DOC 18

CHEMICAL TREATMENT OF
STAINLESS STEEL SURFACES
Second Edition, January 2014
European Hygienic Engineering and Design Group
EHEDG Secretariat
Lyoner Str. 18
60528 Frankfurt, Germany

Tel.: +49 69 66 03-1217 or -1430

Fax: +49 69 66 03-2217 or -2430
E-Mail: [email protected]
Web: www.ehedg.org

THE ENGLISH VERSION OF THIS EHEDG DOCUMENT IS THE OFFICIAL VERSION. THE RESPONSIBILITY
FOR THE PREPARATION, DEVELOPMENT AND ISSUANCE OF SUCH GUIDELINES LIES WITH EHEDG.
DUE TO THE TECHNICAL AND GENERAL NATURE OF THE GUIDELINES, EHEDG MAY NOT ASSUME ANY
LIABILITY RESULTING FORM THE INTERPRETATION, APPLICATION OR USE OF SUCH GUIDELINES.
EHEDG GUIDELINES ARE DEVELOPED IN CO-OPERATION WITH 3-A SANITARY STANDARDS.

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Contents Page
Summary ............................................................................................................................................................. 5 
Introduction ......................................................................................................................................................... 5 
1 Objectives and scope............................................................................................................................ 5 
2 Normative references ............................................................................................................................ 5 
3 Terms and definitions ........................................................................................................................... 6 
4 General ................................................................................................................................................... 7 
5 Pickling ................................................................................................................................................... 8 
5.1 Pickling principles ................................................................................................................................. 8 
5.2 Why Pickling is Necessary ................................................................................................................... 9 
5.3 When Pickling is Necessary ................................................................................................................. 9 
5.4 Pickling Procedure ................................................................................................................................ 9 
6 Passivation ........................................................................................................................................... 10 
6.1 Passivation principles......................................................................................................................... 10 
6.2 Why chemical Passivation is Necessary .......................................................................................... 11 
6.3 When chemical Passivation is Necessary ........................................................................................ 11 
6.4 Chemical Passivation Procedure....................................................................................................... 11 
7 Electropolishing .................................................................................................................................. 13 
7.1 Electropolishing principles and set-up ............................................................................................. 13 
7.2 Why electropolishing is necessary ................................................................................................... 15 
7.3 When electropolishing is necessary ................................................................................................. 15 
7.4 Electropolishing process limits ......................................................................................................... 16 
8 Influences of chemical treatments on plastic and elastomeric materials ..................................... 17 
9 References ........................................................................................................................................... 19 

DOC 18 ©EHEDG 3 of 19
 CHEMICAL TREATMENT OF STAINLESS STEEL SURFACES*

©EHEDG

The present second edition (January 2014) of this document was prepared by
Hans-Werner Bellin (1), Dr. Jochen Blume (2) , Dr. Jochen Brose (3), Johan Dedeene (4),
Dr. Gerhard Hauser (5)**, Benedikt Henkel (6), Dr. Jürgen Hofmann (7), Anneginus Hummel (8),
Dr. Tadeusz Matuszek (9), Dirk Nikoleiski (10), Eric Partington (11), Ferdinand Schwabe (12)

(1) BELLIN.consult, Heidestr. 3, 65326 Aarbergen, Germany

(2) POLIGRAT GmbH, Valentin-Linhof-Str.19, 81829 München, Germany
(3) TDM - Team Deutscher Maschinenexperten, Flemerskamp 19A, 44319 Dortmund, Germany
(4) Clusta VzW, Technologiepark 935, 9052 Zwijnaarde, Belgium
(5) Goethestraße 43, 85386 Eching, formerly: Technische Universität München, Lehrstuhl für Maschinen-
und Apparatekunde, Freising-Weihenstephan, Germany
(6) HENKEL Beiz- und Elektropoliertechnik GmbH u.Co.KG, An der Autobahn 12,
19306 Neustadt-Glewe, Germany
(7) Hygienic Design Weihenstephan, Postfach 13 11, 85313 Freising, Germany
(8) Friesland Campina Nederland B.V., Stationsplein 4, 3818 LE Amersfoort, Netherlands
(9) Gdansk University of Technology, 11/12 G Narutowicza St, 80952 Gdansk, Poland
(10) Mondelez International, Bayerwaldstraße 8, 81737 München, Germany
(11) Nickel Institute, Well Croft, Ampney St Mary, Cirencester, Gloucestershire GL7 5SN, United Kingdom
(12) Bahnhofstrasse 18, 73235 Weilheim, Germany

* Report prepared by the Subgroup “Design Principles” of the European Hygienic Engineering & Design
Group (EHEDG)
** Chairman

This document includes comments kindly provided by:

R. Avery (Nickel Institute/USA), M. Barnickel (LFL Bayern/D), J.C. Bohn (AGC Heat Transfer/USA),
O. Cerf (Alfort Veterinary School/F), T. Schonrock (3-A/USA), F. Schwabe (D)

The previous first edition of this document (August 1998) was co-authored by:
R.R. Maller (3-A/USA)

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Summary
This guideline supersedes Doc. 18 “Passivation of Stainless Steel” (1998) and includes new sections on
pickling and electropolishing of stainless steels.

