Designation: B 322 – 99 Endorsed by American

Electroplaters’ Society
Endorsed by National
Association of Metal Finishers

Standard Guide for

Cleaning Metals Prior to Electroplating1
This standard is issued under the fixed designation B 322; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

INTRODUCTION

This guide is intended to illustrate general principles of cleaning prior to electroplating. It is not
meant to apply to every specific application. In specific cases, cleaning practice may depart from the
general principles given in this guide.

1. Scope Often, depending largely on the amount and type of soil on

1.1 This guide describes the procedure for cleaning metal the workpieces as received, one or more of these stages may be
surfaces to obtain good adhesion of electrodeposited metals. eliminated or modified. Usually, even with light soils, it is
The degree of cleanliness required for metals to be electro- advisable to retain multistage cleaning, thereby increasing the
plated is greater than for most other finishes. Methods of life and efficiency of the cleaning solutions.
removal of heat-treat or mill scale are not included in these 1.5 This standard does not purport to address all of the
methods, because they are covered in practices referring to safety concerns, if any, associated with its use. It is the
specific metals. It should also be understood that while these responsibility of the user of this standard to establish appro-
procedures are broadly applicable, particular substrates may priate safety and health practices and determine the applica-
require certain specific cleaning procedures. bility of regulatory limitations prior to use. (For more specific
1.2 Adequate cleaning requires a proper combination of safety precautionary statements see Sections 11 and 16.)
cleaning procedures. The choice of these procedures must be 2. Significance and Use
based on a knowledge of the metals to be cleaned and of the
soils to be removed. Because most experience and knowledge 2.1 The performance and quality of electroplated articles
in cleaning have been obtained by suppliers of proprietary depend upon the surface cleanliness and condition. Various
processes and formulations, these sources should be consulted metals are electroplated for decorative or engineering finishes.
before setting up a cleaning process. The common electroplates applied are usually copper, nickel,
1.3 A treatment to remove tarnish, light rust, fingerprints, or and chromium for decorative and functional uses. Electro-
oxides is usually provided before immersion of the piece in the plated articles are used in many industries such as the marine,
electroplating tank. This treatment activates the metal and is automotive, plumbing fixtures, and appliance industries.
usually accomplished in acid baths which also serve to 3. Nature of the Soil
neutralize the residual alkaline film from alkaline cleaning.
Alkaline chelated derusting and cleaning solutions, alone or 3.1 Some of the soils commonly encountered in electroplat-
with sodium cyanide, used as a soak or electrocleaner, are often ing are:
preferred before electroplating on ferrous alloys. 3.1.1 Solid buffing compounds containing waxes, fatty ac-
1.4 Invariably several stages are necessary to provide ad- ids, and abrasives.
equate cleaning. These stages are discussed in three parts: 3.1.2 Liquid buffing compounds.
Part I—Precleaning (use of a solvent, emulsion, or alkaline 3.1.3 Drawing and stamping compounds including those
spray) to remove the bulk of the soil. containing fillers (pigments).
Part II—Intermediate (alkaline) cleaning. 3.1.4 Machining oils.
Part III—Final electrocleaning, to remove trace solids and 3.1.5 Rust-preventive slushing oils or greases.
especially adherent impurities. 3.1.6 Electroplater’s stop-off residues.
Part IV—Trouble shooting. 3.1.7 Fingerprints.
3.1.8 Dry dirt from storage or dry pickling smut formed
1
during derusting by pickling.
This guide is under the jurisdiction of ASTM Committee B-8 on Metallic and
Inorganic Coatingsand is the direct responsibility of Subcommittee B08.02on
3.1.9 Rust or oxide scales, especially admixed with oil,
Substrate Preparation. including heat-treat scales after oil quenching.
Current edition approved Nov. 10, 1999. Published January 2000. Originally 3.1.10 Phosphate coating with or without lubricant.
published as B 322 – 58 T. Last previous edition B 322 – 85 (1994).

Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.

