in the pharmaceutical and food indus- Depending on the extent of cleaning required, treatment
tries); and, aesthetic considerations. Local environmental after constructing a tank (for example) might cost as little
requirements must also be considered. Both chemical as 1 – 3% of the total spent on materials and manu-
and mechanical cleaning methods are available. facture. Consequently, as it maximises the return on the
investment, post-fabrication cleaning is not expensive
Good design, planning and methods of manufacture can (see also ref. 9).
reduce the need for post-treatment and thus lower costs.
AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
5
Definitions ling. This can be overcome by applying more pickling
The following terms are often imprecisely used: clean- spray to these spots or by applying a passivator until
ing; post-fabrication cleaning; precleaning; descaling; they disappear. This must be done when the surface
pickling; passivation; and, desmutting. For a better is still wet (i.e. “wet on wet”), just before the pickling
understanding of surface treatment and this publica- spray is rinsed off.
tion, it is important to define these terms.
Welding methods:
Cleaning includes all operations necessary to ensure
the removal of surface contaminants from metals and: MMA = manual metal arc
= (SMAW = shielded metal arc welding)
• Maximise the metal’s corrosion resistance. MIG/MAG = metal inert/active gas
• Prevent product contamination. = (GMAW, gas metal arc welding)
• Achieve the desired appearance. TIG = tungsten inert gas
= (GTAW = gas tungsten arc welding)
Combinations of grinding, degreasing, pickling and SAW = submerged arc welding
passivation may be necessary to obtain a clean surface. FCAW = flux cored arc welding
Post-fabrication cleaning is the process of cleaning MCAW = metal cored arc welding
after fabrication. Its purpose is to remove all contami-
nation associated with the fabrication process. 1.1 Stainless steel grades
Precleaning is the removal of grease, oil, paint, soil, and cleaning
grit and other coarse contamination prior to pickling or In any application, stainless steel grades are selected on
final cleaning. the basis of required properties (e.g. corrosion resist-
ance), design criteria and fabrication requirements.
Degreasing is the removal of grease prior to pickling However, there are many different iron-carbon-chromi-
or final cleaning. um alloys that are collectively referred to as stainless
steels.
Pickling is the use of chemicals to clean a metal by
removing: defects; the surface film of inherent or thick-
ened oxide; and, below this, some micrometres of the
parent metal.
NY HR-BILD
NOx is toxic nitric fumes (NO and NO2) formed during
the pickling process.
6 AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
Figure 4: A pickled, duplex 2304 storage tank
AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
7
Owing to the low chromium content, the corrosion 1.2 Surface finishes and cleaning
resistance of the two steel groups above is lower than A smooth surface that is durable enough to resist crack-
that of the two steel groups below. This lower resist- ing, chipping, flaking and abrasion cannot only resist
ance means they are “easier” to pickle. In other words, the build up of contaminants but also be cleaned easily.
to avoid the risk of overpickling, they need a shorter Engineers and architects choosing stainless steel for a
pickling time or a less aggressive pickling agent. particular purpose have an extensive number of differ-
The addition of nickel to the austenitic and austenitic- ent grades to select from. There are also various surface
ferritic steels further improves their corrosion resist- finishes to choose from.
ance. The decision as to what type of steel is best suited for
Austenitic is the most widely used type of stainless any given purpose is largely based on the corrosivity of
steel. It has a nickel content of at least 7%. This makes the environment. However, surface quality (surface fin-
the steel structure fully austenitic and gives it non-mag- ish) also affects sensitivity to corrosion and the ability
netic properties, good ductility and good weldability. to repel dirt and bacteria. This is of particular import-
Austenitic steels can also be used throughout a wide ance in the food/beverage industry and the pharma-
range of service temperatures. Applications for which ceutical sector.
austenitic stainless steels are used include: housewares; The importance of surface finish goes well beyond
containers; industrial piping; tanks; architectural aesthetic considerations. The rougher a surface, the
façades; and, building structures. This type of stainless more easily contamination sticks to it and the more dif-
steel dominates the market. ficult it is to clean and pickle. Consequently, hot rolled
Austenitic-ferritic (duplex) stainless steels have a fer- surfaces with their rougher finishes are more difficult
ritic and austenitic lattice structure (hence duplex). To to clean and pickle than cold rolled surfaces with their
give a partly austenitic lattice structure, this steel has smoother finishes.
some nickel content. The duplex structure delivers both
strength and ductility. Duplex steels are mostly used Some basic definitions of surface finish
in the petrochemical, paper, pulp and shipbuilding
industries.
criteria
8 AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
Figure 6: A bright annealed (BA) finish after using Avesta Cleaner 401.
• Roughness is the size of the finely distributed • Waviness is deviations that are relatively far apart.
surface-pattern deviations from the ideal smooth
surface. Of these, waviness is the most difficult to detect by eye.
• Lay is the dominant direction of the surface pattern As shown in table 1, surface smoothness increases from
(e.g. grinding marks). hot rolled to bright annealed (BA).
Hot rolled 1 1D Rough and dull A rough, dull surface produced by hot rolling to the specified thickness, followed by heat
treatment and pickling.
Cold rolled 2D 2D Smooth A dull finish produced by cold rolling to the specified thickness, followed by heat treat-ment
and pickling.