Chemical surface treatments such as pickling, passivation and electropolishing can help to assure the
successful functional and corrosion-resistant performance of stainless steels for product contact surfaces in
the food and beverage industry. This document explains the general principles of those three processes
above: Why they are necessary, when and how they should be applied, how they work and which chemicals
are used.

Introduction
Food equipment manufacturers and users choose stainless steels as the predominant materials of
construction because of their excellent mechanical properties (e.g.: strength, formability, ductility and
weldability) combined with a high level of corrosion resistance and cleanability. The latter two attributes, which
are the primary determinants of the material's hygienic behaviour, rely upon the 'passive layer', a chromium-
rich oxide film which naturally forms on all stainless steels. This layer is adequately protective for the vast
majority of food and beverage applications.

Nevertheless, for particularly demanding applications, the strength of the passive layer (and therefore the
corrosion resistance of the surface) can be improved by a treatment known as chemical passivation. The
hygienic quality of the surface can be even further enhanced by electropolishing. However, the need for the
enhancement of the passive layer should be regarded as the exception rather than the rule.

The heat of welding can destroy the passive layer local to the weld and leave a distinctive, coloured 'heat-tint'
which will, itself, exhibit reduced resistance to corrosion. In this case welding must be followed by a pickling
procedure specifically designed to remove heat-tint and allow the passive layer to reform naturally.

This document discusses pickling, passivation and electropolishing in detail.

1 Objectives and scope

The purpose of this document is to provide specifiers, manufacturers and users of food-processing equipment
and also regulatory authorities with essential practical information about chemical surface treatments
applicable to stainless steels.

2 Normative references
The following referenced documents contain provisions that represent requirements of standards and legal
regulations. They are indispensable for the application of this EHEDG guideline. For dated references, only
the edition cited applies. For undated references, the latest edition of the referenced document (including any
amendments) is relevant.

EN 10027-1: Designation systems for steel; Part 1: Steel names, principal symbols

EN 10027-2: Designation systems for steel; Part 2: Numerical system

EN 10088-1: Stainless steels - Part 1: List of stainless steels

ASME BPE Bioprocessing Equipment

ASTM A380/A380M: Standard Practice for Cleaning, Descaling, and Passivation of Stainless Steel Parts,
Equipment, and Systems

ASTM A967/A967M: Standard Specification for Chemical Passivation Treatments for Stainless Steel Parts

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3 Terms and definitions
The definitions in the EHEDG Glossary (see www.ehedg.org/uploads/EHEDG_Glossary_E_2012.pdf) apply to
this guideline.

Passivity
The material specific chemically inactive condition of the passive surface layer of stainless steel.

Passive layer
The passive oxide film (chromium oxide) that develops naturally on the stainless steel surface when exposed
to air or a similar oxidising environment protecting the underlying base metal from corrosion [1]. It can be
supported and optimized (Cr/Fe ratio) by chemical treatment.

Natural Passivation
The formation of a passive layer when a clean stainless steel surface is exposed to oxygen.

Chemical Passivation
The chemical treatment of a stainless steel with a mild oxidant [2] enhancing the natural passive layer.

Cleaning (as a preparation for chemical treatment)

In the context of this document, cleaning is a treatment used to remove free iron as well as other
contaminants from the surface of stainless steels.

Pickling
An acid treatment used to remove from the surface of stainless steel fabrications the tinting caused by the
heat of welding when oxygen is present.

Topography
The geometrical profile of a surface which is measured as surface roughness.

Morphology
The structural and chemical composition of a surface which affects its corrosion behaviour.

Energy Level
A specific material parameter describing the surface tension/surface activity and affecting the adhesion of
soils and the cleanability of the surface

Free Iron
An unalloyed iron on a stainless steel surface.

Good Workshop Practice

The minimisation of the contamination or damage to a stainless steel surface during fabrication ([3], [6]).

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4 General
An important precondition for Hygienic Design is a functional surface of applied materials. It enables optimal
operating procedures by improvement of the surface´s properties topography, morphology and energy level.
The topography of the surface determines the cleaning behaviour, the formation of biofilm and contamination
as well as the emission of particles. The morphology of the surface determines the corrosion behaviour, the
cleanliness of the metal component, the chemical passivity and the emission of particles into the surrounding
media. The energy level and the electric charge of the surface determine the chemical properties of the
surface and the adsorption/desorption of soils or foodstuffs. Stainless steels are one of the first choice to
comply with these requirements.

They contain a minimum of 10.5% (by weight) of chromium and a maximum of 1.2% (by weight) of carbon.
However, within this basic definition there is a family of stainless steels with different contents of chromium,
nickel, molybdenum and a number of other alloying elements each designed to award particular properties to
the material.Table 1 shows the most common grades of stainless steel used in the food and beverage
industries.