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3.1.11 Smut resulting from improper vapor degreasing of type of personnel and equipment all influence the selection of
heavily buffed work. cleaners. Obviously, economics must be considered but an
3.1.12 Smut resulting from annealing parts without pre- initial or per pound cost must be balanced against other factors.
cleaning between drawing operations. 5.2 Cleaners do not work effectively indefinitely. The effec-
3.1.13 Heat-treating salts, with or without quenching oils. tive life of a cleaning bath must be estimated and baths
3.2 Consideration should be given to control of the soil. For discarded when exhausted. Bath life is influenced by some of
example, efforts should be made to avoid overbuffing, leaving the factors mentioned above as well as by the volume of work
excessive compound on the work, or aging of the compound on processed. The concentration of the cleaner should be con-
the part before cleaning. Substitution of liquid for solid buffing trolled by analysis at regular intervals.
compound, if work permits, often gives easier cleaning, if
properly applied, but may require use of a different type of 6. Rinses
cleaner. Drawing compounds with polymerizing oils or white 6.1 Water hardness, acidity or alkalinity, and impurities are
lead pigment are to be avoided because of difficulty in important factors in rinsing (1).2 Distilled or demineralized
cleaning. Additives for lubricating and sulfurized cutting oils water is preferred where impurities in rinse water must be kept
are chosen for their ability to adhebe tenaciously and are to a minimum. Boiler condensate may also be used advanta-
difficult to remove. Prolonged storage or drying of emulsion geously. If the plant conditions water for acidity or alkalinity
drawing compounds after metal working should be avoided so care must be taken to be sure the solids content is not too high
that slimy water-in-oil emulsions do not form. In-process (Note 1). Impurities derived from processing cannot be ig-
cleaning or even a hot-water flush before storage is helpful. nored; that is, rinse waters must be changed frequently or
Emulsion machining lubricants (soluble oils) should be used in overflowed continuously (Note 2). Counterflowing rinses are a
place of sulfurized cutting oils if operations permit. Lower- distinct advantage in obtaining good rinsing with economical
viscosity machining and rust-preventive oils are more easily use of water.
removed. Stop-off materials, when used, should be applied
NOTE 1—Boiler waters which contain cationic corrosion inhibitors may
carefully in order to avoid contaminating significant surfaces. be quite detrimental to the plating process.
The use of clean gloves should be mandatory after buffing or NOTE 2—Floating oil on water can cause poor adhesion.
polishing to avoid fingerprints on the work. Airborne contami-
nants can be avoided by using covers over stored work. It is 7. Equipment
desirable to perform a cleaning operation as soon as possible 7.1 It is important to provide enough room in the plant for
after metal forming, polishing, or buffing to reduce the de- an adequate cleaning cycle. A discussion of equipment is
mands on subsequent cleaning operations, because many soils beyond the scope of this practice (2, 3).
are more easily removed when fresh.
8. Criteria of Cleanliness
4. Metal
8.1 This subject has been treated exhaustively in the litera-
4.1 The properties of the metal and the method of fabrica- ture (4). The atomizer test is the most sensitive one, but the
tion and handling of parts play a role in cleaning. The softness water-break test is most commonly used. This involves visual
and surface finish of the metal are factors in selecting handling observation after a final rinse in clear, cool water. A continuous
methods. The chemical activity of the metal is an important and sheet of water on the part usually indicates a clean surface.
determining factor in cleaner selection. Aluminum requires (Certain precious-metal surfaces, such as gold, may exhibit
care to avoid overetching in alkaline cleaners; both aluminum water break, even though clean.) Some experience is necessary
and zinc are sensitive to pitting attack, zinc and brass to to judge the appearance of a break in the film of water. A
tarnishing. Zinc die castings have surfaces that require special specific drainage time, about 30 s, should be used before
care because of sensitivity to attack by cleaning solutions. If observation.
possible, design of parts should avoid small indentations that 8.2 A dip in clean, dilute acid and reexamination are
tend to trap solid particles or buffing compositions. With die desirable to avoid false water-film continuity due to adsorbed
castings, care must be exercised to avoid cutting through the soaps. Other methods, including electroplating and testing of
surface by excessive buffing. The subsurface is usually more the electroplate, should be used occasionally to confirm visual
sensitive than the“ skin” of the casting. Some surface defects examination. (One procedure involves scrubbing with pumice
may not show up until cleaning and electroplating cycles are and then comparing the surface produced by this method with
completed. that produced under production conditions.)
5. Cleaner PART I—PRECLEANING
5.1 It is essential that proper cleaners and operational
conditions be selected. Attention should be given to proper 9. Purpose
procurement since, even in the same category, not all cleaners 9.1 Precleaning is designed to remove a large excess of soil,
are equally effective. A cleaner may be very effective for one especially deposits of buffing compound or grease. It is also
group of soils, yet poor for other soils. This is true of
electrocleaners as well as soak or spray cleaners. Soil, type of
water, available time, rinsing facilities, type of metal, heating, 2
The boldface numbers in parentheses refer to the reports and papers appearing
and agitation available, facilities for disposal of cleaner, and in the list of references at the end of this practice.