Cold rolled 2B 2B Smoother than 2D A bright, cold-rolled finish commonly produced in the same way as a 2D finish followed
by skin passing. The most common surface finish. Good corrosion resistance, smoothness
and flatness.
Cold rolled BS 2R Smoother than 2B, BA finish produced by cold rolling followed by bright annealing in an inert atmosphere.
bright and reflective
AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
9
1.3 Welding methods and cleaning • When using forklifts, avoid direct contact between
The different welding methods can result in problems carbon steel forks and stainless steel.
that have different consequences for surface cleaning. • At installation, use fasteners (e.g. nails, screws and
Particular attention must be paid to preparation before bolts) made of stainless steel.
pickling.
• In areas exposed to moisture, avoid the risk of gal-
Table 2: Welding methods vanic corrosion between stainless steel components
and plain carbon steel components (e.g. by providing
Welding method Possible problems* Solution (before pickling) electrical insulation).
MMA (SMAW) Slag residues Brushing (grinding)
Tarnish (heat tint) • Use clean tools that are free from residues of plain
FCAW Tarnish (heat tint) Brushing (while warm) carbon steel (e.g. swarf and iron particles from pre-
Slag residues vious work).
MIG (GMAW) Heavy bead oxidation Grinding (brushing)
Slag residues • Remove the protective plastic film only when it is
Spatter no longer needed, i.e. when the construction phase
TIG (GTAW) Small slag islands Grinding (if possible) is over and the local environment is free of debris
(“black spots”) and dirt particles. Some plastic films deteriorate in
SAW Sometimes slag Brushing (grinding) sunlight and can become difficult to strip.
residues
*depending on filler metal, welding position, overheating, gas 1.5 Industrial trends and cleaning
mixture, etc.
Higher quality demands from industry in general are
opening a growing number of applications for stain-
1.4 Correct handling and cleaning less steels. In the past, the use of stainless steels was
The correct handling of stainless steels limits surface mainly restricted to closed, corrosive environments in
defects and minimises the need for post-fabrication the chemical process industry. Now, the material has
cleaning. become more consumer oriented and can be found in
many new applications such as those listed below.
On delivery from the manufacturer, stainless steel
plates, tubes and pipes are normally clean and passiv- • Civil constructions such as bridges (e.g. the Bilbao
ated. In other words, the material has a natural Bridge in Spain).
corrosion-resistant film over its entire surface. It is im- • Public transport such as buses and trains (e.g. the
portant to maintain as much as possible of the stainless X2000 high-speed train).
material’s original appearance and corrosion resistance.
Especially as regards exterior building components, • Kitchen equipment and fixtures (e.g. cookers, fridges
the instructions below must be borne in mind at every and freezers).
stage from project design to production and installa-
tion. • Fittings in public places (e.g. street furniture, railings
and building façades).
• Do not use steel brushes or steel tools made of
carbon steel. Today’s quality standards have resulted in stainless
steels being introduced into a large number of applica-
• Do not carry out shot blasting using carbon steel tions, all of them with their own specific stipulations as
blasting materials or blasting materials that have regards surface treatment. They have also led to other
been used for carbon steels. trends and the development of new methods. The fol-
lowing are a few examples:
• Hydrochloric acid, or cleaners containing chlorides,
must not be used for cleaning stainless steels. • The use of high-alloy steel grades (e.g. duplex) for
construction of chemical tankers and 6% Mo grades
• Do not use hydrochloric acid to remove cement or for desalination plants.
mortar residues from stainless steels.
• New welding methods such as FCAW, pulse MIG,
• Throughout storage, avoid contact between stainless automatic TIG and laser welding.
steel and carbon steel.
10 AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
• Increased production of hot rolled plates (thanks to 1.6.4 Rough surface
lower production costs).
Uneven weld beads and grinding or blasting too
• Great demand for bright finishes. heavily give rough surfaces. A rough surface collects
deposits more easily, thereby increasing the risk of both
The need for industry to minimise any negative impact corrosion and product contamination. Heavy grinding
it has on the environment has put the surface treat- also introduces high tensile stresses. These increase
ment of stainless steels in the spotlight. A number of the risk of stress corrosion cracking and pitting cor-
measures can easily be taken to comply with new local rosion. For many applications, there is a maximum
requirements: allowed surface roughness (Ra value). Manufacturing
methods that result in rough surfaces should generally
• Changing to more environment-friendly pickling be avoided.
products.
AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
11
2.
Cleaning procedures
As detailed on page 5, the extent of, and methods for, that have previously been used for grinding low-
post-fabrication treatment are determined by a number alloy steels.
of factors.
• Avoid producing a surface that is too rough. Rough
Different chemical and mechanical methods, and some- grinding with a 40 – 60 grit disc must always be fol-
times a combination of both, can be used to remove the lowed by fine grinding using, for example, a higher
defects mentioned. Chemical cleaning can be expected grit mop or belt to obtain a surface finish correspond-
to produce superior results. This is because most me- ing to grit 180 or better. If surface requirements are
chanical methods tend to produce a rougher surface very exacting, polishing may be necessary.
while chemical methods reduce the risk of surface con-
tamination. However, chemical cleaning may be limit- • Do not overheat the surface. In order to avoid creat-
ed not only by local regulations on environmental and ing further heat tint or higher stresses, apply less
industrial safety, but also by waste disposal problems. pressure when grinding.