Molyb-
EN AISI EN Type Carbon Chromium Nickel
denum
% % % %
1.4301 304 X5CrNi 18-10 Austenitic < 0·07 17 - 19·5 8 - 10·5 —
1.4306 304L X2CrNi 19-11 Austenitic < 0·03 18 - 20 10 - 12 —
1.4307 304L X2CrNi 18-9 Austenitic < 0·03 17·5 - 19·5 8 - 10 —
1.4401 316 X5CrNiMo17-12-2 Austenitic < 0·07 16·5 - 18·5 10 - 13 2·0 - 2·5
1.4436 316 X3CrNiMo 17-13-3 Austenitic < 0·05 16·5 - 18·5 10·5 - 13 2·5 - 3·0
1.4404 316L X2CrNiMo 17-12-2 Austenitic < 0·03 16·5 - 18·5 10 - 13 2·0 - 2·5
1.4432 316L X2CrNiMo 17-12-3 Austenitic < 0·03 16·5 - 18·5 10·5 - 13 2·5 - 3·0
1.4435 316L X2CrNiMo 18-14-3 Austenitic < 0·03 17 - 19 12·5 - 15 2·5 - 3·0
1.4006 410 X12Cr13 Martensitic 0·08 - 0·15 11·5 - 13·5 < 0·75 —
1.4512 409 X2CrTi12 Ferritic * < 0·03 10·5 - 12·5 — —
1.4460 329 X3CrNiMoN27-5-2 Duplex < 0·05 25 - 28 4·5 - 6·5 1·3 - 2
* Titanium stabilised.

Table 1: Grades of stainless steel commonly used for food and beverage equipment

Stainless steels with higher levels of chromium, nickel and molybdenum generally exhibit better corrosion
resistance, although these grades may be more expensive. All stainless steels self-passivate.

Certain food products (e.g.: salty or acidic foods) and some cleaning procedures may damage even a
passivated surface. It is therefore a pre-requisite of design that the intended conditions of use are considered
carefully and that an appropriate grade of stainless steel with sufficient inherent corrosion resistance is
selected. For instance, in a salty environment the material EN 1.4401 (AISI 316), which contains about 2.25%
Molybdenum, will exhibit a greater resistance to pitting corrosion than EN 1.4301 (AISI 304).

The formation of an effective passive layer on any stainless steel depends upon the surface being free from
both physical and chemical contaminants. Mill-scale (a thick, visible oxide scale) must be removed ―
although this is invariably carried out at reputable steel mills before the material is delivered to the equipment
fabricator.

Soils like grease, oils, adhesives, footprints, fingerprints and paints must be washed away with appropriate
chlorine-free degreasing agents or solvents. Both liquid and vapour degreasers are used. Liquid cleaning is
often done by caustic detergents (e.g. blends of non-phosphate detergents, buffers and surfactants) or hot
alkaline solutions also containing various additives (e.g. blends of sodium and potassium hydroxides and
surfactants). Organic solvents (e.g. isopropyl alcohol) can be applied by spraying or swabbing.

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Embedded iron particles (common contaminants resultant from poor workshop practices where carbon steels
have been processed - e.g.: machined, ground, wire-brushed, blasted or welded - adjacent to stainless steel
stock) must be removed by an acid treatment (e.g. by citric or nitric acid) appropriate to the extent of the
contamination. After each of these treatments, the surface must be rinsed thoroughly.

Given a clean surface and sufficient oxygen (from the air or from oxygenated water), stainless steels will
naturally and spontaneously establish a tenacious passive layer on all exposed surfaces.

If the passive layer is physically damaged during or after the fabrication of the equipment, it must be afforded
the opportunity to repair itself, which it will do spontaneously as soon as the surface is clean and exposed to
oxygen again. The passive layer will also be damaged by welding so post-weld pickling may be necessary.

If demanded by the particular application the strength, and therefore the corrosion resistance, of the passive
layer can be enhanced by a chemical passivation treatment and/or by electropolishing.
Pickling, chemical passivation and electropolishing should be seen as separate treatments and not as
alternatives. Each should only be carried out with care by qualified contractors. It must be remembered that
chemical surface treatments of an integrated system may adversely affect elastomeric, plastic and glass
materials. It is therefore important to apply to assembled equipment surface treatments only which are
appropriate to all the materials with which they might come into contact.

5 Pickling
Pickling is an acid treatment intended to remove a thin (usually 1 to 3 µm) layer of corrosion-susceptible
material which has resulted from the exposure of a stainless steel surface to high temperatures in the
presence of oxygen (e.g. welding with shielding gas containing more than 40 ppm of oxygen [5]). Used in
moderation, pickling does not adversely affect the surface topography nor its cleanability.