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useful in reducing the viscosity of waxes and heavy oils, to 10.4 Emulsion Cleaners—Oils and high-boiling hydrocar-
enable later cleaning stages to be more effective, or to surround bons such as kerosene have the ability to dissolve most greases,
fingerprints and dry dust with an oily matrix to facilitate particularly at high temperatures. The addition of emulsifiers,
removal by alkaline cleaners. soaps, and wetting agents enhances the penetrating power of
the organic solvent and permits removal of the latter and
10. Types associated soil by power flushing. Further, intimate contact of
10.1 Cold solvent, vapor degreasing, emulsifiable solvent, the metal surface with the aqueous phase permits removal of
solvent emulsion spray, invert-type emulsion cleaners, or hot materials not soluble in the hydrocarbon phase.
alkaline spray with or without solvent emulsion can be used 10.4.1 The principle of emulsion cleaning can be applied in
(5). a variety of ways including the use of straight emulsifiable
10.2 Cold Solvent (6)—Mineral spirits; trichloroethylene; solvents, unstable emulsions (diphase cleaners), invert-type
perchloroethylene; 1,1,1,-trichloroethane (methylchloroform); emulsion cleaners, and stable emulsions. Additions of rust
methylene chloride; or trichlorotrifluoroethane can be used for inhibitors or of alkali cleaners can be made to the water phase.
cold cleaning. Combining these with hand brushing is excellent Since agitation is important to good cleaning, the power-spray
but does not lend itself to production conditions. On the other cleaners find wide applications.
hand, simple dipping in solvent is frequently ineffective. The 10.4.2 Emulsion cleaners are used at temperatures up to
chlorinated solvents are very effective for many soils, but not 82°C. The higher temperatures remove soils more quickly and
as effective in removing soap-based or other solvent-insoluble effectively, but caution must be used with cleaners containing
soils. Before electroplating, cold cleaning with solvents must organics of low flash point. Some cleaners containing chlori-
be followed by additional cleaning such as alkaline cleaning to nated solvents are used above the flash point of some of the
remove slight oily residues. components since the chlorinated portion will volatilize to
10.3 Vapor Degreasing (7)—Trichloroethylene and, to a extinguish flashes.
lesser extent, perchloroethylene, trichlorotrifluoroethane, and 10.5 Biological Cleaners (14)—Highly emulsifying soak
methylene chloride are used for vapor degreasing. In vapor cleaners are combined with living microorganisms to permit
degreasing, the work is usually sprayed with clean solvent or the removed oils, greases, and other complex organic com-
given a thorough immersion in boiling or warm solvent for pounds to undergo a natural process known as bioremediation.
mechanical removal of tenacious soil or solids. This is fol- Living microbes break down organic compounds, such as oil
lowed by immersion in cold solvent to cool the parts. Then and grease into carbon dioxide and water and the cleaners, if
follows exposure to condensation of hot, clean solvent vapors properly maintained, may run for years without changing the
on the work. This final step also removes any last traces of oil bath at all. Since the cleaning fluid is kept free from contami-
and grease and dries the part. For removal of caked-on oils and nants, the such systems allow more effective cleaning for a
compounds, a predip in cool solvent can be used to wet and greater length of time.
loosen the soil before the degreasing operation. 10.5.1 In order to maintain a healthy biosystem, operating
10.3.1 Vapor degreasing can be used to clean all types of conditions are critical. Typically, optimum pH range for these
metal, including steel, steel alloys, light metal alloys, special types of cleaning systems is 8.5 to 9.5. Too high a pH will
bronze, nonferrous metals, nickel, and titanium. This method result in lowering of the bacteria action, and oil will be
simplifies the cleaning of parts containing several metals built-up. Too low a pH will render the bacteria too active
because it cleans by solvent action instead of chemical action; resulting in consumption of the wetter and other organics
there is no danger of over-cleaning or under-cleaning because necessary for proper cleaning. Temperature also is a critical
of any difference in chemical activity of the metals present. operating parameter. Optimum metabolism of oil and grease is
Because of the rapid penetrating action of the solvent and achieved around 40 – 50°C.
solvent vapor, this method is effective in cleaning parts 10.5.2 Air agitation is critical to maintaining an oxygenated
containing recesses, blind holes, perforations, crevices, and environment to maintain sufficient biological activity and only
welded seams. Where the soils are present on surfaces that are aerobic bacteria. Without air during operation, anerobic bacte-
not readily accessible, the process is sometimes supplemented ria are produced and the cleaner will take on a noticeable,
by ultrasonic cleaning in the solvent rinse chamber. unpleasant odor. Air sparging also improves overall cleaning
10.3.2 Vapor degreasing is effective on solvent-soluble soils efficiency by promoting transfer of oil and grease particles
and chemically active lubricants. Insoluble soils (buffing grits, from part surface into the cleaning solution. In order for
metal chips and dust, etc.) are flushed away as the soluble soils bioremediation to proceed, particles must be detached from the
(greases and oils) dissolve in the solvent. It is not effective on part surface.
metallic salts, scale, carbon deposits, many inorganic soldering
or welding fluxes, and fingerprints unaccompanied by oil or 11. Precautions
grease. This process is frequently competitive in cost with wet 11.1 The use of solvents and emulsions of diphase cleaners
cleaning methods. Its lower equipment, floor space, and heat requires special attention to safety hazards. Petroleum and
requirements offset the higher cost of solvent. aromatic solvents of low flash point, for example less the 55°C,
10.3.3 For some applications (steel stampings, buffed zinc- must be used with caution. Underwriters Laboratories-
base die castings, etc.), the degreased work can go directly to approved containers and adequate ventilation should be pro-
mild electrolytic cleaning and subsequent electroplating with- vided to avoid the accumulation of fumes in explosive concen-
out the need for an intermediate alkaline cleaning step. trations. Diluted emulsion cleaners usually have flash points