12 AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
2.1.3 Brushing the obvious risk of pitting corrosion, chloride-containing
For the removal of heat tint, brushing using stainless agents such as hydrochloric acid (HCl) must be avoided.
steel or nylon brushes usually provides a satisfactory The main factors determining the effectiveness of pick-
result. These methods do not cause any serious rough- ling are as set out below.
ening of the surface. However, they do not guarantee
complete removal of the chromium-depleted zone. • Steel grade
The other mechanical methods present a high risk of Table 3 shows the most common stainless steel grades
contamination. Consequently, it is important to use and the matching welding consumables from Avesta
clean tools that have not been used for processing Welding and Böhler Welding. Pickleability has been
carbon steels. tested and the steels arranged into four groups. The
groupings are based on the ease with which the steels
can be pickled.
2.1.4 Summary
After a typical manufacturing programme, a final Steel group 1: Owing to the low chromium content,
mechanical cleaning stage could be as set out below. the corrosion resistance of this group is lower than that
of the groups below. The lower resistance of the steels
How to clean mechanically (when pickling has not in this group means they are “easier” to pickle. In other
been selected):* words, to avoid the risk of overpickling, they need
a shorter pickling time or a less aggressive pickling
1. Use grinding to remove welding defects.
agent. Special care must be taken to avoid overpickling!
2. Remove material affected by high temperatures and, The pickling result may be unpredictable.
if possible, remove iron impurities. The mechanical
Steel group 2: The steels in this group are standard
method chosen must not make the surface unaccept-
grades and fairly easy to pickle.
ably rough.
Steel groups 3 – 4: The steels in this group are high-
3. Remove organic contaminants (see section 1.6.5).
alloy grades. Being more corrosion resistant, they need
4. A final passivation/decontamination should be car- a more aggressive acid mixture and/or higher tempera-
ried out (strongly recommended). ture (to avoid an excessively long pickling time). The
risk of overpickling these steel grades is much lower
* In most cases, pickling is essential for optimal corro- (see table 3).
sion resistance.
• Surface finish
A rough, hot rolled surface may be harder to pickle
2.2 Chemical methods than a smooth, cold rolled one.
Chemical treatments can remove high-temperature
oxide and iron contamination. They also restore the • Welding method and resultant thickness and type
steel’s corrosion-resistant properties without damaging of oxide layer
the surface finish. Thickness and type depend largely on the welding
procedure used. To produce a minimum of oxides,
After the removal of organic contaminants, the normal weld using an effective shielding gas that is as free of
procedures are commonly pickling, passivation/decon- oxygen as possible. For further information, see the
tamination and/or electropolishing. Avesta Welding Manual and the Böhler Welding Guide.
Particularly when pickling high-alloy steel grades,
mechanical pretreatment to break or remove the oxides
2.2.1 Pickling might be advisable.
Pickling is the most common chemical procedure used
to remove oxides and iron contamination. Besides • Precleaning
removing the surface layer by controlled corrosion, The surface must be free of organic contamination.
pickling also selectively removes the least corrosion-
• Temperature
resistant areas such as the chromium-depleted zones.
The effectiveness of pickling acids increases with
Pickling normally involves using an acid mixture temperature. Thus, the pickling rate can be consider-
containing nitric acid (HNO3), hydrofluoric acid (HF) ably increased by increasing the temperature. However,
and, sometimes, also sulphuric acid (H2SO4). Owing to there are upper temperature limits that must also be
AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
13
Table 3: Stainless steel grades and pickleability considered. Especially when using a bath, the risk of
overpickling increases with high temperatures. When
Stainless steel grades Welding Welding consumables
method using pickling paste/gel/spray/solution at high tem-
EN ASTM Avesta Böhler
designation designation
peratures, evaporation presents the risk of poor results.
Besides an uneven pickling effect, this also leads to
Group 1: Very easy to pickle*
rinsing difficulties. To avoid these problems, objects
1.4006 410 MMA – FOX KW 10
must not be pickled at temperatures above 45ºC or in
1.4016 430 MMA – FOX SKWA direct sunlight.
1.4016 430 MMA – FOX EAS 2
1.4016 430 FCAW – EAS 2-FD • Composition and concentration of the acid
1.4313 410NiMo MMA – FOX CN 13/4
mixture
1.4313 410NiMo MCAW – CN 13/4-MC • Pickling method
Group 2: Easy to pickle There are three different pickling methods.
1.4301 304 MMA 308L/MVR FOX EAS 2
Pickling with pickling paste/gel: Pickling paste (or
1.4301 304 MIG 308L-Si/MVR-Si EAS 2-IG(SI)
gel) for stainless steels is suitable for pickling limited
1.4401 316 MMA 316L/SKR FOX EAS 4 M-
areas, e.g. weld-affected zones. It is best applied using
1.4401 316 MIG 316L-Si/SKR-Si EAS 4 M-IG(Si) an acid-resistant brush. Rinsing with water must be
1.4404 316L MMA 316L/SKR FOX EAS 4M- TS carried out before the paste dries. Even if, for environ-
V-joint
mental and practical reasons, neutralisation of the pick-
1.4404 316L MMA 316L/SKR FOX EAS 4M ling paste is carried out on the metal surface, thorough
1.4404 316L MMA 316L/SKR FOX EAS 4M-A rinsing with water is vital.