If used more aggressively and under strict control, pickling can effect the removal of as much as 8 µm of a
surface. However, excessive pickling can damage a surface and reduce its corrosion resistance (see Fig. 3b
and 3c).

5.1 Pickling principles

Pickling of a welded area should be preceded by any mechanical treatments, such as grinding or abrading,
which are necessary to remove oxidation products, and such treatments should be followed by the degreasing
of the affected area. However, pickling should be carried out before any chemical passivation treatment.

Pickling should not be confused with de-scaling, which is the removal of a thick, flaky oxide scale from the
surface. This oxide is usually dark grey and is routinely removed in the manufacturing steel mill before the
steel is delivered [4].

Pickling is not appropriate for the removal of free iron particles. If poor workshop practices have resulted in
free iron particles which are too deeply embedded for removal by pickling acid, more aggressive chemicals
can be used that are able to remove embedded iron completely. But it is important that all the free iron is
removed and not spread to other areas of the stainless steel fabrication surfaces.

Pickling should not be confused with chemical passivation (see section 6), which is a process which may be
used to help thicken, and therefore strengthen the protective passive layer which is the source of stainless
steel's corrosion resistance.

Pickling is not intended to smooth stainless steel surfaces or rough welding seams. Nor is it intended to
correct surface changes like grain deformation or modification which may have resulted from the cold forming
of stainless steel components; for these, surface grinding may be more appropriate.

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5.2 Why Pickling is Necessary

During welding the localised heating of the stainless steel causes the originally transparent passive layer to
increase in thickness. After welding, the effect of this will be clearly visible as bands of colour, known as 'heat
tint', on the weld and in the 'Heat-Affected Zones' (HAZ) on either side of it (see Fig. 1). The heat also causes
chromium to be drawn to the surface because chromium combines with oxygen in the atmosphere more
readily than the iron in the steel. This outward diffusion of chromium leaves a layer at and just below the heat-
tinted surface with a lower chromium level than that of the bulk of the steel. This will exhibit reduced
resistance to crevice or pitting corrosion. It is therefore good workshop practice to remove all visible heat tint.

Pickling is not only used after welding. It can also be used for cleaning surfaces to remove fabrication residues
such as iron oxides.

5.3 When Pickling is Necessary

All surfaces which exhibit heat tint in excess of the 'straw yellow colour' limit described in EHEDG Doc. 35 [5]
have to be pickled. Even those welds not easily visible (such as on the insides of pipe-work) should be pickled
and, deemed if necessary, chemically passivated before service. Ideally, equipment should be designed such
that individual components (e.g.: lengths of pipe-work) can be pickled separately prior to assembly.
Where the colour of the heat-tint is lighter than straw yellow (see Fig. 2), pickling may be considered
unnecessary, particularly if the weld is in an area difficult to treat (e.g. inside pipe-work).

Fig. 1: Heat tint inside a tube at Fig. 2: Only minimal heat-tint inside
the location of the weld the tube at the location of
(Source: HENKEL) the weld (Pickling not essential)
(Source: HENKEL)

5.4 Pickling Procedure

Mixtures of nitric and hydrofluoric acids (HNO3 and HF) are usually used for pickling stainless steels (see
Table 2). Pickling acids can be applied by tank immersion, circulation in pipe-work or by spray, and are also
available as brush-on pastes or gels for localised treatment of components too large to be immersed.

Grade of stainless steel HNO3 * + HF * Temp Time

Volume % Volume % °C minutes
300 series with > 16% Cr 15 - 25 + 1.0 – 8.0 at 21 - 60 for 5 - 30
400 series with < 16% Cr 10 - 15 + 0.5 – 1.5 at 21 - 60 for 5 - 30

*Solutions prepared from reagents of the following weight %: HNO3 67; HF 70.

Table 2: Typical compositions of pickling solutions (Source: [3] Table A1.1)

These aggressive nitric/hydrofluoric acid (HNO3/HF) pickling preparations are specifically designed to remove
oxides such as the heat-tint resultant from welding. They should not be used for the general cleaning or
chemical passivation of a stainless steel surface.

After pickling, all acids, residues and contamination should be completely rinsed from the surface of the steel
so that it remains stain-free and can achieve maximum corrosion resistance. At this stage, the surface will be
free of scale, free iron and exogenous foreign matter and ready for any chemical passivation deemed
necessary.

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It should be mentioned that after pickling the complete rinse may include removal and/or replacement of
gaskets and seals because residues of pickling acids may remain in small crevices.

Because HNO3/HF acid pickling does remove a small amount of metal from a surface, its use should be
limited. Strong pickling acids can cause some unacceptable surface etching if used to excess. Excessive
exposure to pickling acids should be avoided (see Fig. 3b and 3c).

Fig. 3: Weld showing heat tint a) without any pickling treatment (left) and correctly pickled
(right), b) and c) excessively pickled weld (Source: HENKEL)

Some pickling procedures can unacceptably degrade a shiny surface, and so, where appropriate, the final
surface finish after pickling should be agreed and specified. Quantification of the effect of the pickling process
can be achieved by measuring reflectivity and gloss parameters.