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above 70°C and emulsifiable solvents of high flash point are effectively removed and contamination of the electrocleaning
now available. bath is lessened. The specific applications will not be given in
11.2 Trichloroethylene and perchloroethylene are nonflam- detail here (5, 6, 7). Manufacturers of degreasing solvent or
mable under the conditions of the vapor degreasing process and equipment should be consulted for details.
are among the least toxic of the chlorinated hydrocarbons; up
to 100 ppm of either is tolerable in the working atmosphere for 13. Types
a normal 8-h working day. Trichlorotrifluroethane (1000 ppm 13.1 Soak alkaline cleaning is carried out at 30 to 120 g/L of
tolerable limit) is also used. With proper equipment design and alkaline cleaner at temperatures of 82°C to boiling, for periods
operation, solvent vapors in the working area are easily of 3 to 15 min. If used ultrasonically, temperatures may be
maintained well below recommended safe limits. Degreaser 70°C to boiling. The cleaners usually contain surface-active,
tanks should preferably be cleaned and maintained from soap-like materials which foam if agitated vigorously.
outside the tank. Entry into a tank should be made only after all 13.2 Spray alkaline cleaning is usually carried out at 4.0 to
solvent and vapors have been removed and then only with an 15 g/L at temperatures of 50 to 82°C for 1 to 3 min with spray
observer on the outside. Proper ventilation cannot be over- pressures of 69 to 345 kPa (10 to 50 psi). Foaming may be a
stressed because workmen will often discard a recommended problem, unless the cleaner is properly designed.
gas mask. For cold-solvent operations, adequate ventilation 13.2.1 Foam is also a major problem because of accumula-
must be provided in the work area. tion of soaps in the cleaner from the action of the alkali on
11.3 Because soils accumulate in solvents, the solvents must some organic soils and drag-in of wetters from precleaners. For
be discarded or purified by distillation. In vapor degreasing this reason, it frequently is desirable to use low concentrations
equipment, the solvent is recovered by distillation and the soil of cleaner, for example, 4.0 g/L, and to discard the solution
discarded. The use of automatic auxiliary stills in conjunction often, even though cleaning is adequate. For the same reason,
with the degreaser allows continuous cleaning operation and it is sometimes necessary to operate at lower pressures even
solvent recovery. though higher pressures give better cleaning.
11.4 Emulsifiable solvents must be discarded occasionally, 13.3 Barrel alkaline cleaning is usually carried out at 7.5 to
although frequently most of the soil is flushed off in the rinse. 45 g/L. Temperatures are usually lower than for soak cleaning
Emulsion cleaners represent a particular problem of bath because of mechanical factors. Although agitation is better than
contamination because of the lack of adequate analytical in some cleaning, control is frequently not as good.
controls to determine bath life. Because emulsion cleaners
yield a water-shedding surface, the effect on water-break due to 14. Factors Influencing Good Alkaline Cleaning
accumulated oils is difficult to differentiate from that due to the 14.1 Concentration—The optimum concentration of the
solvent. Because of the low cost of diluted emulsion cleaners, cleaning solution should be determined by actual tests because
it is economical to discard these baths at frequent intervals. many factors are involved.
Soap-base emulsion cleaners can cause difficulties where 14.2 Temperature—Best results are obtained near the boil-
acidic soils are introduced; here mixed alkalies and emulsion ing point if other conditions permit. The high temperature
cleaners can also require water conditioning in hard-water reduces the viscosity of the soil. A rolling boil provides
areas to avoid precipitation of hard-water soaps. Good house- agitation. In some cases, cleaner formulation may be such as to
keeping is desirable to avoid bacterial contamination of emul- make lower temperatures optimal.
sion cleaners. Bacteriostats can be included in the formulations 14.3 Time—Alkaline cleaners, operating by the mechanism
of cleaners to prevent the unpleasant odors that result from of lifting the oil film, require a reasonable time to permit the
bacterial action. surface-active materials to act on the surface. This time is
11.5 As indicated in 14.7.8, disposal of emulsion cleaners shortened if agitation is vigorous, temperatures high, and
can present problems. concentration high. Age of solution and contamination retard
cleaning.
PART II—INTERMEDIATE (ALKALINE) CLEANING 14.4 Agitation:
14.4.1 Spray Cleaning (2)—As in emulsion cleaning, much
12. Purpose of the effectiveness of spray cleaners in removal of solids is
12.1 Intermediate alkaline cleaning removes solvent resi- due to the mechanical action of the solution sprayed on the
dues and residual soil which has been softened or conditioned surface. Hence, every effort should be made to obtain efficient
by precleaning. Spray or soak alkaline cleaning also can be impingement at high pressure without pushing the work out of
used as a precleaning stage followed by additional alkaline the spray area (or off the racks). Foaming after soap accumu-
cleaning, if the soil and metal lend themselves to this treatment. lation also limits spray pressure. The action of spray alkaline
This is not so for metals that are sensitive to alkaline cleaning, cleaners depends on detergency as well as mechanical action;
such as zinc, because the time in the alkaline cleaner should be the proper materials and conditions should be used. Spray
minimal. Some electroplaters use the term precleaning for nozzles should not be allowed to clog with solids and vesti-
alkaline cleaning before electrocleaning, especially when sol- bules should be provided at each stage of the machine to avoid
vent cleaning is carried out at a different part of the plant. contamination by overspray. Agitation is very good in spray
12.2 Although industrial practice is limited, vapor degreas- cleaning (if the sprays hit the solid surfaces directly).
ing alone is sometimes used before electrocleaning. Most oils 14.4.2 Soak Cleaning (3)—Suggested methods of agitation
and greases and some buffing and drawing compounds are in soak cleaning are as follows:

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14.4.2.1 Complete withdrawal and reimmersion, especially 14.7.4 Method of Application (4)—There is no universal
at about half the total time allotted in the cleaner, cleaner that can be efficiently applied by all methods of
14.4.2.2 Pumping the solution over the work with proper cleaning. The cleaner should be formulated for its method of
intake and adequate pressure. application. Cooperation of purchaser with vendor in permit-
14.4.2.3 Rapid motion of the work in the cleaner, ting study of equipment, and availability of heating facilities
14.4.2.4 Maintenance of a rolling boil, will minimize problems such as incomplete cleaning, excessive
14.4.2.5 Use of an air line or a mixer, foaming, dry down of cleaning solution before rinsing, etc.
14.4.2.6 Ultrasonic agitation, and 14.7.5 Degree of Cleanliness Required (5)—The degree of
14.4.2.7 Use of an overflow weir assists in separating cleanliness required for the next operation should be deter-
unemulsified oils, grease, and other solids. mined by the purchaser and explained to the vendor. If parts are
to be held over between operations, a light oil or alkaline
NOTE 3—Electrocleaning represents a special method of agitation and
is considered in 15.4. protective film may be advantageous to prevent rusting. Parts
going immediately to electroplating should be free from any
14.5 Age and Degree of Contamination—A long bath life is objectionable films that might prevent adhesion of electrode-
desirable, not only for economy but also to avoid the necessity posits.
for constant supervision. Alkaline cleaners vary in this respect; 14.7.6 Unit Cost—Many factors enter into the cost of a
much depends on the amount of soil present on the work being cleaning operation. Among them are: yearly cost of space
cleaned. Care must be taken to avoid redeposition of the soil as occupied by the equipment, capital costs and amortization of
parts exit from the cleaner. Cleaners should be discarded equipment, utilities (water, heat, power, etc.), maintenance by
periodically because of accumulation of debris, etc. Surface oil laboratory control, make-up, additions, and disposal of spent
should be skimmed frequently, preferably by overflowing into solutions, labor, cost of cleaning compounds, and cost of
a properly designed skim trough. The cleaner should be reprocessing rejects. To obtain true costs per thousand square
buffered to have a high tolerance for acidic soils. Tolerance for feet of work processed all these factors must be included.
soaps, formed by reaction with the soils, can be designed into 14.7.7 Safety—Consideration must be given to the safety of
the cleaner when necessary. operators and equipment and parts being cleaned (see 11.1,
14.6 Rinsing (see Section 6)—Double rinses are desirable to 11.2, 11.3, and Section 16).
reduce the concentration of cleaner in the rinse. A first hot rinse 14.7.8 Disposal of Spent Solutions and Rinse Waters—
gives more efficient cleaner removal, while a second cold rinse Local, state, and Federal regulations must be consulted before
reduces the tendency to rusting and tarnishing during transfer final selection of a cleaning material can be made. Increasing
to the next stage. If rinsing is inadequate, the components of attention to reduction of stream pollution throughout the
the cleaner must be selected to promote easy rinsing. Selection country means that this factor is a more decisive one in
of a free-rinsing cleaner may require some sacrifice in cleaning selection of cleaning materials. Examples of materials that
properties. Rinse tanks should have adequate overflow rate, come under such regulations are: chromates, cyanides, nonbio-
skimming troughs of good design, and proper positioning of degradable detergents, phenolics, spent solvent emulsions, and
the intake water line. phosphates.
14.6.1 Agitation of work in the rinse tank is desirable. Water
must also flow through hot rinses, although a reduced rate is 15. Formulations of Alkaline Cleaners (8)
often desired for economy. Spray rinsing is very effective, 15.1 General—Actual compositions of cleaning materials
especially if coupled with soak rinsing by having a spray of for various metals, soils, methods of application, degree of
clean water hit the work as it exits from the rinse tank. Drying cleanliness required, and other specific conditions are beyond
of the cleaner on the work before rinsing should be avoided by the scope of this document. The fact that individual suppliers of
having fog nozzles after cleaning tanks, if necessary, or by proprietary cleaning materials have hundreds of standard
decreasing transfer time or operating temperatures. With some products available indicates the complexity of this field. In like
cleaners, adequate rinsing is difficult to obtain after the cleaner manner, the recommendations for their application vary
has dried on the work. widely. Some requirements for formulations of cleaning mate-
14.7 Selection of the Cleaner—Important factors to be rials are listed below:
considered are as follows: 15.2 Soak Cleaners:
14.7.1 Soil (see 3.1 and 3.2)—If the soil is rich in soaps, the 15.2.1 Ability to saponify animal and vegetable oils, if
cleaner should be lean in this respect and should have built-in conditions such as paint stripping require it on steel parts.
high soap tolerance. Because of the specific action of the Otherwise, this requirement can be undesirable where sensitive
individual cleaners on certain soils, this is a prime factor in metals are involved, because attack on the metal may occur
cleaner selection. thereby.
14.7.2 Metal (see 4.1)—Special cleaners are designed to 15.2.2 Wetting and emulsifying action supplied by soaps or
avoid harmful effects on zinc, aluminum, and brasses. Iron, synthetic surface agents to wet oily and greasy deposits and,
steel, magnesium, and copper have better tolerance to alkaline with agitation, suspend the deposits in an emulsified state until
cleaners. rinsing is accomplished.
14.7.3 Water—Hard water frequently requires cleaners rich 15.2.3 Deflocculating action or colloidal properties to at-
in water softeners, such as sequestering and chelating agents, tract solid particle soils and suspend them in a free rinsing
largely to prevent difficulties during rinsing. condition, so that redeposition of the soil is prevented.

