2002 Handbook Cover 9/24/02 11:33 AM Page 1

$
39.95 Third Edition

TH E A Q U E O U S C LE A N I N G H A N D B O O K McL A U G H LI N / Z I S M A N
ince their first use in healthcare and laboratory
settings, aqueous critical cleaners—cleaners
which leave no interfering residues—have
THE
Aqueous
found increasing application in a wide range of
industries as an environmentally benign alter-
native to ozone-depleting compounds and haz-
ardous solvents.
This book distills and presents practical infor-
mation covering the history of such cleaners—what
they are, how they work, and how to make best use

Cleaning
of them in cleaning products and components in
electronics, metalworking, precision manufacturing;
pharmaceutical, food-and-beverage, and chemical
processing; and many other industrial applications.
It is written by a medical doctor, Alan Zisman,
and a director of aqueous-cleaner marketing,
Malcolm McLaughlin, who also has academic

Handbook
training and professional experience in chemistry.
Both are employed by Alconox, Inc., a New York
firm which has been a leading developer and sup-
plier of aqueous cleaners for laboratory, healthcare,
and industrial applications for more than 50 years.

ABOUT THE AUTHORS

Malcolm McLaughlin, M.A. is Vice President,
Marketing, for Alconox, Inc., a leading developer and
manufacturer of critical-cleaning aqueous detergents. He
A GUIDE TO CRITICAL-CLEANING
earned his M.A. in Chemistry from Columbia University. PROCEDURES, TECHNIQUES, AND VALIDATION
Alan Zisman, M.D. is President and Director of Alconox,
Inc. He earned his M.D. at Columbia University’s College
of Physicians and Surgeons.
Malcolm C. McLaughlin, M.A.
Alan S. Zisman, M.D.
and the
Technical Services Staff of Alconox, Inc.
 THE
Aqueous
Cleaning
Handbook
A GUIDE TO CRITICAL-CLEANING
PROCEDURES, TECHNIQUES, AND VALIDATION

Malcolm C. McLaughlin, M.A.

Alan S. Zisman, M.D.
and the
Technical Services Staff of Alconox, Inc.
 © 1998 Alconox, Inc.
© 2000 Alconox, Inc.
Second Printing
© 2002 Alconox, Inc.
Third Printing
Contents
All rights reserved under Pan-American Copyright
FOREWORD v
Conventions.
Published in the United States by
INTRODUCTION ix
AL Technical Communications, LLC,
White Plains, NY CHAPTER ONE
Unauthorized reproduction of this book is forbidden by law. What Is an Aqueous Cleaner? 1
International Standard Book Number CHAPTER TWO
0-9723478-0-1 The Chemistry of Aqueous Cleaning 9
Library of Congress Catalog Card Number
2002110614 CHAPTER THREE
Aqueous-Cleaning Processes 19

CHAPTER FOUR
Special thanks to Peter Levin, Elliot Lebowitz, and
Selecting an Aqueous-Cleaning Detergent 41
Andrew Jacobson of Alconox, Inc.; Jim Morris-Lee, Mary Kane, Steve Smith
and Mea Andreasen of The Morris-Lee Group; without whose tireless
(but now at least not thankless) help this book would not have been possible. CHAPTER FIVE
Testing and Selecting a Detergent and Cleaning System 51

CHAPTER SIX
Industrial Cleaning Applications 65

CHAPTER SEVEN
Standard Operating Procedures 97

ii iii
CHAPTER EIGHT
Cleaning Validation 119

CHAPTER NINE
Wastewater Treatment and Cleaner Recycling 129

CHAPTER TEN
Measuring Cleanliness 141

CHAPTER ELEVEN
Environmental Health and Safety Considerations 155 Foreword
APPENDIX
I Clean Air Act Amendments 162
Most cleaning practitioners are familiar with the story: the
scientists who developed chlorofluorocarbons (CFCs), first as
II Cleaner Types from Alconox, Inc. 163 refrigerants and then as solvents, had struck upon what they
IIIDetergent Selection Guide 164 thought were safe, inert materials. CFCs would replace petro-
leum-based chemicals known for their health hazards. CFCs
IV Glossary of Essential Terms 165 were relatively inexpensive, readily available and most impor-
V Application Case Histories 171 tantly, they worked.
Optical Substrate 171 What the researchers did not know was the impact these
chlorine-containing substances would have on the ozone layer:
Metal Valves 172 that portion of the atmosphere responsible for shielding the
Pharmaceutical Equipment 173 earth from some of the solar system’s most harmful ultraviolet
Glass 174 (UV) rays.
Chlorine (Cl) atoms participate in the destruction of ozone
Filter Membranes 175 (O3) as they randomly make their way into the upper atmos-
Wine Tasting Glasses 176 phere. The reaction is catalytic with the potential for one (1) Cl
Laboratory Pipets 177 atom to destroy thousands of O3 molecules. The introduction
of hydrochlorofluorocarbons (HCFCs) as secondary replace-
VI Index 179 ment chemicals reduced but did not eliminate this danger.
CFCs and HCFCs also increase global warming by interfer-
For every book printed, Alconox, Inc. will donate one dollar to ing with the atmosphere’s natural ability to radiate heat away
American Forests to support forestry conservation and tree-planting from the planet. This exacerbates the Greenhouse Effect most
projects. American Forests has been promoting protection and sus- noticeably impacted by fossil fuel burning.
tainable management of forest ecosystems since 1875. For informa- The international Montreal Protocol treaty and the U.S.
tion, contact Alconox, Inc., 30 Glenn Street, White Plains, NY 10603,
Clean Air Act Amendments govern the usage and production
USA, 914-948-4040, fax 914-948-4088, cleaning@alconox.com,
www.alconox.com. of most of these compounds, including VOC (volatile organic