Nitric/hydrofluoric pickling acids can also damage the surfaces of elastomeric and plastic components (see
chapter 8 below).

6 Passivation
Passivation is the process by which stainless steel becomes protected against corrosion by a passive layer.

Reference [3] identifies a number of common uses of the term 'passivation', whether spontaneous or assisted,
and so, for clarity, the meanings attributed by this Guideline are given below.

The passive layer on stainless steel forms without intervention in an oxygen-containing environment provided
that the surface has been thoroughly cleaned and de-scaled ([3] par. 1.1.1.1). This document will refer to this
spontaneous process as 'natural passivation'.

When required by the intended application of a stainless steel component, this passive layer may be
enhanced or strengthened by a chemical treatment ([3] par. 1.1.1.3) which this document will refer to as
'chemical passivation'.

6.1 Passivation principles

The passive layer on stainless steel is a surface condition and not a property of the bulk material itself. The
passive layer is a dense transparent surface layer of approximately 2 - 8 nm thickness containing mainly
chromium oxides but also other compounds such as iron oxides and ions. The quality of the passive layer is
primarily determined by its chromium to iron ratio. The corrosion resistance is related to its semiconducting
properties that allow electrons to penetrate but not ions.

´Natural` formation of a passive layer is spontaneous and involves the reaction of oxygen from the
surroundings with chromium from the material surface without any chemical intervention. This requires a clean
surface as well as sufficient oxygen content. The time for the formation of the passive layer is dependent on
the purity of the surface, the composition of the alloy, its state or structure and the environment.

If the passive layer is physically damaged, it re-forms spontaneously under the influence of oxygen from air or
water, so long as the scratches are not contaminated (see Fig. 4).

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 a well-formed damage to the self-repair of the
passive layer passive layer passive layer

Fig. 4: Stainless steel builds up on its surface an invisible, protective,

self-repairing oxide film, known as 'the passive layer' (Source: Euro Inox).

The passive layer can be damaged during the fabrication of semi-finished parts or the assembly/ manufacture
of equipment (e.g.: rolling, milling, grinding, mechanical blemishing, welding and weld-repairs), by chemical
and environmental conditions (e.g.: the composition of the food, the use of abrasive or chlorine-containing
cleaning substances or an insufficient supply of oxygen to repair damage) or by contamination during storage
(e.g.: contact with rusting carbon steels).

6.2 Why chemical Passivation is Necessary

Chemical passivation is necessary if natural passivation is demonstrably inadequate. It optimises the layer
with respect to composition and thickness of the layer.

6.3 When chemical Passivation is Necessary

If a hazard analysis of the materials of construction, the food product, the cleaning regimes or the
environmental conditions indicate that there is insufficient confidence in the passive layer then chemical
passivation should be considered.

The final selection of chemical passivation or re-passivation procedure depends on the material specification
(the type/grade of the stainless steel), fabrication specifications (e.g.: for welding and for installation, and
specified procedures after commissioning), operational procedures at the end user (e.g.: concentration and
temperature of product and of cleaning chemicals), regulations governing safety at work and environmental
safety

Evidence for the absence of ferritic contaminations and effective passivation can be provided using
appropriate tests ([3] section 7.2).

6.4 Chemical Passivation Procedure

A typical procedure for the chemical passivation of equipment at the manufacturers contains the following
steps:

1. cleaning with potable water,

2. cleaning/degreasing with alkaline and/or acidic chloride free detergents (see section 4)
3. rinsing with potable water (high pressure if possible)
4. surface cleaning (e.g. chlorine-free chemical pickling, electro polishing)
5. rinsing with potable water (high pressure if possible)
6. chemical passivation; optimisation of passive layer (examples of solutions Table 3)
7. rinsing with potable water (high pressure if possible)
8. testing of optical characteristics, measurement of pH, free iron tests (if required) ([3] section 7.2.5)
9. final rinsing with potable water or (if required) purified water.

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If a test for free iron (e.g. when the surface is ground or blasted) is satisfactory, steps 1 to 3 implement the
requirements for “natural passivation” and steps 4 and 5 can therefore be omitted.

The inspection procedure for cleaning and chemical passivation after assembly and before initial operation will
omit steps 6 and 7.