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15.2.4 Water-softening ability to sequester or chelate cal- 15.4.4 Water-softening ability is required to prevent forma-
cium and magnesium ions by combining with them to form tion of insoluble soaps by combination of hard-water salts with
water soluble nonionic complexes. soaps formed by reaction of soils and alkaline constituents.
Such insoluble soaps adhering to surfaces decompose in
NOTE 4—Use of polyphosphate-type sequestering agents is limited to
temperatures below 80°C, because decomposition into orthophosphates subsequent acid dips and leave objectionable films of fatty
occurs above this temperature. Organic chelating agents are stable to acids on parts to be electroplated. The sequestering polyphos-
above 100°C. Chelating agents also have the ability to form water-soluble phates are used for this purpose where operating temperatures
complexes with di- and trivalent insoluble metallic salts, such as iron do not exceed their decomposition range, about 80°C. The
oxides. Thus, specially compounded soak cleaners can remove rust, heat organic chelating agents are stable and offer another advantage
scale, and iron or zinc phosphate deposits as well as oily or other soils. over the polyphosphates in that they solubilize light oxide films
15.2.5 Buffering action to maintain the optimum pH range, on the metal parts and provide a more active surface for
despite introduction of acidic or alkaline soils. subsequent electroplating.
15.2.6 Proper inhibitors for prevention of attack of sensitive 15.4.5 Buffering action is required in electrocleaners as in
metals. other types to maintain the optimum pH range, despite intro-
15.3 Spray Cleaners: duction of acidic soils.
15.3.1 The short duration of spray washing operations 15.4.6 Inhibition to prevent attack of sensitive metals is
generally precludes necessity for inclusion of saponifying required for the undesirable condition where a single electro-
action. cleaning solution is used as a precleaner and final cleaner. On
15.3.2 Wetting and emulsifying action is incorporated in ferrous alloys no inhibition is required. Where sensitive metals
this type of cleaner, but to a much lesser degree than in soak have been precleaned, a slight attack or oxidation of the
cleaners, to prevent excessive foaming. Special low-foaming surface, when anodically cleaned, is considered beneficial.
surface-active agents are generally used. Otherwise, antifoam- This action, plus subsequent acid dip, before electroplating,
ing ingredients are a part of the formulations. removes disturbed metal surfaces and promotes better adhe-
15.3.3 Deflocculating action, or use of colloidal materials, is sion.
beneficial in suspending solid particle soils. However, unless
properly compounded, they can cause excessive foaming. 16. Precautions (9)
15.3.4 Water softening to prevent formation of insoluble 16.1 Some alkaline cleaners generate considerable heat
calcium scales on heating coils, spray nozzles, etc., is a when dissolved in water. Rate of solution, however, is fre-
necessary requirement of these cleaners. quently very slow in cold water. It is most advantageous to
15.3.5 Because of the large area of work going through have the water at a temperature of about 50°C while the cleaner
spray washing machines and the lower concentrations of is carefully sprinkled in small quantities over the surface of the
cleaner used, buffering action is an essential part of a spray tank, as with a shovel. Others prefer the safer but slower
cleaner, to maintain effective life. process of adding the cleaner directly to the tank of water at
15.3.6 Depending on the type of metal parts being cleaned, room temperature with provision for agitation to avoid caking.
an inhibitor may or may not be required. A caked cleaner dissolves slowly. If alkali gets on the skin, it
15.4 Electrocleaners: should be washed profusely with water and medical attention
15.4.1 High electrical conductivity is essential. Sodium received promptly.
hydroxide alone could impart this property, but it lacks the
detergent action to remove oils, greases, and solid particle PART III—FINAL ELECTROCLEANING
soils. Therefore, other materials must be incorporated with the
sodium hydroxide. 17. Purpose
15.4.2 Wetting and emulsifying action supplied by nonionic 17.1 The objectives of metal cleaning before electroplating
(low-foaming) and some anionic surface-active agents are have been summarized as follows (10):“ In electrodeposition a
required to increase solubility of the nonionics. These must be surface is required which will receive a smooth, adherent metal
in sufficient quantity to wet and emulsify residual oil and deposit, but this is not necessarily an absolutely clean surface.
grease films remaining from precleaning operations. However, In general, an acceptable surface is one on which objectionable
their concentration must be low enough to prevent excessive surface films have been replaced by films more suitable and
foaming caused by the evolution of hydrogen and oxygen at the acceptable for electroplating.”
electrodes. The type of foam produced should be “brittle,” 17.2 Assuming that the metal parts have been precleaned by
rather than tenacious, and short lived, but be able to prevent methods described above, the “objectionable surface films” are
annoying spray from the alkaline solution from escaping into precleaner residues, minor amounts of soils such as oils and
the atmosphere. The organic surface-active agents chosen solid particles not completely removed by previous cleaning
should not be decomposed into tarry residues by heat, high treatments. Thus, the final electrocleaning process is insurance
alkalinity, or oxidation at anodes. They should have a mini- that only films remain that are“ more suitable and acceptable”
mum tendency to “deposit out” on the electrodes. for the electroplating operations.
15.4.3 Deflocculating or colloidal properties are necessary
to suspend solid particle soils removed from the work in a 18. Types of Electrocleaning
free-rinsing condition. Again, these agents should have a 18.1 Electrocleaning is soak cleaning with agitation pro-
minimum tendency to “deposit out” on the electrodes. vided by the upward movement of bubbles of hydrogen or