1.4404 316L FCAW 316L/SKR EAS 4M-FD
Pickling with pickling solution/spray: Pickling
1.4404 316L MIG 316L-Si/SKR-Si EAS 4M-IG
solution (or pickling gel in spray form) is suitable for
1.4404 316L MCAW – EAS 4M-MC
pickling large surfaces, e.g. when the removal of iron
Group 3: Difficult to pickle
contamination is also desired.
1.4539 904L MMA 904L FOX CN 20/25 M
1.4539 904L MIG 904L CN 20/25 M-IG Pickling in a bath is a convenient method if suitable
1.4539 904L MMA P12–R FOX NIBAS 625-
equipment is available.
1.4501 S32760 MMA 2507/P100 FOXCN 25/9 CuT
1.4161 S32101 MIG LDX 2101 – 2.2.2 Passivation and decontamination
1.4161 S32101 FCAW LDX 2101 CN 24/9 LDX-FD This procedure is carried out in a manner similar to
1.4362 S32304 MIG 2304 – pickling. The passivator, applied by immersion or
1.4362 S32304 FCAW 2304 CN 24/9 LDX-FD spraying, strengthens the passive layer. Because the
1.4462 S32205 MMA 2205 FOX CN 22/9N passivator also removes free iron impurities from the
1.4462 S32205 MIG 2205 CN 22/9 N-IG
surface, the treatment is more important after mechani-
cal cleaning and operations involving a risk of iron
2.4605 N06059 MMA – FOX NIBAS C 24
contamination. It is for this reason that the method can
2.4360 N04400 MMA – FOX NIBAS 400
also be referred to as decontamination.
Group 4: Very difficult to pickle
1.4547 S31254 MMA P12-R FOX NIBAS 625
1.4547 S31254 MIG P12 NIBAS 625-IG
2.2.3 Electropolishing
1.4565 S34565 MMA P16 FOX NIBAS C 24 Electropolishing normally produces a surface that
1.4565 S34565 MIG P16 NIBAS C 24-IG
guarantees optimal corrosion resistance. It does not se-
lectively remove areas of inferior corrosion resistance,
1.4410 S32750 MMA 2507/P100 FOX CN 25/9 CuT
but polishes microtips from the surface. The mate-
* Group 1 is very easy to pickle but, at the same time, difficult to treat. rial gains a fine lustre and, most importantly, an even
There is a risk of overpickling. Great attention must be paid to pickling
microprofile that meets extremely stringent hygiene
time and temperature.
requirements. For these reasons, electropolishing is
normally used as a final treatment after pickling. This
method is not covered in the present publication.
14 AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
2.3 Choice of method If it is not, decontamination, probably with nitric acid,
The choice of method and the amount of final cleaning will be necessary. Where surface finish and corro-
required depend on: corrosion resistance requirements; sion resistance requirements are exacting, the choice
hygiene considerations (pharmaceuticals, food, etc.); of method is more critical. In such cases, a treatment
and, the importance of the steel’s visual appearance. sequence based on pickling gives the best chances of
Removal of welding defects, welding oxides, organic superior results.
substances and iron contaminants is normally a basic The figure below shows the results of a test where the
requirement and usually allows a comparatively free samples (steel grade 1.4404/316L with MMA welds)
choice of final treatment. were post-weld cleaned using three different methods.
Provided that the surface roughness so permits, both They were then exposed to a marine environment for
mechanical and chemical methods can be used. How- two weeks.
ever, if an entirely mechanical cleaning method is de-
cided on, the manufacturing stage has to be very well
planned in order to avoid iron contamination.
AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
15
2.4 A COMPLETE CLEANING PROCESS 2.4.1 Case details
After a typical manufacturing programme, a complete Landaluce, a company in Spain’s Cantabria, has manu-
cleaning process could be as set out below. factured a total of 90 beer tanks for Heineken and its
brewery in Seville. Made in ASTM 304 hot rolled stain-
How to carry out a complete less steel, the 4.5 m diameter tanks are 18 m long.
cleaning process The beer tanks went through complete cleaning using
1. Inspect. the following Avesta Products:
2. Pretreat mechanically. • Cleaner 401.
• RedOne™ Spray 240 (tank exteriors).
3. Preclean. • Pickling Bath 302 (tank interiors).
4. Rinse. • FinishOne™ Passivator 630.
5. Pickle.
6. Desmut.
7. Rinse.
8. Passivate.
9. Neutralise.
10. Inspect.
Figure 10: Stainless steel beer tanks ready for shipping after complete cleaning using Avesta products (photo courtesy of
Landaluce)
16 AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
3.
3.1 Avesta products ous products must be available. Local and national
Avesta Finishing Chemicals offers a wide programme regulations must also be available. See, additionally,
of cleaning preparations. section 6.1.
In order to avoid health hazards and/or environmen- • A washing facility must be available, preferably
tal problems, pickling must be carried out in a special including a high-pressure water jet.
pickling area, preferably indoors. In this context, com-
• A first-aid kit must be available against acid splashes.
pliance with the recommendations below should be
See also section 6.1
regarded as compulsory.