In operation the passive layer can be damaged by fouling (e.g.: deposits, biofilms) or by harsh operating
conditions (e.g.: high temperatures combined with aggressive chemicals). The cause of harsh operating
conditions has to be analysed and eliminated if possible. The restoration of the surface function and/or a re-
passivation is then necessary. In order to determine which chemical passivation procedure has to be used to
restore the passive layer to the quality appropriate to the application (assuming that natural passivation is
deemed inadequate) requires a situation analysis. This should include, but is not limited to:

— applicability of possible chemical or electrochemical procedures with respect to the existing

equipment/plant
— determination of the procedure and the course of action between operating company and service provider
— safety at work and environmental safety when carrying out the procedure
— feasibility in the available time frame

Grade of stainless steel Nitric acid Citric acid Temp Time

Volume % Weight % °C minutes
300 series 20 - 45 at 21 - 32 for > 30
or 4 - 10 at 21 - 49 for > 20
400 series 45 - 55 at 49 - 54 for > 30
or 4 - 10 at 21 - 49 for > 20

Table 3: Typical compositions and application parameters of chemical

solutions (Source: [2] par. 6.1.1 and 7.1.1)

The classic passivation treatment with nitric acid (HNO3) as an oxidising medium (examples see Table 3)
leads to formation of chromium oxide.

Chemical passivation of high-carbon stainless steels and some hardenable stainless steels using nitric acid is
not advisable ([3] par. A2.2 and A2.4).

Citric acid compositions (examples see Table 3) act as chelates. These are ‘chemicals that form soluble,
complex molecules with certain metal ions, inactivating the ions so that they cannot normally react with other
elements or ions to produce precipitates or scale’ ([3] par. 6.2.7). Iron-ions are bound by the citric acid forming
iron complexes which diffuse the metal surface. Oxygen (from the composition) reacts with free chromium to
chromium oxide. Thus, the passive layer can be improved [7]. Citric acid as a non-oxidising acid does not
itself form chromium oxide. In comparison with nitric acid, citric acid is a low hazard waste product.

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7 Electropolishing
Electropolishing is an electro chemical surface treatment which does not involve physical contact with the
surface. It should not be confused with mechanical polishing.

7.1 Electropolishing principles and set-up

By electropolishing topography, morphology and energy level can be optimized. Electropolishing is a

relatively-new procedure for effecting a lasting improvement of significant functional (surface)-properties of
components made of different metallic alloys. Especially with components made of austenitic stainless steel
alloys, not only the corrosion resistance can be improved substantially and sustainably by electropolishing
which optimises the passive layer formation on the surface but also the cleaning behaviour due to a micro-
smoothening of the surface.

Industry sectors in which electropolishing may be advantageous include biotechnical (vessels, tubes and
fittings), semi-conductor (tubes and fittings), food and beverage (plant components) and high vacuum
technique (recipients). Fig. 5. shows examples of electropolished equipment.

Fig. 5: Electropolished components of material 316L: Tanks (left), tubes (right)

(Source: HENKEL)

A lasting improvement effect of the surface regarding topography, morphology and energy level by
electropolishing is achieved with material removals of minimum approx. 10 - 15 µm. If dimensional tolerances
need to be kept, the component must be manufactured with appropriate allowances.

Flash electropolishing (material removal < 5 µm) is too short to generate such benefits.

Electropolished surfaces must not be pickled as this would destroy the electropolished surface. In the case of
already-installed electropolished tube systems, any welding processes must be particularly carefully carried
out so as to minimise heat tint [5] because post-weld pickling of an electropolished surface is not appropriate.

During electropolishing, anodic dissolution of metal ions takes place in a suitable electrolyte using an external
direct current source. This dissolution is current density selective (i.e. it depends on the distance between the
anode and the cathode). Normally, phosphoric and sulphuric acid electrolytes are used for electropolishing
austenitic stainless steels. The principal of the electropolishing set-up is illustrated in Fig. 6.

DOC 18 ©EHEDG 13 of 19
 1 = Rectifier
2 = Anode: the positive pole of the rectifier. This will be the
stainless steel component
3 = Cathode: the negative pole of the rectifier. This is made
of copper (Cu).
4 = Electrolyte (phosphoric acid H3PO4 + sulphuric acid
H2SO4 + additives) at approximately 50ºC
5 = Agitator (stirrer).

Fig. 6: Setup for austenitic steel electropolishing (Source: HENKEL)

A typical procedure for electropolishing is:

— alkaline pre-cleaning of surface (with chlorine free detergents)

— rinsing with water (e.g.: demineralised water)
— electropolishing according to calculated process parameters
— rinsing with water (demineralised water)
— special acidic rinsing operation/possible chemical passivation
— rinsing with water (e.g.: demineralised water)
— drying (e.g.: air or nitrogen)

The use of demineralised water as a rinsing medium helps to remove ionic residues and to minimise staining.

The electrochemical removal rate depends on current density and exposure time. Specific process
parameters for electropolishing are:

— electrolyte (constitution, density, metal content, temperature),

— cathode material,
— anodic electrical contact (with component),
— electropolishing parameters (current density, current, voltage),
— electropolishing removal rate/exposure time,
— pre-/post-cleaning (degreasing, a special acidic rinsing operation/possible chemical passivation).

After electropolishing a special acid rinsing/chemical passivation operation is necessary to remove metal salts
residues of the electropolished surface and to enhance the protective chromium-oxide enriched passive layer.