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oxygen formed by the electrolytic decomposition of water in PART IV—TROUBLE SHOOTING
the solution. Because of this electrolytic action special types of
cleaners are required (see 15.4). 19. General
18.2 Cathodic—Parts negatively charged in the electro- 19.1 Trouble in cleaning may be quite obvious or may be
cleaner tank are cathodically or direct current cleaned. Hydro- very obscure. Electroplating operations generally are complex
gen gas is evolved on the surface. Positively charged ions and and consist of many steps, so that very often it is not obvious
whether trouble is due to cleaning or some other phase of the
colloids are attracted to the cathode.
electroplating operation. It can be accurately stated, however,
18.2.1 Cathodic cleaning provides greater agitation be cause that many electroplating troubles can be traced to faulty
two volumes of hydrogen are evolved on the surface, as cleaning. When trouble occurs and faulty cleaning is suspected,
compared with one volume of oxygen at the anode. In cathodic an initial close observation of the work should be made after
cleaning, little or no tarnish or attach of nonferrous metal each cleaning and rinsing step. Things to look for are water
occurs. breaks (especially after acid dips), excessive darkening or
18.2.2 Cathodic cleaning attracts positively charged metal- etching, smuts, irregularity in appearance, and stains. Good
lic ions, soaps, and other colloidal materials in the solution lighting is required for accurate observation, and also, the
causing them to“ deposit out” as loose smuts on parts being observer should be one who knows from experience how
cleaned. Since hydrogen is evolved on the parts it may correctly cleaned parts should look after each cleaning step.
penetrate and become occluded in hardened steel parts, causing Parts emerging from rinses and acid dips should also be
embrittlement. Cathodic electrocleaning solutions are more examined for evidence of films either being picked up or not
sensitive to chromic acid contamination than anodic electro- being removed.
cleaning solutions. 19.2 Cleaner concentrations and any special standards rec-
18.3 Anodic—Parts positively charged in the electrocleaner ommended by the supplier such as pH also should be deter-
solution are anodically or reverse current cleaned. Oxygen gas mined, along with tank temperatures, the possibility of tanks
is evolved on the surface. Negatively charged ions and colloids being skipped if it is a hand line, the current density in
electrocleaners, polarity, time in tanks, and transfer times.
are attracted to the parts.
These all have a bearing on the proper functioning of cleaners.
18.3.1 A higher degree of cleanliness is obtained owing to If any of these have been changed, they are to be considered a
the“ deplating” action resulting from the positively charged possible source of the trouble.
surface repelling positively charged metallic ions, soils, and 19.3 The nature of the soils being removed must also be
smuts. Oxygen gas does not enter metals as hydrogen does. considered. If buffing or drawing compounds or oils have
Anodic electrocleaning solutions have much more tolerance for changed, the new soils may be more difficult to clean.
chromic acid contamination. Sometimes a change in soils may require a change in cleaners
18.3.2 Less agitation occurs at the anode surface because or a change in the method of cleaning. Likewise, a substantial
only one volume of oxygen gas is evolved from the decompo- increase in the quantity of soil, such as buffing compound,
sition of the water. could cause trouble.
19.4 One good way to establish whether cleaning is the
NOTE 5—Nonferrous metals are tarnished or attacked if anodic cleaning cause of the trouble is to hand scrub a few parts with a bristle
is prolonged in an uninhibited electrocleaning solution. However, this
brush and pumice powder, rinse, and then place them directly
action may be beneficial as discussed in 15.4.6. Alloys of lead, nickel, or
silver and nickel, and silver electroplated surfaces should not be anodi- in the electroplating solution without cleaning or acid dipping.
cally cleaned. Lead alloys are rapidly attacked and nickel and silver If the same trouble is evident on these parts, it can usually be
surfaces become passivated, requiring special activating treatments for concluded that the trouble is in the electroplating baths or
subsequent electrodeposits. elsewhere and not in the preparatory part of the cycle.
18.4 Periodic Reverse (PR) Current Cleaning—A modifi- 20. Detecting Trouble in Specific Cleaning Operations
cation of normal electrocleaning methods is the use of a 20.1 Soak or Hot Still-Tank Cleaning:
number of cycles of periodic reverse current to assist in 20.1.1 Heating—Check the temperature. There should be
removal of soils, instead of a single application of direct or sufficient heating capacity to keep the solution at the proper
reverse current cleaning, or a combination of them. Details of temperature during full production. If steam coils are used,
electrical equipment for production of periodic reverse current check for leaks diluting the solution. Check that the heating
are outlined in a recent book (11). Users of PR cleaning, unlike element is not insulated from the solution by scale or sludge.
PR electroplating, prefer a PR cycle in which the cathodic Check the operation of the thermostat.
(direct-current) time equals the anodic (reverse-current) time. 20.1.2 Agitation Shield and Overflow Dam—The solution
To prevent deposition of loose metallic smuts, the work should should be properly agitated by bringing fresh cleaner solution
be removed from the electrocleaner during the deanodic continuously to the work. The soils should be skimmed from
portion of a cycle. PR cleaning gives improved smut removal, the solution surface over the dam.
accelerates cleaning operations, and provides a more active 20.1.3 Contamination—Heavier production can cause un-
surface for subsequent electroplating (12). PR cleaning im- due soil loading of the cleaner. Check the age of the cleaner.
proves electrolytic removal of rust and scale in alkaline Investigate introduction of any new soils that might cause the
chelating solutions (13). cleaner to become exhausted prematurely.