iv The Aqueous Cleaning Handbook Foreword v

compound) emitters. The U.S. Environmental Protection
Agency’s (EPA) Significant New Alternatives Policy (SNAP)
identifies acceptable substitutes. These laws purposefully dev-
astated organic and chlorinated solvent markets while foster-
ing research and development. Hundreds of companies spe-
cializing in surface preparation, cleaning, rinsing, drying and
inspection owe their economic feasibility to regulatory drivers.
In addition, the U.S. EPA’s Toxic Release Inventory (TRI)
provides a powerful tracking tool for looking at the places and
the reasons hazardous chemicals are used. This transpired
against a back drop of Right-to-Know legislation and chemical
accidents culminating, in no small measure, with the incep-
tion of Material Safety Data Sheets (MSDSs). The occurrence
of the words “test data unavailable” or “unknown” on many of
these documents helped set the stage for other environmental
initiatives.
Initiatives in northern Europe have begun to reflect the
precautionary principle. This is the EH&S equivalent to the
Hippocratic medical oath, “First do no harm.” The translation:
sell no product whose environmental, health and safety con-
cerns have not yet been elucidated.
The principle represents a radical departure from conven-
tional thinking that may be lost on those not directly involved
in the chemical industry Thousands of new chemicals enter
the market each year while little is known about the vast
majority of existing chemicals. This would no longer be toler-
ated under a system that demands thorough environmental
and health information before exposure (as opposed to after a
potential, unknown disaster). Chemical manufacturers would
have stronger stewardship responsibilities. Products would
take longer to reach the marketplace. And once a substance
was deemed safe, who would be liable for any errors that are
sure to occur? It remains to be seen whether American society,
steeped in litigation, can rise to the occasion.
Testing parameters other than those based on the cancer
paradigm need to be determined. The study of chemicals’
effects at low concentrations, should be expanded (negative
impacts from low-dose exposures include hormone mimickers
and endocrine disrupters). The effects of chemical mixtures,
individually thought to be benign, bear more investigation.
vi The Aqueous Cleaning Handbook
Methods of extrapolating test data as well as gender and age
differentials require review.
Other problems remain. Most government policies focus
on chemical handling and use. They do not necessarily take
into account a chemical’s life cycle or environmental fate. Nor
do they fully consider the drain that chemical manufacture
can place on natural resources and raw materials. Risks may
simply be shifting from the site of usage to the chemical’s pro-
duction plant (or power plant) rather than real progress being
made. This is especially worrisome in light of environmental
justice issues.
It is no wonder, then, that many industries are rediscover-
ing water (H2O) as the ideal cleaning medium, the only uni-
versal solvent truly non-toxic to both humans and the environ-
ment. Like the CFC and HCFC designers, today’s formulators
will undoubtedly push aqueous (i.e., water-based) cleaners to
the scientific limits of the day. This is no time for intellectual
arrogance. Chemical exposures effect workers, consumers and
communities. Early partnering with stakeholders may amelio-
rate the mistakes historically associated with the discovery
process.
The constituents and mechanisms of aqueous cleaners
must be understood. Surfactants and emulsifiers, alkaline
builders and the dependence on water and energy (increasing-
ly precious resources in an over-populated world), all matter
to the concerned scientist. One suspects that not all aqueous
cleaners are created equal.
There are challenging opportunities for advancement. It is
possible to envision the day when manufacturers will no
longer be forced to use hazardous materials for surface clean-
ing in the production of quality goods and services.
Furthermore, toxic-free analytical techniques for surface eval-
uation will be invented that are superior to those now in use.
Based on the cornerstones of pollution prevention and
cleaner production,* pursuit of this vision minimizes or elimi-
nates environmental impacts and health and safety risks
linked to many industrial cleaning applications. These objec-
tives support a more sustainable business plan, leading to bet-
ter job security and overall quality of life.
Alconox, Inc. deserves much credit for its self-imposed
Foreword vii
mission to educate the public about aqueous cleaning.
Readers, prepare to learn well from this Handbook.

— Carole LeBlanc
Toxics Use Reduction Institute
University of Massachusetts • Lowell

Introduction
Today , the terms precision or critical cleaning include any
cleaning process where residue can cause a failure in the func-
tion of the surface being cleaned. In general industry this
includes electronic component cleaning and surface prepara-
tion of metals prior to coating or bonding. It can also include
cleaning applications in industries such as chemicals, food
and beverage, pharmaceuticals, and cosmetics where solids
and liquids come into contact with plastic, glass, and metal
piping and processing equipment.
Current practice for critical cleaning includes the use of
volatile solvents, corrosive chemicals, and aqueous detergents.
In today’s hazard-sensitive workplace, however, many compa-
nies are closely examining their use of volatile-solvent and cor-
rosive-chemical cleaners. In that regard, aqueous cleaning rep-
resents an economical, environmentally benign alternative. In
many cases aqueous cleaning is also the best available technol-
ogy and provides a viable long-term solution to environmental
issues.
It is important that these cleaners not contain high con-
centrations of volatile organic compounds or solvents due to
their air-pollution and ozone-depletion potential. They should
also be formulated to minimize worker hazards yet still deliver
*The term cleaner production refers to safer, greener, and more sustain-
able manufacturing methods and materials and not the production of
critical-cleaning performance in the intended application.
chemical cleaners. This handbook is designed to help laboratory and plant
personnel select aqueous cleaners and systems more wisely

viii The Aqueous Cleaning Handbook Introduction ix

and maximize their cleaning performance. While by no means
CHAPTER ONE
exhaustive, it represents the culmination of more than 50
years experience with aqueous-cleaning technology by the
staff of Alconox, Inc., a leading developer and supplier of
aqueous-cleaning detergents.
In its pages you will find handy, easy-to-read summaries of
what aqueous cleaning is and how it works—its chemistry and
mechanical properties. This handbook also contains critical
information on how to select an aqueous cleaner and make the What Is an
most of the cleaning potential of an aqueous-cleaning system.
To make it easy for you to find important information,
cleaning considerations for each industry are also presented.
Aqueous Cleaner?
If you have any questions that are not included in this
handbook, please feel free to contact our technical services
department at Alconox, Inc. (877-877-2526). In fact, many
An aqueous cleaner is a blend of ingredients designed to
enhance the cleaning ability of water. Typically an aqueous
ideas for new aqueous-cleaning compounds have come from cleaner contains a surface active agent (surfactant) and
such contact, and you’ll find our technical service staff ready builders to help the surfactant. The surfactant acts as a wet-
and willing to help with your questions or concerns. ting agent to allow the cleaning solutions to penetrate into
Whether you have used aqueous cleaners and systems for crevices and around and under soils. The surfactant will usual-
some time or are just now considering switching to aqueous ly also act as an emulsifier to help form emulsions with water-
cleaning, we hope you find this handbook helpful. insoluble oils. The builders usually react with dissolved metal
— Alan S. Zisman, M.D. ions in the water to help stop them from interfering with
Malcolm M. McLaughlin, M.A. cleaning. (Chapter Two of this handbook provides a thorough
Alconox, Inc. discussion of these ingredients.)