• If the rinse water is recycled, care must be taken to
• Handling instructions and essential information (e.g.
ensure that the final rinse is performed using deion-
product labels, safety data sheets, etc.) for the vari-
AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
17
ised water. This is particularly important in the case
of sensitive surfaces and applications. How to use Avesta Cleaner 401
1. I nspect the surface to be treated and ensure
• A storage facility must be available. See also section 6.3. that all non-stainless material has been pro-
tected.
3.3 Precleaning/degreasing 2. U
sing an acid-resistant pump
Contamination on the surface can impair the pickling (Avesta SP-25), spray the pro-
process. To prevent this, thorough cleaning prior to duct onto the surface. Apply
pickling is recommended. Where loose dust, finger- an even layer that covers the
prints, shoeprints and tool marks are the contaminants, entire surface. Do not apply
acid cleaning (e.g. Avesta Cleaner 401) is usually in direct sunlight!
adequate.
3. A
llow the product suffi-
cient reaction time, but
avoid letting it dry. If the contaminants are
stubborn (difficult to remove) and in thick
layers, mechanical brushing with a hard plastic
or nylon brush will help.
4. P
referably using a high-
pressure water jet, rinse
thoroughly with clean
tap water. To reduce acid
splashing, prewashing at
Figure 12: Surface rust – before and after removal using tap-water pressure
Avesta Cleaner 401. (3 bars) is recommended. Ensure that no
residues are left on the surface. Use deionised
water for the final rinsing of sensitive surfaces.
18 AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
3.4 Pickling
Pickling products can be applied in three different How to use Avesta pickling pastes/gels
ways: 1. P
retreat oxides, slags and weld defects me-
chanically. This should preferably be done
• Brushing, using a pickling paste/gel while the welds are still warm and the weld
oxides less hard.
• Spraying, using a pickling solution
2. A
fter any welding, give the area to be pickled
• Immersion/circulation in/with a pickling bath
time to cool down to below 40ºC.
The different methods are presented in the following
3. T
o remove organic contamina-
pages.
tion, degrease using Avesta
Cleaner 401.
4. B
efore using, stir or shake the
paste.
5. U
sing an acid-resistant brush,
apply the pickling paste. Do
not pickle in direct sunlight!
6. G
ive the product sufficient
time to react (see table 4). At high tempera-
tures, and when prolonged pickling times are
required, it might be necessary to apply more
of the product after a while. This is because the
product can dry out and thus
cease to be as effective.
Figure 13: Brush pickling
7. P
referably using a high-
3.4.1 Pickling with paste pressure water jet, rinse
Creating a better working environment, Avesta thoroughly with clean tap
BlueOne™ Pickling Paste 130 is a unique pickling water. Ensure that no pickling
product. Using BlueOne™, there are virtually none of residues are left on the surface. Use deionised
the toxic nitric fumes normally formed during pickling. water for the final rinsing of sensitive surfaces.
Pickling Paste 130 can be used as a universal paste on
8. S
o that it can be neutralised, collect the waste
all stainless steel grades.
water. See also chapter 4.
AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
19
How to use Avesta spray-pickling gel 9. W
hen pickling, the pickling spray must not be
1. I nspect the surface to be treated and ensure allowed to dry. Drying may cause discolora-
that all non-stainless material has been pro- tion of the steel surface. This means that at
tected. high temperatures, and when prolonged pick-
ling times are required, it may be necessary to
2. P
retreat oxides, slags and weld defects me- apply more of the product after a while.
chanically. This should preferably be done
while the welds are still warm and the weld 10. Preferably using a high-pressure water jet,
oxides less hard. rinse thoroughly with clean tap water. To re-
duce acid splashing, prewashing at tap-water
3. A
fter any welding, give the area to be pickled pressure (3 bars) is
time to cool down to below 40°C. recommended. En-
sure that no pickling
4. To remove organic contamination, degrease residues are left on the
using Avesta Cleaner 401. surface. Use deionised
water for the final
5. Before using, stir the spray gel well.
rinsing of sensitive
6. U
sing an acid-resistant surfaces.
pump (Avesta SP-25), ap-
11. Passivation must be carried out directly after
ply the product as a spray.
wet-on-wet rinsing. Spray Avesta FinishOne™
Gently apply an even layer
Passivator 630 evenly over the entire surface.
of acid that covers the entire
surface. Do not pickle in 12. Leave to dry.
direct sunlight!
13. Carry out inspection and process verification.
7. Allow the product sufficient pickling time.
14. All treated surfaces must be ocularly inspected
8. D
esmutting is necessary if dark areas appear for oil residues, oxides, rust and other contami-
on the surface. Apply either more solution or nants.
Avesta FinishOne™ to these spots until they
disappear. This must be done when the surface 15. So that it can be neutralised, collect the waste
is still wet (i.e. “wet on wet”), just before the water. See also chapter 4.
pickling spray is rinsed off. Spraying
FinishOne™ on top of the pickled surface also
reduces the production of NOx gases.
Pickling equipment: To achieve a good spraying result, 3.4.3 Typical pickling times for brush and
a suitable pump is necessary. The pump must be made spray pickling
of an acid-resistant material and must provide an even
The pickling times given in table 4 must be seen as
application pressure. Avesta Spray Pickle Pump SP-25
indicative only. They are stated as intervals because, for
was specially designed to meet these requirements. It is
the same steel grade, the time required depends on the
a pneumatic, quarter inch pump of the membrane type
surface finish and the welding method (see also chapter
and has an adjustable valve.