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20.2 Spray Washing Machines: insulated from the tank. Insulated joints on steam, drain, and
20.2.1 Heating—Check thermostats, scale on heating coils water lines should be provided.
or tubes, and solution temperature. Descale the machine, if 20.4 Rinses—Rinses should be kept clean and overflowing.
necessary, with inhibited hydrochloric acid or a proprietary Some cleaners require warm rinses for maximum efficiency.
descaling chemical to improve heating efficiency. The cleaner supplier’s instructions should be followed. It is
20.2.2 Spray Risers—There should be enough spray risers, poor practice to use a common rinse tank for several purposes,
properly positioned and directed to contact all surfaces. The such as following a soak cleaner, electrocleaner, and an acid
nozzles should be periodically cleaned. dip. Air agitation in rinses is beneficial.
20.2.3 Pumps and Lines—Check on the return side to be
21. Failures Attributable to Cleaning
sure no air is being sucked into the system causing excessive
foaming. NOTE 6—There are a number of other reasons for these failures, not
20.2.4 Baffles—The cleaning and rinsing stages must be associated with cleaning.
properly baffled to prevent one from contaminating or diluting 21.1 Blisters, Peeling, or Poor Adhesion—These defects
the other. may be caused by improper polarity in the electrocleaner,
20.2.5 Contamination—Excessively dirty cleaning solu- overcleaning (current density too high or cleaning time too
tions cannot be expected to function properly. Grease overflow long), no current in the electrocleaner, and oil and grease not
dams must function properly. Production must not be excessive completely removed. In certain circumstances, especially with
before a new cleaner is made up. materials used in the electronic industry, such electroplating
20.3 Electrocleaners: defects may arise from other factors as well.
20.3.1 Current Density—Too high a current density when 21.2 Pitting—Pitting may be due to oil and grease not being
cleaning metals anodically may etch a buffed surface or cause completely removed. If pitting is general and on all parts, the
excessive tarnishing. Too high a current density when electro- trouble is probably in the electroplating tanks.
cleaning cathodically will cause electroplating out of dissolved 21.3 Strains—This is a problem associated with bright-
metals and some colloids as a smut. Too low a current density electroplated work. The most common cause is cleaner drying
(cathodic or anodic) can be the cause of poor cleaning. Check on the work during transfer. It can be eliminated by lowering
the current with tong ammeters if available and calculate the cleaner temperature, decreasing transfer time, installing fog
current density. Good steel electrocleaning requires a minimum nozzles to keep parts wet until they reach rinse tanks, or by
of 5 A/dm2; 8 to 10 is better. Brass and zinc die castings and using cleaners designed to prevent staining of sensitive non-
nickel deposits normally are cleaned at 2 to 4 A/dm2. ferrous metals. It also can be caused by incomplete soil
20.3.2 Bus Bars—Be sure that the bus bars are of ample size removal, particularly tightly adherent oils of a polar type
to carry the current required for a work load (normally 158 almost impossible to remove in alkaline cleaners. Solvent
A/cm2. cross section of copper bar). Be sure that the bus bars degreasing or emulsifiable solvent predips may be required.
are clean to ensure good contact. 21.4 Roughness—This is caused by failure to remove smut
20.3.3 Polarity—Be sure that the polarity is proper for the or other solid particles. Sometimes this can be traced back to
job. Cathodic cleaning should seldom be used as a final vapor degreasing which removes the oil but not the solid
electrocleaning step because of the danger of “depositing out” particles. If this is a cause, a high-pressure solvent spray will
dissolved metals. There are exceptions to this rule, as in often help. Roughness also may be caused by incomplete
electrocleaning lead, magnesium, nickel, silver, and some rinsing of alkaline soak or electrocleaners due to excessive
stainless steels. If doubt exists as to polarity, check with a water hardness or an exhausted cleaner bath. Magnetically
voltmeter, or trace back the conductors to the current source. charged particles can cause roughness on electroplated steel
20.3.4 Insulation—Be sure that the tank is insulated from parts.
the floor, and that the work, electrode rods, and electrodes are

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REFERENCES

(1) Kushner, J. B., Plating, Vol 38, 1951, pp. 933–935. (8) “Heat Treating, Cleaning and Finishing,” Metals Handbook, Vol 2, 8th
(2) Lux, G. A., and Linford, H. B., Electroplating Engineering Handbook, ed., pp. 320, 616, and 640.
Graham, A. K., Editor, 2nd ed., Reinhold Publishing Co., New York, (9) Spring, S., Metal Cleaning, Reinhold Publishing Co., New York, NY,
NY, 1962, pp. 153–176. 1963, pp. 202–207.
(3) Spring, S., Metal Cleaning, Reinhold Publishing Co., New York, NY,
1963. (10) Lyons, E. H., Transactions, Electrochemical Society, Vol 88, 1945, p.
(4) Linford, H. B., and Saubestre, E. B., Plating, Vol 37, 1950, p. 1265: 281.
Linford, H. B., and Saubestre, E. B., in AES Research Report, Serial (11) Ceresa, M., Electroplating Engineering Handbook, Graham, A. K.,
No. 18, “Cleaning and Preparation of Metals for Electroplating,” Editor, 2nd ed., Reinhold Publishing Co., New York, NY, 1962, pp.
American Electroplaters’ Society, Newark, NJ. 689–704.
(5) Baker, M. E., and Hetrick, G. H., Electroplating Engineering Hand- (12) Spring, S., Metal Cleaning, Reinhold Publishing Co., New York, NY,
book, Graham, A. K., Editor, 2nd ed., Reinhold Publishing Co., 1962, 1963, p. 140.
pp. 126–153.
(13) U.S. Patent 2,915,444, Dec. 1, 1959.
(6) ASTM Committee D-26 Cold Cleaning with Halogenated Solvents,
ASTM STP 403, ASTM, Philadelphia, PA 19103. (14) McNally, T. W., Parts Cleaning, Witter Publishing, Flemington, NJ,
(7) ASTM Committee D-26 Handbook of Vapor Degreasing, ASTM STP p. 20–27.
310, ASTM, Philadelphia, PA 19103.

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