HISTORY OF CLEANING
Surface cleaning or degreasing can be defined as the removal
of contamination or unwanted material from a surface and the
need to remove soils—defined as any extraneous or unwanted
material deposited on, or attached to a substrate surface—for
esthetic, medicinal, social, and scientific reasons. The history
of cleaning includes the development and use of four types of
cleaning compounds:
• Soaps—which use salts of organic acids with cleaning
properties such as sodium stearate in hand bar soap that
make a surface active agent with wetting and emulsifying
properties.
• Solvents—which use solvency to remove soils by dissolving
them with the solvent to form a homogeneous mixture.

x The Aqueous Cleaning Handbook What Is An Aqueous Cleaner? 1

 • Synthetic solvents—which use manmade hydrocarbon-
based compounds such as CFCs, HCFCs, and PFCs.
• Aqueous cleaners—which use blends of detergent com-
pounds with surface active agents together with other
cleaning chemicals that use detergency to lift soil from a
surface by displacing it with surface active materials that
have a greater affinity for the surface than for the soil.
Soaps—A name stemming from the soapberry, the common
name for about 13 species of deciduous or evergreen trees in
the soapberry family whose fruit contains a soapy substance
called saponin—a natural cleansing agent produced by the
reaction of an alkali, typically sodium hydroxide (NaOH) and
animal fat or vegetable oil. Its use dates at least from the third
millennium BC. (In fact, clay tablets in Mesopotamia con-
tained a recipe for soap that included potash—potassium car-
bonate—and oil.)
The second-century writings of the Greek physician,
Galen, referenced soap as a cleansing, medicinal product that
helped to cure skin ailments. Later, the ancient Romans
shared their knowledge of soap formulation (sapo, the Latin
word for soap is still used to describe the saponifiers often
added to today’s synthetic detergents) and by the Middle Ages
commercial soapmaking centers were established in such
European countries as France and Spain as well as in
England. Manufacturing methods were crude, however, until
discoveries by Nicholas LeBlanc in the 1800s and a century
later by Michel Chevreul made it possible to make predictable
soap formulations.
Solvents—To understand solvents and their strengths and lia-
bilities as cleaning materials, it’s important to understand “sol-
vency”—the ability to dissolve. A solvent is usually a liquid
substance that is capable of forming a physical, homogeneous
solution. Some materials are soluble in certain other materials
in all proportions, while others are soluble only up to a specif-
ic percentage and any excess precipitates out of the solution.
Another important aspect of a solvent is its volatility,
which is highly related to its boiling point. Solvents that have
reasonably low boiling points are more volatile and can be
2 The Aqueous Cleaning Handbook
more readily removed from a reaction mixture by distillation
or evaporation. In cleaning substrates, the most common
application for industrial solvents is to put dirty solid matter
(parts, products, etc.) into the solvent where foreign matter on
the surface is dissolved into the solvent. The substrate is then
removed from the solvent-dilute-foreign-matter mixture which
evaporates and deposits a relatively much smaller amount of
foreign matter left over from the dilute mixture—leaving a
proportionally clean substrate.
The principle of ‘like dissolves like’ was discovered early in
human history by simple observation. In this trial-and-error
process some terpenes, natural organic compounds occurring
in the essential oils and oleoresins of plants (lemon, orange)
and conifers (balsam, pine), were found to have solvating pow-
ers. It is very important to match the solvent character of your
soil or foreign matter to the type of solvent with which you are
cleaning. A given solvent will be “like” some soils and “unlike”
other soils where it will not be able to dissolve and clean as
well as a solvent with like properties.
Synthetic Solvents—Nonaqueous solvent cleaners include
chlorocarbons, chlorofluorocarbons (CFCs), and hydrochloro-
fluorocarbons (HCFCs). Chlorocarbons are carbon-chlorine
based solvents. Halocarbons are halogen-carbon compounds
(chlorine, fluorine, bromine, and iodine).
The most common examples used in cleaning are carbon
tetrachloride, trichlorocarbon (TCA, “trike,” or methylchoro-
form), and perchloroethylene (PCE, or “Perc”). Chlorofluoro-
carbons (CFCs) are carbon, fluorine, and chlorine based sol-
vents. The most common example used in cleaning is CFC-
113. Hydrofluorochlorocarbons (HCFCs) are modified CFCs
with the addition of hydrogen. The HCFCs were developed as
less hazardous replacements for CFCs.
The chlorocarbons have good cleaning properties but
unfortunately have toxic vapors, usually with a narcotic effect.
The vapors also contribute to smog formation. Chlorocarbons
are volatile organic compounds (VOCs).
The chlorofluorocarbons (CFCs) are less toxic than chloro-
carbons, but unfortunately their vapors contribute to ozone
depletion in the atmosphere which can also contribute to glob-
What Is An Aqueous Cleaner? 3
al warming. The CFCs are ozone depleting substances (ODS),
they have ozone depleting potential (ODP) and they have glob-
al warming potential (GWP).
The history of halocarbon chemistry played an important
role in the development of solvents and synthetic industrial
solvent cleaners—and was used to eventually foster develop-
ment of aqueous cleaners as a replacement for environmental
reasons. Carbon tetrachloride (“carbon tet”)—an important,
nonflammable solvent for fats and oils, asphalt, rubber, bitu-
mens and gums, initially used as a degreasing and cleaning
agent in the dry-cleaning and textile industries—was first pro-
duced in Germany in 1839 and marketed as a grease remover.
Its vapors, however, are highly toxic. Carbon tetra-chloride is
also a volatile organic compound (VOC). Evaporating into the
atmosphere at ambient conditions, VOCs include almost all
synthetic and plant-derived solvents as well as fuels. The cal-
culation of the amount of VOC in a particular product or
process is important since ozone, the primary component of
smog, is affected by VOC emissions.
In the 1890s Swarts discovered that the carbon-fluorine
bond could be formed with antimony fluoride and the addition
of trace quantities of pentavalent antimony as a fluorine carri-
er to form chlorofluorocarbons (CFCs) from chlorocarbons
such as carbon tetrachloride. Through his work, carbon tetra-
chloride also became known as tetrachloromethane, the chem-
ical precursor of CFCs—and led to the development of the first
commercial refrigeration systems some thirty years later.
During the following 50 years, continuous reactor process-
es were developed to control the degree of fluorination of the
carbon molecule for the manufacture of refrigerator coolants,
some of which exhibited excellent characteristics as a solvent
and cleaning agent.
There are a number of carbon-derived cleaning com-
pounds, including hydrocarbons, halocarbons, chlorofluorcar-
bons (CFCs), hydrochlorofluorocarbons (HCFCs), hydrofluo-
roether, and perfluorocarbons (PFCs). While each has its own
cleaning advantages, they all have built-in environmental lia-
bilities—CFCs, HCFCs and PFCs are believed to contribute to
global warming. Manufacture of ozone-depleting compounds
was phased out after a world meeting among industrial and
4 The Aqueous Cleaning Handbook
developing nations to restrict their use and manufacture. This
agreement known as the Montreal Protocol on Substances that
Deplete the Ozone Layer was signed by 24 countries, including
the U.S., on September 16, 1987. Today, more than 160 coun-
tries have signed the Protocol.
In addition to the above-mentioned compounds, brominat-
ed hydrocarbons, dibromomethane (for example, methylene
bromine), are also used for cleaning, although on a much
smaller scale. In addition to immersion, vapor degreasers are
often employed with these types compounds in industrial
cleaning, but their mechanical action can be viewed as sec-
ondary because of their excellent solvating properties.
In an effort to continue the use of CFC-related compounds,
hydrochlorofluorocarbons (HCFCs) were developed. These are
generally less toxic than chlorocarbons, and have less ozone
depleting potential than the CFCs. Nonetheless, the HCFCs
have sufficient ozone depleting potential and global warming
potential to be of concern to end users.
SEMIAQUEOUS CLEANERS
The acute and chronic toxicological profiles of the aforemen-
tioned organic and first-alternative CFC cleaners, coupled with
the negative environmental impact of second-generation
HCFC substitutes, stimulated the development of new, innova-
tive cleaning techniques and a rebirth of aqueous and semi-
aqueous cleaning.
Semiaqueous cleaning incorporates the principles of aque-
ous and organic cleaners. This is accomplished by combining a
surfactant with a low-volatility hydrocarbon such as a terpene,
in particular limonene and pinene (citrus or pine in origin), to
form a cleaning blend. Terpenes are homocyclic hydrocarbons
and have a characteristic strong odor; turpentine is an illustra-
tive solvent that is a mixture of terpenes. Semiaqueous cleaning
involves cleaning with a solvent or solvent/water mixture fol-
lowed by rinsing with water as in traditional aqueous cleaning.
Unlike traditional vapor degreasing, however, cleaning
with semiaqueous cleaners does not rely on boiling liquids,
nor is it restricted to a constant boiling composition. In its
simplest form, semiaqueous cleaning involves using its organ-
ic components to dissolve soils and its water component to
What Is An Aqueous Cleaner? 5
remove blend-based residues and any other water-soluble soils. Figure 1A
Surfactants are used when the water-solubility of the solvent is
limited or to improve the emulsifying properties of the cleaner. H (∂+) H (∂+) Partial Positive Charge