1). For hot rolled surfaces, pickling times should nor-
mally be increased. Similarly, depending on the shield-
ing gas used, MIG welds might need longer than MMA
or FCAW welds.
20 AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
Table 4: Typical pickling times for brush and spray pickling (cold rolled surfaces)
Stainless steel grades Welding Welding consumables Pickling paste Picking spray
EN ASTM method Avesta Böhler Avesta Recommended Avesta Recommended
designation designation designation time (minutes) designation time (minutes)
Group 2: Easy to pickle
1.4301 304 MMA 308L/MVR FOX EAS 2 BlueOne™ 130 30 – 60 RedOne™ 240 45 – 90
1.4301 304 MIG 308L-Si/MVR-Si EAS 2-IG(SI) BlueOne 130
™
30 – 60 RedOne 240
™
45 – 90
1.4401 316 MMA 316L/SKR FOX EAS 4 M- BlueOne™ 130 30 – 60 RedOne™ 240 45 – 90
1.4401 316 MIG 316L-Si/SKR-Si EAS 4 M-IG(Si) BlueOne™ 130 30 – 60 RedOne™ 240 45 – 90
1.4404 316L MMA 316L/SKR FOX EAS 4M- TS BlueOne 130
™
30 – 60 RedOne 240
™
45 – 90
V-joint
1.4404 316L MMA 316L/SKR FOX EAS 4M BlueOne™ 130 30 – 60 RedOne™ 240 45 – 90
1.4404 316L MMA 316L/SKR FOX EAS 4M-A BlueOne 130
™
30 – 60 RedOne™ 240 45 – 90
1.4404 316L FCAW 316L/SKR EAS 4M-FD BlueOne™ 130 30 – 60 RedOne™ 240 45 – 90
1.4404 316L MIG 316L-Si/SKR-Si EAS 4M-IG BlueOne 130
™
30 – 60 RedOne 240
™
45 – 90
1.4404 316L MCAW – EAS 4M-MC BlueOne™ 130 30 – 60 RedOne™ 240 45 – 90
Group 3: Difficult to pickle
1.4539 904L MMA 904L FOX CN 20/25 M BlueOne™ 130 90 – 180 RedOne™ 240 120 – 240
1.4539 904L MIG 904L CN 20/25 M-IG BlueOne™ 130 90 – 180 RedOne™ 240 120 – 240
1.4539 904L MMA P12-R FOX NIBAS 625- BlueOne 130
™
90 – 180 RedOne 240
™
120 – 240
1.4501 S32760 MMA 2507/P100 FOXCN 25/9 CuT BlueOne™ 130 90 – 180 RedOne™ 240 120 – 240
1.4161 S32101 MIG LDX 2101 – BlueOne™ 130 90 – 180 RedOne™ 240 120 – 240
1.4161 S32101 FCAW LDX 2101 CN 24/9 LDX-FD BlueOne 130
™
90 – 180 RedOne 240
™
120 – 240
1.4362 S32304 MIG 2304 – BlueOne™ 130 90 – 180 RedOne™ 240 120 – 240
1.4362 S32304 FCAW 2304 CN 24/9 LDX-FD BlueOne™ 130 90 – 180 RedOne™ 240 120 – 240
1.4462 S32205 MMA 2205 FOX CN 22/9N BlueOne 130
™
90 – 180 RedOne 240
™
120 – 240
1.4462 S32205 MIG 2205 CN 22/9 N-IG BlueOne™ 130 90 – 180 RedOne™ 240 120 – 240
2.4605 N06059 MMA – FOX NIBAS C 24 BlueOne™ 130 90 – 180 RedOne™ 240 120 – 240
2.4360 N04400 MMA – FOX NIBAS 400 BlueOne 130
™
90 – 180 RedOne 240
™
120 – 240
Group 4: Very difficult to pickle
1.4547 S31254 MMA P12-R FOX NIBAS 625 BlueOne™ 130 120 – 240 RedOne™ 240 150 – 300
1.4547 S31254 MIG P12 NIBAS 625-IG BlueOne 130
™
120 – 240 RedOne™ 240 150 – 300
1.4565 S34565 MMA P16 FOX NIBAS C 24 BlueOne™ 130 120 – 240 RedOne™ 240 150 – 300
1.4565 S34565 MIG P16 NIBAS C 24-IG BlueOne 130
™
120 – 240 RedOne 240
™
150 – 300
1.4410 S32750 MMA 2507/P100 FOX CN 25/9 CuT BlueOne™ 130 120 – 240 RedOne™ 240 150 – 300
The pickling was preceded by mechanical pretreatment of the weld joints and precleaning using Avesta Cleaner 401.
AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
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3.4.4 Pickling in a bath
(40 – 50 g/l), the bath solution should be partially or
totally emptied out and fresh acid added.