All operations should be pre-defined and described in work instructions. This documentation should include
any mechanical pre-treatment processes (e.g.: grinding, blasting, etc.), all surface testing (e.g.: visual
checking, roughness measurements, classification of defects, etc.) and the electropolishing procedure itself.
After the electropolishing operation itself, all the procedures used and all the actual process parameters
should be recorded in detail for traceability.

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7.2 Why electropolishing is necessary

The advantages of electropolishing are

— high-quality surfaces to improve corrosion resistance,

— smooth surface structure to facilitate cleanability,
— reduced surface roughness values (e.g. Ra, Rz) including micro smooth surface with a minimised surface
area to facilitate cleaning,
— elimination of particle emission of surfaces,
— removal of embedded foreign bodies resulting from manufacturing (e.g. grit from mechanical polishing),
— reduction of the surface energy,
— crystalline clean surfaces as pre-treatment for subsequent surface treatment (e.g. plating),
— deburred and micro-deburred edges,
— shiny surfaces for design reasons and improved appearance.

The objectives of the electropolishing process need to be defined exactly and specified beforehand. The same
applies to the process documentation and surface inspection before and after.

7.3 When electropolishing is necessary

A significant advantage of electropolishing is the creation of very smooth surfaces (typically Ra < 0.2 µm). The
smoothing of the surface by means of electropolishing is demonstrated in Fig. 7. Moreover, metallically clean
surfaces are created by electropolishing. In comparison with other treatment procedures, the formation of
optimal passive layers of austenitic stainless steels regarding Cr/Fe-relation and passive layer thickness for
maximum corrosion resistance can be achieved.

a b c d e

30 µm

Fig. 7: Smoothing of surfaces by increasing the removal of surface material by electropolishing

a) Original Tube 12.7 x 1.65 mm, longitudinally welded, cold redrawn and solution annealed in H2
atmosphere, Ra = 0.23 µm (light microscope/magnification approx. 500x) (Source: HENKEL)
b) electropolished: removal ~ 2...3 µm, Ra = 0.33 µm
c) electropolished: removal ~ 5 µm, Ra = 0.25 µm
d) electropolished: removal ~ 10 µm, Ra = 0.19 µm
e) electropolished: removal ~ 25 µm, Ra = 0.12 µm

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The pitting potential in relation to the surface finish is shown in Fig. 8. The pitting potential is dependent on
alloy composition and may be used as a relative measure of pitting tendency (corrosion resistance) for various
alloys. The diagram shows clearly that for higher demands on corrosion resistance electropolishing or
procedures optimising the passive layer should be considered.

Fig. 8: Pitting potential effect Y (mV) for AISI 316L versus surface finish X (re-passivation and resting
potential are not shown): higher pitting potentials indicate increased corrosion resistance
(Source: Practical ennoblement of stainless steel surfaces by appropriate surface finish, Joint research VAL/HENKEL, 1988;
published in technical report Henkel No. 51, 2002)

A) Welding discoloration: a1) yellow, a2) brown, a3) blue/black,

B) Mechanical surface finish: b1) K60, b2) K220, b3) K600, (K = ground grit grade)
C) Chemical/electrochemical surface finish:
c1) chem. pickled (HF + HNO3 + Additives) + final chemical passivation (HNO3 + Additives)
c2) electropolished (H3PO4 + H2SO4 + Additives) + final chemical passivation (HNO3 + Additives)

Furthermore, electropolishing enables the removal of micro-porous smear layers (so called Beilby-Layer)
which are due to mechanical treatment procedures (e.g. mechanical grinding). Also surface layers with
residual stress can be removed by electropolishing which creates low-energy surfaces.

The effect of electropolishing on micro-porous smear layers caused by honing or grinding is demonstrated in
Fig. 9.

Electropolishing also assists in the detection of defects such as cracks and pores by simple visual inspection.

7.4 Electropolishing process limits

Process limits of electropolishing are geometrical dimensions (e.g. size of the electropolishing baths,
tube/bore diameter of the component < 0.5 mm). For material removals > 100 µm a combination with
mechanical removal processes is recommended. Concerning installations (e.g. tube systems) electropolishing
is only possible with increased effort and expense.

Large surface areas or extensive components such as big vessels can be electropolished in situ by a mobile
electropolishing technique. This electropolishing process can be applied also for field work on components in
the industry and does not limit electropolishing due to reasons of geometrical dimensions of components or
size of components to be transported. This mobile electropolishing technique also supports refurbishment of
equipment on-site.