Dipole Moment
AQUEOUS CLEANERS
The first aqueous cleaners were soaps as discussed earlier.
Detergents, sometimes referred to as synthetic soaps, were
first introduced in the 1930s and were found to perform better
than soaps in hard-water (mineral-laden) applications because
they contained water softeners to effectively treat dissolved
O
(∂-)
Water Molecule (H2O)
Partial Negative Charge

magnesium and calcium ions. The development of complex

phosphates used to soften water following the Second World The electronegativity that attracts electrons toward Oxygen (O) and away from
War increased the cleaning power of these detergents. Hydrogen (H) gives water an electrical polarity or dipole moment
Aqueous cleaners are synthetic detergent cleaning agents
used in a water solution. Water, considered by many to be the
Figure 1B
“universal solvent,” is an important component of aqueous
cleaners because it dissolves many types of soils. Water—
which may be municipal tapwater, or deionized or distilled
H (∂+) H (∂+)
water based on the cleaning application—also functions as a
carrying medium for detergent compounds. But while water is
capable of dissolving many inorganic and some organic conta-
O (∂-)
(∂+) (∂-)
O (∂-)
minants, not all soils dissolve readily in water. For this reason,
aqueous detergent cleaners are complex mixtures specifically H (∂+) H (∂+)
formulated to create greater chemical and mechanical clean-
ing action. Water Dissolved Polar Soil Water
Water is a polar solvent that is good at dissolving a wide
range of polar soils. Water has a unique “V” shaped structure Simplified three body model showing possible stabilized arrangement of polar
with two hydrogen atoms at the top of the “V” and an oxygen soil molecule with water molecules with dipole moments arranged negative to
at the bottom (see figure 1A). One can think of the oxygen as positive
being a large, dense electron rich atom. This gives the entire In addition to having a desirable dipole moment that
water molecule an overall net negative, electron-rich end at helps dissolve other polar soils, water is capable of bonding to
the base of the “V” (d-) and an electron-poor positive end (d+) soils by a mechanism called hydrogen bonding. The ability of
of the molecule towards the hydrogen top of the “V.” This water to undergo hydrogen bonding is relatively unique
directional net-negative charge towards the base of the “V” is among solvents. This additional bond capability gives water
called a dipole moment. Polar molecules such as water have a significant additional ability to dissolve soils as compared with
dipole moment. other solvents.
This dipole moment is important because it allows stable Aqueous cleaners start with water as their basic “solvent”
solutions of other dissolved polar-soil molecules to become and add ingredients that enhance the ability of water to hold
arranged in more thermodynamically stabile alternating posi- soils. (The chemistry of, and cleaning mechanisms for, these
tive and negative ends of molecules (fig. 1B). ingredients are discussed in the next chapter.)

6 The Aqueous Cleaning Handbook What Is An Aqueous Cleaner? 7

 Today, aqueous agents are used in the same wide range of
CHAPTER TWO
industry applications as solvent cleaning systems. Many aque-
ous cleaners now offer comparable or better cleaning perfor-
mance to solvent-cleaning systems without using volatile sol-
vents, or hazardous chemicals and without appreciable ozone-
depletion potential. By switching to appropriate aqueous
cleaning technologies now, it is possible to both eliminate
ozone-depletion potential and eliminate changes which may
be required under volatile organic compound (VOC) restric- The Chemistry of
tions associated with The Clean Air Act Amendments and state
or local VOC restrictions. Aqueous Cleaning
REFERENCES
C. LeBlanc, The Evolution of Cleaning Solvents, Precision Cleaning, May
1997, p. 11–16.
Before reviewing the technologies and processes involved in
aqueous cleaning, it is important to understand how aqueous
D. Noether, Encyclopedic Dictionary of Chemical Technology (VCH cleaning works, and this begins with the cleaner itself.
Publishers, 1993).
Aqueous cleaners are typically composed of surfactants for
F. Swarts, Bull. Acad. R. Belg. 24, 309 (1892).
emulsifying, wetting, and penetrating; builders for neutraliz-
H. Clauser, Materials Handbook, Thirteenth Editor (McGraw-Hill, 1991).
National Center for Manufacturing Sciences, Focus (April, 1993).
ing water hardness interference, chelating of inorganic soils,
United Nations Environment Programme, Report of the Technology & and saponification of natural oils; and additives for corrosion
Economic Assessment Panel (1991). inhibition, anti-redeposition, and rinsing.
L. Manzer, The CFC-Ozone Issue: Progress on the Development of
Alternatives to CFCs, Science, Vol. 249 (6 July 1990). KEY DEFINITIONS OF
Shell Solvents: The VOC Challenge (Houston, TX, SC: 212–94).
Toxics Use Reduction Institute, Surface Cleaning Series Fact Sheet No.
AQUEOUS-CLEANER INGREDIENTS
SC-2. HCFCs and Cleaning (University of Massachusetts, Lowell, MA Surfactant—Short for “surface active agent,” it is an organic
01854-2866, 1996). molecule with a hydrophobic (water-hating/oil-loving) end and
U.S. Federal Register, Vol. 61, No. 173 (Thursday, September 5, 1996). a hydrophilic (water-loving) end. Surfactants are often emulsi-
Toxics Use Reduction Institute, Surface Cleaning Series Fact Sheet NO. fiers, wetting agents, and dispersants (see other definitions).
SC-1, Surface Cleaning (University of Massachusetts, Lowell, MA
01854-2866, 1996).
The most common surfactant is sodium Linear Alkylbenzene
Toxics Use Reduction Institute, Handout, Hands On Cleaning and Sulfonate (called LAS for short). The alkylbenzene portion of
Degreasing Workshop, (University of Massachusetts, Lowell, MA the molecule is the hydrophobic/oleophilic end of this surfac-
01854-2866, 1996). tant and the negatively charged sulfonate molecule is the hy-
U.S. Environmental Protection Agency, Solvent Alternative Guide, (SAGE, drophilic end of the molecule. Surfactants are typically classi-
version 2.1).
fied as anionic, nonionic, and cationic. The class of surfactant
A.S. Davidsohn and B. Milwidsky, Synthetic Detergents, chapter on
Development of the Detergent Industry. determines the class of the cleaner.