Figure 16: Bath pickling (photo courtesy of Kurt Jensen) Group 2 steels: 1 part 302 into 3 parts water
Group 3 steels: 1 part 302 into 2 parts water
Group 4 steels: 1 part 302 into 1 part water
The stainless steel grade and the type of heat oxide deter-
mine the acid mixture and the bath temperature Temperature, composition and circulation need to be
(20 – 65ºC). Pickling low-alloy stainless grades at exces- controlled to get the best results. The composition of the
sive temperatures, or for a long period of time, presents bath is controlled through regular analysis. Together with
the risk of overpickling. This gives a rough surface. new mixing instructions to optimise the effect of the bath,
Avesta Finishing Chemicals can offer such analyses.
The effectiveness of pickling is affected not only by
acid concentration and temperature, but also by the free The pickling times given in the table below must be seen
metal content (mainly iron) in the bath. For pickling as indicative only. They are stated as intervals because,
times to be the same, the temperature in a bath with an for the same steel grade, the time required depends on
elevated iron content has to be higher than that in a bath the surface finish and the welding method (see also
with a lower iron content. A rough guideline is that the chapter 1). For hot rolled surfaces, pickling times might
free iron (Fe) content measured in grams per litre must be increased by 50%. Similarly, depending on the shield-
not exceed the bath temperature (ºC). When metal con- ing gas used, MIG welds might need longer than MMA
tents in the bath reach excessive levels or FCAW welds.
22 AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
3.4.5 Fume reduction during pickling
How to use Avesta bath pickling Environmental impact:
1. P
retreat oxides, slag and weld defects mechani-
cally. The toxic nitric fumes generated during pickling have a
number of effects.
2. A
fter any welding, give the area to be pickled
time to cool down to below 40°C. • Health: High nitric fume levels may lead to respira-
tory problems (e.g. infections). In the worst case,
3. T
o remove organic contamination, degrease inhalation may cause lung oedema.
using Avesta Cleaner 401.
• Environmental: Acidification of groundwater and
4. Check the bath temperature (refer to table 5). damage to plants.
5. I mmerse the object in the bath. Typical pickling Using modern pickling products such as Avesta
times are shown in table 4. Avoid overpickling. BlueOne™ Picking Paste 130 and Avesta RedOne™
This can produce a rough surface. Spray 240, toxic fume levels can be reduced by up
to 80%.
6. Allow the product sufficient pickling time.
Relative NOx-levels
7. If dark spots appear on the surface, desmut-
ting is necessary. Apply either more solution 100%
8. W
hen lifting the object, allow 20%
time for the bath solution to
flow off above the bath. 0
0 2 4 6 8 10 12 14
9. R
inse thoroughly using a high-pressure water Time (min)
jet. Ensure that no pickling residues are left on
Relative NOx-levels
the surface. Use deionised water for the final
100%
rinsing of sensitive surfaces.
Standard Pickling Spray
10. So that it can be neutralised, collect the waste 80%
water. See also chapter 4.
60%
11. As the pickling acid in the
bath is being constantly
Avesta
RedOne Diagram
Spray
™ red
consumed and metals pre- 40%
cipitated, analysis of bath
contents is important. Bath 20%
contents affect the pickling
reaction.
0
0 2 4 6 8 10 12 14
Time (min)
3.5 Passivation and desmutting Desmutting removes the dark spots caused by exces-
Avesta Finishing Chemicals’ Avesta FinishOne Pas- ™ sive iron left on the surface by faulty cleaning.
sivator 630 is a passivating agent that is free of nitric Fume reduction: While bath pickling, spraying Avesta
acid and has a low environmental impact. Because it is FinishOne™ Passivator 630 on the pickled object while
neutral after passivation, there is no need for a neutrali- lifting it from the bath reduces the toxic nitric fumes
sation stage. The product can passivate, desmut and generated during bath pickling.
reduce fumes.
How to use Avesta FinishOne passivator • Using an acid-resistant pump (Avesta SP-25),
• To passivate after mechanical treatment, first apply the product as a spray. Apply an even
use Avesta Cleaner 401 to preclean the surface. layer of acid that covers the entire surface.
Next, rinse with water and apply the passivator • Using an acid resistant pump (Avesta SP-25);
“wet on wet”. Leave it to react for 3 – 5 minutes. apply the passivator as an even layer that cov-
• To desmut or avoid smut formation during ers the entire surface.
spray pickling, the passivator must be applied • Preferably using a high-pressure water jet, rinse
before rinsing while the surface is still wet thoroughly with clean tap water. Ensure that
(“wet on wet”). Leave it to react for 10 – 15 min- no acid residues are left on the surface. Use
utes. deionised water for the final rinsing of sensitive
• To use for fume reduction after bath pickling, lift surfaces.
the object over the surface of the bath and spray • There is no need to neutralise the waste water
FinishOne™ as a mist on the object’s surface (“wet (it is neutral and acid free).
on wet”).
24 AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
4.
4.1 Neutralisation
The waste water from pickling is acidic and contami- How to neutralise
nated with heavy metals (mainly chromium and nickel 1. S
tirring all the time,
that have been dissolved from the steel). This waste add the neutralising
water must be treated in accordance with local regu- agent to the rinse
6 7 8
lations. It can be neutralised using an alkaline agent water.
(slaked lime, or soda) in combination with a settling 2. The neutralising
agent. reaction takes place
instantly.
1. Adjusting the pH value of the waste water causes the
heavy metals to be precipitated as metal hydroxides. 3. U
sing litmus paper
Precipitation is optimal at pH 9.5. (for example), check the pH of the mixture.