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 Description of surface treatment:
a b c
Columns a and b are mechanically
7 0 ground with different roughness. Column
3 6
2 c is electropolished
Description of grain structure:
10 µm
1 Austenite
5 2 Austenite and cold formed Ferrite
1 1
4 20 µm 3 Cold formed Ferrite
3 4 Cold formed Ferrite and formed
Austenite
30 µm 5 Formed Austenite
2 6 Heavily formed grains with oxidized
inclusions
1 40 µm 7 Various oxides

Fig. 9: Schematic description of surface treatment and its impact on grain structure - especially also
referring to the morphological changes into the depths (Studies by Wulff on material
1.4301/AISI 304)
(Source: P. Wulff, Stainless Steel Surface Morphology; Stainless Steel Conference New York (USA), 1947)

The final roughness value Ra depends on the condition of the pre-material. Even with ideal pre-conditions a
final roughness Ra < 0.05 µm is only just attainable.

Repairing of defects from mechanical pre-treatment (e.g. scratches) is not possible by electropolishing alone.

Titanium stabilised alloys (e.g. EN 1.4571/AISI 316Ti) can also be electropolished. Due to material-specific
inclusions (Ti-carbides) electropolishing of very shiny surfaces is only possible to a limited extent.

8 Influences of chemical treatments on plastic and elastomeric materials

The properties of the finished plastics or elastomers not only depend on their type but also strongly on the
filler system, the cross-linking system, and the other ingredients of the formulation. Also, the mixing of the
compound, the curing time and temperature as well as the post-curing procedure is of strong influence on the
quality of the finished product. That is why it is nearly impossible to give reliable general recommendations.

It has to be considered that not only the chemical compatibility is important for application of pickling and
passivation procedures, but also the physical properties (e.g. mechanical strength, hardness or modulus).
Especially in hygienically designed grooves, volume swell of gaskets caused e.g. by any chemical solution as
well as thermal expansion at higher temperatures can cause problems and lead to damage.

The suitability of the various chemical compatibility guides is limited. It is important to recognise that when
using them, the ratings they show are based on published data and immersion tests. These tests are
conducted under laboratory conditions predominantly at room temperature and may not represent adequately
the condition in the field. Relative short term laboratory tests may not pick up all the additives and impurities
which may exist in long term service applications.

Care must be taken to ensure that all aspects are considered carefully when a material is to be approved for a
pickling or passivation procedure. For example, at elevated temperatures some aggressive fluids can cause a
much more marked effect on an elastomer than at room temperature. Physical properties as well as fluid
compatibility need to be considered. Compression set, hardness, abrasion resistance, and thermal expansion
can influence the suitability of a material for a particular application. It is recommended that users conduct
their own tests to confirm the suitability of the selected material. In this case, a sample of the plastic material
could e.g. be placed in the chemical solution using the applied concentration, temperature and time. Typical
changes can be swelling, extraction (loss of elasticity) hardening or increasing of surface porosity. However,
the best choice is to contact the supplier of the plastic or elastomeric material to give advice.

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Table 4 shall give a general estimation if a certain material group might be chemically and physically (swell)
resistant against the procedures described. The assessment of resistance is based on intended single use
after assembly of the equipment and may be one or two repetitions after maintenance and repair. This
estimation cannot give guarantees, because within the same material group, there are differences in material
quality, depending on formulation and manufacturing.

Pickling procedures Passivation procedures

Chemical Medium HNO3/HF Chemical Medium HNO3 HNO3 Citric Acid

Temperature [°C] 50 Temperature [°C] 60 30 70
Max. concentration [%] 10/2 Max. concentration [%] 25 45 10
Time of exposure [min] 30 Time of exposure [min] 30 30 5

Elastomers Elastomers
ISO 1629/ASTM 1418 ISO 1629/ASTM 1418
EPDM EPDM
FKM FKM
FKM high fluorinated FKM high fluorinated
FVMQ FVMQ
HNBR HNBR
HR HR
NBR NBR
VMQ VMQ
PU/EU (TPU) PU/EU (TPU)

Table 4: Estimated approximate resistance of some elastomers to pickling and passivation

procedures (red = not recommended, yellow = limited resistance, green = generally suitable).
A certain assessment cannot be made on the influence of the surface structure and surface
deterioration of the rubber. To establish more knowledge tests are necessary
(Source: Schwabe, Cutler, Trelleborg)

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9 References
[1] ASME BPE: 2012, Bioprocessing Equipment

[2] ASTM A967/A967M-13, Standard Specification for Chemical Passivation Treatments for Stainless Steel
Parts

[3] ASTM A380/A380M-13, Standard Practice for Cleaning, Descaling, and Passivation of Stainless Steel
Parts, Equipment, and Systems

[4] Pickling and Passivating Stainless Steel Second Edition 2007 (Materials and Applications Series, Volume
4 C3 Euro lnox 2007)

[5] EHEDG Guideline Doc 35: Hygienic Welding of Stainless Steel Tubing in the Food Industry, July 2006

[6] EuroInox Stainless Steel in the food and beverage industry, Materials and Applications Series, Vol. 7,
2006, chapter 5

[7] Bayer Technology Services, Report H0022-8, 04/2010

Order information on EHEDG guidelines can be obtained under www.ehedg.org > Guidelines > Ordering
Guidelines (http://www.ehedg.org/index.php?nr=9&lang=en)

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