Anionic surfactant—This is a surfactant that has a negatively

RESOURCES charged end of the molecule that gives it the hydrophilic part
www.alconox.com
of the molecule. These negatively charged parts of the mole-
www.cleantechcentral.com
www.colin-houston.com cules are usually sulfonates, sulfates, or carboxylates, that are

8 The Aqueous Cleaning Handbook The Chemistry of Aqueous Cleaning 9

usually neutralized by positively charged metal cations such as
sodium or potassium. Examples include sodium alkylbenzene
sulfonates, sodium stearate (a soap), and potassium alcohol
sulfates. Anionic surfactants are ionic and are made up of two
ions—a positively charged usually metal ion and a negatively
charged organic ion.
Nonionic surfactants—These are surfactants that have no
ions. They derive their polarity from having an oxygen-rich
portion of the molecule at one end and a large organic mole-
cule at the other end. The oxygen component is usually
derived from short polymers of ethylene oxide or propylene
oxide. Just as in water chemistry, the oxygen is a dense elec-
tron-rich atom that gives the entire molecule a partial net-neg-
ative charge which makes the whole molecule polar and able
to participate in hydrogen bonding with water (as discussed in
the first chapter). Examples of nonionic surfactants are alco-
hol ethoxylates, nonylphenoxy polyethylenoxy alcohols, and
ethylene oxide/propylene oxide block copolymers.
Cationic surfactants—These are positively charged molecules
usually derived from nitrogen compounds. They are not much
used as cleaning agents in hard-surface cleaners because of
the tendency of the cationic positively charged molecule to be
attracted to hard surfaces (that usually have a net-negative
charge). Many cationic surfactants have bacteriacidal or other
sanitizing properties that are useful in creating disinfectants
that leave a cationic disinfectant film on the surface. Cationic
surfactants are usually incompatible with anionic surfactants,
because they will react with the negatively charged anionic
surfactant to form an insoluble or ineffective compound.
Amphoteric surfactants—Those surfactants that change their
charge with pH. They can be anionic, nonionic, or cationic
depending on pH. Usually, any one amphoteric can be any two
of the three charge states.
Dispersant—This is a cleaner ingredient that helps disperse or
suspend solid particles in solution. Dispersants include water-
soluble surfactants or water-soluble polymers (long-chain
10 The Aqueous Cleaning Handbook
organic molecules) that are electrostatically attracted to par-
ticulates, creating a bridge between the water and the water
insoluble solid particulate (in some cases even repelling the
solid surface to help lift the particles into suspension).
Emulsifiers—These cleaner ingredients help emulsify water-
insoluble oils into solution by helping to create a liquid-liquid
mixture. Surfactants that use their hydrophobic (water-hating
or repelling) or oleophilic (oil-loving) end of their molecule to
mix with water-insoluble oils and their hydrophilic (water-lov-
ing) end to mix with water create a bridge to emulsify water-
insoluble oils into solution. The specific structure of the bridge
is called a micelle that can be thought of as a hollow, oil-filled
round ball with a skin made of surfactants with their
hydrophilic ends facing out in contact with the water solution
and the hydrophobic ends facing in to the oil-filled ball.
Wetting Agents—These are surfactants that lower the surface
tension of water and allow the cleaning solution to wet sur-
faces and penetrate into, under and around soils and surface
crevices. They create a bridge between the water and any
hydrophobic (water-hating or repelling) surface. You can think
of a wetting agent as having one end of the molecule attracted
to the surface while pulling the water solution towards the oth-
erwise water-repelling surface, allowing the water solution to
be in contact with more of the surface that needs to be cleaned.
Builders—These cleaner ingredients react with interfering
calcium, magnesium, or iron ions that may be present in the
water solution. They stop them from reacting with soils and
other detergent ingredients to form water insoluble and diffi-
cult-to-clean calcium, magnesium, or iron salts. These metals
are present to varying degrees in all water, particularly tap
water. Builders are usually alkaline salts, chelating agents,
and/or sequestering agents.
Alkaline salt builders—These are inorganic salts such as sodi-
um carbonate or sodium phosphates. They react with calcium,
magnesium, or iron to form water soluble or water dispersible
compounds that tie up the calcium, magnesium, and iron.
The Chemistry of Aqueous Cleaning 11
Chelating agents—These are negatively charged or oxygen
containing molecules that react with positively charged metal
ions to form a stable complex. They have multiple locations in
the molecule to react with multiple positive charges that may
be present on multivalent metal ions that have more than one
positive charge on them. An example of a chelating agent is
EDTA, ethylene diamine tetraacetic acid. EDTA has four acetic
acid groups giving it a potential for four negatively charged
acetates to bond with up to four positively charged sites in
metal ions with multiple positive charges, such as calcium
which has two (2) positive charges associated with it.
Sequestering agents—These are chelating agents (see above)
that bind particularly tightly with metal ions and sequester or
separate them from reacting with other compounds.
Detergents use both chemical and physical action to clean,
which are affected in turn by temperature, time, type of mechan-
ical action, cleaner concentration, and additives. Mechanical
action is provided by immersion, spray, or ultrasonics.
The detergents’ chemical action saponifies certain oils,
producing water-soluble soap material. The surfactants used
in a cleaning formulation then work to physically reduce the
surface tension of the solution, in the process emulsifying and
lifting soils away from the substrate being cleaned. These sur-
factant molecules can be both free and aggregate forms called
micelles, and their ratio is based on the type of surfactant, its
HOW ALKALINE CLEANERS WORK
12 The Aqueous Cleaning Handbook
concentration, and the temperature of the cleaning formula-
tion. The surfactant lifts oils off the metal surfaces to form a
suspended oil-water-surfactant emulsion which is then
removed by rinsing.
Typically, immersion cleaning involves submerging parts in
a bath and providing air agitation, turbulation, and mechani-
cal brushing or ultrasonics to realize desired levels of cleanli-
ness while spray cleaning uses a pressurized wash stream to
create even higher soil-removal rates.
Cleaning is then followed by water rinsing. In most aque-
ous cleaning systems, more water is used in rinsing than in
cleaning. Also, rinse water must be purified by a recycling sys-
tem to a higher level than the detergent solution. Rinse water
also requires different separation equipment, since the rinse
water is the last solution to touch the surface being cleaned.
The chemical and mechanical action involved in aqueous
cleaning is actually a number of processes. These can be
described as:
• Solubilization—a process whereby the solubility of a
substance is increased in a particular medium
• Wetting—to lower surface and interfacial tensions so
that the cleaner penetrates small spaces while getting
under the soil to lift it from the substrate
• Emulsification—creating an oil/water mixture by coat-
ing of oil droplets with surfactant to keep them from
recombining and migrating to the surface of a cleaning
bath (see previous emulsifier discussion)
• Deflocculation—breaking down soil into fine particles
in order prevent agglomeration by dispersing them
through the cleaning medium
• Sequestration—reacting with ions such as calcium,
magnesium, or heavy metals to prevent the formation of
insoluble byproducts (such as soap scum)
• Saponification—alkaline hydrolysis of fat by the reac-
tion of fatty acids with alkalies to form water-soluble
soaps
To encourage such chemical and mechanical cleaning
(unlike organic and chlorinated solvents, aqueous cleaners
may not depend on solvent penetrability for their cleaning effi-
The Chemistry of Aqueous Cleaning 13
ciencies), aqueous cleaners may include a number of the fol-
lowing ingredients, formulated to provide maximum cleaning
effectiveness for specific for various types of substrates and
soils by reducing surface tension, forming emulsions, and sus-
pending insoluble particles for removal in the cleaning bath:
• Surfactants—alkaline surfactants that react with fatty
acids to form soap. They improve cleaning action by
reducing the water’s surface tension which also allows
for greater penetration or wetting of the liquid onto the
part surface. Used to either emulsify a soil from a sub-
strate or increase the surface’s wettability. Substances
with both hydrophilic (water soluble) and lipophilic (oil
soluble) groups that may be cationic, anionic or nonionic
depending on the charge of the hydrophilic end. Anionic
surfactants are generally poor cleaners because of their
negative charge. Cationic or positively-charged surfac-
tants are water soluble and are commonly used in
immersion cleaning. Nonionic surfactants with no
charge are used for surface cleaning when a lower-foam-
ing detergent is required. A class of synthetic com-
pounds, nonionic surfactants are prepared by attaching
ethylene oxide molecules to water-insoluble polymers,
but are usually biodegradable in aqueous cleaners. In
addition to wetting, surfactants can also enhance the
emulsifying and dispersing properties of a cleaner.
• Builders—inorganic salts that provide alkalinity and
buffering capacity common to almost all aqueous clean-
ers (pH may be alkaline >7, neutral ~7, or acidic <7).
Alkalinity may be provided by hydroxides, carbonates,
borates, silicates, phosphates, or zeolites (crystalline
hydrated aluminosilicates). Builders also soften water or
help with saponification or deflocculation.
• Emulsifiers—substances that can form liquid-liquid
mixtures (e.g., oil and grease) that do not dissolve in
water. Emulsifiers are useful for low soil loading, but
their concentration in a detergent limits bath life.
Separation of soil and cleaner may be accomplished by
making the emulsion unstable by lowering the pH and/or
temperature. They are chemically similar to the semi-
aqueous cleaners described below.
14 The Aqueous Cleaning Handbook
• Saponifiers—Alkalies that react with fatty acids in oils
to form soaps. Chemistry may be mineral (sodium or
potassium) or organic-based (such as solutions of
ethanol amines).
• Solvents—Aqueous or organic chemistries designed to
enhance the removal of oily soils by dissolving them
(e.g., glycol ethers, ethylene [Butyl Cellosolve], and
propylene compounds).
• Additives—act primarily as contaminant dispersants,
anti-redeposition agents, brighteners, viscosity modifiers,
antifoaming agents, and corrosion inhibitors or they may
have special detergency on a specific soil type. Examples
include enzymes, amine compounds, and various poly-
mers.
• Sequestering agents—produced as powders or liquids
to combine with calcium, magnesium, and other heavy
metals in hard water. They form molecules in which
these ions are held securely, or sequestered, so that they
can no longer react undesirably with other species in
solution. Polyphosphates and polyacetates are commonly
used.
• Chelating agents—employed to solubilize hard water
salts so that they remain in solution. Produced in both
powdered and liquid forms, they do not degrade or lose
their potency at elevated temperatures, which make them
ideal for aqueous cleaning. However, they can interfere
with the ability of other chemicals to remove emulsified
oils and dissolved metals from solution, which can lead
to waste disposal problems. In addition to EDTA, nitrilo
tri acetate (NTA) is also used.
• Corrosion Inhibiting agents—are often added to aque-
ous cleaners to minimize their effect on metal substrates.
They are used for cleaning at high pH and as rust
inhibitors to prevent the rusting or oxidation of cleaned
parts (or cleaning equipment that is not constructed of
stainless steel).
• Stabilizers—added to extend the shelf life of detergent
ingredients and to maintain the uniformity of detergent
blends. For example, dilute cleaner solutions may have a
tendency to grow microbes. The presence of biocidal
The Chemistry of Aqueous Cleaning 15
 additives in a formulation may be indicative of a formu- to aid in cleaning. Less foam is generally produced with the
lation that is not concentrated (assuming the cleaner is use of a neutral cleaning agent. There are also semiaqueous
not designed as a biocidal cleaner). In contrast, coupling cleaners which form neutral solutions upon dissolving or
agents and hydrotropes that are included in detergent emulsifying in water.
formulations are indicative of highly concentrated for- The first issue in selecting a cleaner on the basis of pH
mulations because these are used to increase the solubili- (there are other factors, as we’ll see in later chapters) is how
ty and costability of various active detergent ingredients. fast it needs to work. Most cleaners are alkaline in nature
• Extenders—fillers which are added to detergent that do since hydrolysis—and the chelation and dispersing of soils—
not improve detergency (and which also tend to increase typically occurs most effectively at alkaline pH levels.
the packaging and handling costs associated with the However, the higher the pH the more corrosive the cleaner:
cleaner itself). For example, water may be added to a
concentrated cleaner, or inert powders may be added to TYPE OF CLEANER pH RANGE SOILS REMOVED
dilute a concentrated powder cleaner. It is occasionally Mineral-acid cleaner 0-2 Heavy scales
necessary to add a small amount of inert powders as
process aids in order to improve the freeflowing charac-
Mild acid 2-5 1/2 Inorganic salts, water, and soluble
teristics of a powdered detergent. However, one needs to
metal complexes
be careful not to purchase a cleaner that is diluted with Neutral 5 1/2 to 8 1/2 Light oils, small particulates
excess, cheap inert powder, since these types of extenders Mild alkaline 8 1/2-11 Oils, particulates, films
do not improve detergency and also increase packaging Alkaline 11-12 1/2 Oils, fats, proteins
and handling costs. Corrosive alkaline 12 1/2-14 Heavy grease/soils