Precipitation of the heavy metals is optimal at
The heavy metals form a sludge that can then be pH 9.5.
separated from the neutralised clear water. This sludge
must be treated as heavy metal waste and disposed of 6 7 8 9 10 11 12 pH
accordingly.
CLEAR WATER
SLUDGE
4.2 Waste treatment
Pickling creates waste that requires special treatment.
Besides what comes from the chemicals themselves, the
packaging must also be considered as waste.
4. W
hen the waste water has reached an accept-
The sludge obtained after neutralisation contains heavy able pH value, wait for the sludge to sink to
metals. This sludge must be sent away for disposal in the bottom and for the water to become clear.
accordance with local waste regulations. Adding a special settling agent improves the
All materials used in the packaging (plastic containers, precipitation of heavy metals.
cardboard boxes, etc.)6of Avesta
7 8 Finishing
9 10 11 Chemicals’
12 pH
products are recyclable.
CLEAR WATER
SLUDGE
Clear water and sludge
6. T
he sludge contains heavy metals and must be
sent to a waste-treatment plant.
AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
25
5.
26 AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
Table 6: Surface defects and corrective actions
Surface defects Caused by Corrective action Precautions
AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
27
6.
Figure 23: Personal protection equipment Figure 24: Storage of pickling products
6.1 Safety rules 5. A First Aid kit containing calcium glucontate gel,
Pickling products are hazardous substances and must Hexaflourine® (Avesta First Aid Spray ) or other prod-
be handled with care. Certain rules must be followed to ucts suitable for an immediate treatment/rinsing of
ensure that the working environment is good and safe: acid splashes caused by pickling products, should be
easy available. For more information check the SDS for
1. Pickling chemicals must only be handled by per- the Avesta Pickling Products.
sons with a sound knowledge of the health hazards
associated with such chemicals. This means that the 6. The pickling area must be ventilated.
material safety data sheet (SDS) and the product 7. To avoid unnecessary evaporation, the containers/
label must be thoroughly studied before the chemi- jars must be kept closed.
cals are used.
8. To minimise the environmental impact, all pickling
2. Eating, smoking and drinking must be forbidden in residues must be neutralised and all heavy metals
the pickling area. separated from the process water and sent to a waste
3. Employees handling pickling chemicals must wash treatment plant.
their hands and faces before eating and after finish-
ing work. 6.2 Personal safety
4. All parts of the skin that are exposed to splashing Health hazards can be avoided by the use of breathing
must be protected by an acid-resistant material, ac- equipment and skin protection. If a high degree of
cording to SDS. This means that employees handling personal safety is to be ensured, we strongly recom-
pickling chemicals (including during rinsing) must mend that the following measures be regarded as
wear protective clothing as stipulated in the SDS for compulsory.
the product in question.
28 AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
For personal safety, a face mask (equipped with breath-
ing apparatus) must always be worn in connection
with pickling.
6.3 Storage
Pickling chemical containers must be stored indoors
at 10 – 35°C. They must be kept in an upright position
with the lids tightly closed. The storage area must be
clearly defined and inaccessible for unauthorised per-
sons. Pickling chemicals are sensitive to high tempera-
tures.
AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
29
References
1. “Outokumpu Corrosion Handbook for Stainless 9. “Post Fabrication Cleaning: Benefits and
Steels”, 2004. Practicalities”, International Conference, Stainless
Steel America 2004, Houston, USA Oct 2004,
2. “Standard Practice for Cleaning and Descaling C Baxter, A Bornmyr and R Stahura.
Stainless Steel Parts, Equipment and Systems”,
ASTM A-380. 10. Tappi Tip, “Post-fabrication cleaning of stainless
steel in the pulp & paper industry”, 2007, Chris
3. “Standard Specification for Chemical Passivation Baxter (Outokumpu Stainless), Elisabeth Torsner
Treatments for Stainless Steel Parts”, ASTM A 967. (Outokumpu Stainless), Anders Bornmyr
(Avesta Finishing Chemicals) and Ralph Davison
4. “Code of Practice for Cleaning and Preparation of
(Technical Marketing Resources).
Metal Surfaces”, BSI CP 3012.
11. Outokumpu website.
5. “Rahmenvorschrift für die Oberflächenbehandlung
austenitischer CrNi-Stähle, Chromstähle, 12. “The Avesta Welding Manual – Practice and
Nickellegierungen”, KWU Arbeitsvorschrift RE- products for stainless steel welding”.
AVS 8.
13. “The Böhler Welding Guide”.
6. “Beizen von nichtrostenden austenitischen Stählen”,
Hoechst AG, Praxis WN 87-0417. 14. “STAINLESS – stainless steels and their properties”,
Béla Leffler, Outokumpu Stainless.
7. “Traitement de Surface”, Framatome RCCM F-5000-
6000.
30 AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
Disclaimer
Information given in this manual may be subject to
alteration without notice. Care has been taken to en-
sure that the contents of this publication are accurate
but Böhler Welding Group Nordic and its subsidiary
companies do not accept responsibility for errors or for
information which is found to be misleading.
AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K
31
I002523:6EN-GB Centrumtryck, Avesta 2009
32 AV E S TA F I N I S H I N G C H E M I C A L S / P I C K L I N G H A N D B O O K