TYPES OF AQUEOUS CLEANERS
It is important to keep in mind that a cleaner’s pH value can
have a direct effect on cleaning effectiveness. Technically
speaking, pH is the “negative log of the hydrogenion concen-
tration.” This means that the higher the pH, the greater the in-
crease in hydroxide concentration and the faster hydrolysis—
the breaking down of a natural fat or oil into a soap—occurs.
Aqueous cleaners are classified according to pH value as
being neutral, acidic, or alkaline on a scale of zero to 14, with
a pH of 7 being neutral. Thus, a pH value of less than seven is
considered acidic, and higher than seven, alkaline.
Each detergent formulation has maximum effectiveness at
a specific pH value. An acidic solution with a pH of 4.5, for
example, would be effective for removing metal oxides or scale
prior to pretreatment or painting. And an alkaline (basic) solu-
tion with a pH of 13.5 could be formulated to remove carbona-
ceous soils, heat scale, rust, oil, and grease. Neutral cleaning
solutions include alcohols and other water-soluble formulas,
and generally contain detergents or other surfactant additives
Alkaline cleaners work best when the soil can be hydro-
lyzed (typically natural oils and fats, fingerprints, natural
greases, some types of food products, and protein residues).
The cleaning process should be enclosed to avoid exposure
hazards. (Workers should use personal protective equipment
with handheld sprays.)
Time, temperature, and agitation also play important roles
in cleaning. But while maximum detergency is achieved at
high temperatures with high agitation over long periods of
time, the substrate must be robust since corrosion is also a
factor.
As a rule of thumb, it is best to use the mildest cleaner
possible.

16 The Aqueous Cleaning Handbook The Chemistry of Aqueous Cleaning 17

REFERENCES CHAPTER THREE
Personal interview, University of Massachusetts at Lowell, Toxics Use
Reduction Institute.
Alkaline Cleaner Recycle Handbook, Membrex, Inc., Fairfield, NJ, 1994, p.
5.
Ibid., pp. 4–5.
Ibid., pp. 3–5.
Closed-Loop Aqueous Cleaning, University of Massachusetts, Toxics Use
Reduction Institute, Lowell, MA, 1995, p. 6.
Ibid, p. 10.
Aqueous-Cleaning
Salinas, M. “Water Works.” Parts Cleaning, Vol. 1, No. 2; July/August,
1997.
Seelig, S.S.”Making Aqueous Systems Work.¸” CleanTech ’97 Proceedings,
Witter Publishing, May, 1997.
Processes
Quitmeyer, J. “All Mixed Up: Qualities of Aqueous Degreasers.” Precision
Cleaning, Vol. 5, No. 9; September, 1997. Before testing aqueous cleaners, it is important to understand
a few basic processes regarding their use. The major variables
Rolchigo, P.M. and Savage, G. “The Fundamentals of Recycling Alkaline
Cleaners Using Ultrafiltration.” CleanTech ’96 Proceedings, Witter in cleaning using aqueous methods include:
Publishing, May, 1996 1. Precleaning handling
Davidson A S & Milwidsky B, “Synthetic Detergents, 7th Ed.” Longman
Scientific and Technical copublisher John Wiley & Sons, New York,
2. Cleaner
1987 3. Agitation
4. Temperature
5. Cleaning time
RESOURCES 6. Rinse used
www.alconox.com 7. Drying method
www.stepan.com
www.pilotchemical.com
8. Postcleaning handling
www.rhodia-ppd.com
The way parts and substrates are handled prior to cleaning
can have a significant impact on their degree of difficulty in
cleaning. Soils can be more difficult to clean if they are:
• Allowed to dry, set up and cross link
• Stored in a dirty environment
• Stored in a humid or corrosive environment.

As a rule, it is important to clean parts as soon as feasible

after they are soiled. In some instances it makes sense to take
parts directly from a manufacturing process and put them into
a soak solution where they may be able to sit for extended
periods of time prior to cleaning.
Alternatively, parts can be placed in protective packaging,
dipped in a protective coating or immerse in oil or grease to
keep them in a state that will not increase the burden on the
cleaning process.

18 The Aqueous Cleaning Handbook Aqueous Cleaning Processes 19

CLEANER
The cleaner or detergent used should be matched to the
desired cleaning method, and the surface and types of soils
being cleaned. For instance, a low-foaming detergent should
be used for spray or machine cleaning, a good anti-redeposi-
tion detergent for soak and ultrasonic cleaning, a high emulsi-
fying and wetting detergent for manual cleaning. The deter-
gent, temperature, and degree of agitation should be strong
enough to remove the soil to the desired level of cleanliness
without harming the substrate being cleaned.
There are some particularly critical aspects to understand
in selecting and using a low- or nonfoaming detergent for
spray or machine washing. It is very important to not have
foam when cleaning in or with a machine that relies on spray-
ing for mechanical agitation.
Foam may build up and spill over from the machine creat-
ing a mess. Foam will also build up on the substrate and inter-
fere with the mechanical cleaning energy of the spray. And
finally, foam may get sucked into recirculation pipes causing
problems with pumps in the machine. Foam is formed by the
presence of agitation at an air/solution interface when a foam-
ing agent is present.
Surfactants are often foaming agents. Most aqueous clean-
ers have surfactants in them. There are three basic types of
aqueous cleaners that are suitable for machine washing: clean-
ers with no surfactant, cleaners with a nonfoaming surfac-
tants, and cleaners with low- or controlled-foam surfactants.
There are important differences among these types of clean-
ers. Remember that foam forms in the presence of an agitated
foaming agent where air is present. Many soils are foaming
agents. In particular, soap formed by saponifiers in electronic
solder flux cleaning is a foaming agent. A surfactant-free
cleaner will not protect against foam formed by soils. You
should only clean nonfoaming soils with surfactant-free clean-
ers. A nonfoaming cleaner usually has a nonionic polymer sur-
factant. These surfactants have a unique property of coming
out of solution at elevated temperatures and forming an oil
slick on top of the solution. This oil slick is a barrier to air
contact which stops foam from forming or being stable. These
cleaners will suppress foam from soils. They only work prop-
20 The Aqueous Cleaning Handbook
erly if the temperature is hot enough. You need to know the
minimum temperature at which to use these cleaners.
Finally, there are controlled foam cleaners that usually
have limited foam suppressing capabilities. The surfactants
themselves do not foam excessively, but they will not be able
to control much foam that results from soils.
It is critical that the detergent be scientifically formulated
to clean effectively and to rinse away without leaving interfer-
ing residues. A scientifically formulated detergent will typical-
ly have appropriate surfactant ingredients and nondepositing
rinse-aids. The surfactant should have sufficient surface ten-
sion lowering properties to assist in proper rinsing. A surface
tension below 35 dynes per centimeter for the cleaning solu-
tion as used is often sufficient for the surfactant to contribute
to good rinsing. Nondepositing rinse-aids can help complete a
formulation to meet the rinsing requirements of critical clean-
ing.
In addition, the detergents should be manufactured with
appropriate quality-control procedures. In many critical-clean-
ing applications it is desirable to choose a detergent that has
lot number tracking and can be supplied with certificates of
analysis from the manufacturer. These certificates document
each lot of detergent to assure consistency and quality control
from lot to lot in order to control for potential cleaning failure
due to inconsistencies in manufacturing or unannounced for-
mulation changes. It is desirable to choose a detergent from a
manufacturer that maintains quality control on their raw
materials and in turn keeps retained samples of each lot of
detergent that is used to be able to respond to concerns about
a particular batch.
The detergent should be widely available and economical
to use (for optimum economy, a concentrated detergent is typ-
ically used at 1:100 to 2:100 dilutions). The detergent concen-
trate should be diluted according to the manufacturer’s in-
structions; typically, warm (about 50°C) or hot (about 60°C)
water is used. Ambient temperature water may be acceptable,
especially for presoaking. For difficult soils, very hot water
should be used (over 65°C), and the recommended detergent
concentration doubled.
Aqueous Cleaning Processes 21
AGITATION
Agitation can be a form of nonagitation (such as soaking), or
performed through manual (cloth, sponge, brush), ultrasonic,
flow-through clean-in-place (for pipes, tanks and tubes), spray
cleaning (a dishwasher, for example), and high-pressure spray
cleaning. In general, the more agitation, the more effective the
cleaning on bulk soils.
Cleaning often can be enhanced by presoaking, particular-
ly if soils are dried or baked onto the part to be cleaned. It is
always desirable, whenever possible, to clean prior to soils
becoming dried or baked onto surfaces.
Different agitation methods are often chosen with (1) time
required and (2) number of parts being cleaned as the major
considerations. If large numbers of parts must be cleaned
quickly, then a fast, high-agitation method such as spray wash-
ing often is used with an aggressive detergent. For smaller
numbers of batch or batch-continuous quantities of parts,
ultrasonic soak cleaning with a milder detergent may be used.
TEMPERATURE
In general, higher-temperature cleaning solutions result in bet-
ter cleaning. In practice, there is typically an optimum temper-
ature for a given combination of cleaning variables. Many
soak, manual, and ultrasonic cleaning methods work best, for
example, at 50˚C to 55˚C. Many spray washing techniques
work best at 60˚C to 70˚C. Waxy or oily soils are more easily
cleaned at somewhat higher temperatures. Particulate soils
tend to be more easily cleaned at slightly lower temperatures.
These are, of course, broad generalizations. It is not always
necessary or practical to clean at the optimum temperature.
You may have both waxy and particulate soils present, or the
part being cleaned may not be able to withstand the optimum
temperature.
CLEANING TIME
In general, the longer the cleaning time, the more thorough
the cleaning. Many cleaning mechanisms such as emulsifying,
dissolving, suspending, and penetrating are time-dependent.
Up to the point where cleaning has been completed, the longer
they’re employed, the more cleaning is accomplished.
22 The Aqueous Cleaning Handbook
Cleaning time can be accelerated by increased agitation,
more aggressive detergents, and by increasing temperature. If
agitation, detergent, or temperature cannot be increased—per-
haps because the substrate is too delicate or the proper equip-
ment is unavailable—then one must be prepared to use longer
cleaning times to achieve the desired cleanliness. While manu-
al cleaning may take minutes, and spray cleaning might even
take seconds, soaking for hours, or even overnight, may be
required to reach similar levels of cleanliness.
There are some instances when long cleaning times may
promote substrate corrosion, weakening, or swelling. The opti-
mum cleaning time should be chosen relative to the specific
substrate, temperature, cleaning method, and detergent.
RINSE USED
With aqueous cleaning, the last thing to come into contact
with the cleaned surface is the rinse water. A thorough rinse
will remove soils which have been cleaned from the surface
and any residue from the detergent itself. Whatever contami-
nants are present in the rinse water to begin with can be pre-
sent after rinsing. Therefore, the more stringent the cleaning
requirement, the greater the need for rinse water purity.
The important consideration is to remove whatever conta-
mination or residues are present to levels that will not inter-
fere with the further use of the parts or equipment.
• Standard critical cleaning. A thorough tap water rinse
followed by a deionized water or distilled water rinse is
usually sufficient. In general, a thorough rinse means
rinsing with at least three times the amount of rinse
water as the cleaning solution used, (for example, a
spray washing cycle of five minutes should be followed
by three rinse cycles of five minutes each in a spray
washing machine).
In soak or ultrasonically agitated rinsing, it is desir-
able to have two counterflow-cascade rinse tanks with
dripping “over the tank” for reduced dragout. Higher lev-
els of cleaning may require the exclusive use of deion-
ized or distilled water and in some cases more than three
times the volume of rinse water.
Aqueous Cleaning Processes 23
 • Electronic component and circuit board cleaning.
Deionized water is preferred rather than tap water or
distilled water because deionized water has less potential
for metallic cation deposition which leave conductive
residues on sensitive electronic components. On metal
parts, the use of deionized rinse water reduces the likeli-
hood of depositing calcium, magnesium, and other
water-spotting salts.
With soak or ultrasonically agitated rinsing, it is
desirable to have two counter-flow cascade rinse tanks
with dripping “over the tank” to reduce dragout. In all
cases, running water or otherwise agitated rinse is better
than a static soak-tank rinse.
Higher levels of cleaning may require the exclusive
use of deionized or distilled water and in some cases
more than three times the volume of rinse water.
For most cleanroom, electronic component, and cir-
cuit board cleaning, deionized water is preferred over
either tap or distilled water because of its lesser potential
for metallic cation deposition on sensitive electronic
components, leaving conductive residues. On metal
parts, the use of deionized rinse water reduces the likeli-
hood of depositing calcium, magnesium, or other water
spotting salts.
DRYING METHOD
Drying can affect residues and corrosion since impurities from
rinse water can be deposited during evaporation. Water, par-
ticularly high-purity rinse water, can be corrosive to metal
substrates during heated and air drying. The use of physical
removal or drying techniques or the addition of corrosion in-
hibitors (with the tolerance of corrosion inhibitor residues) to
the rinse water can help minimize such corrosion.
With aqueous systems, adequately drying any remaining
water from a part is critical to avoid corrosion of metals, par-
ticulates sticking to surfaces, poor paint adhesion, short-cir-
cuiting of electronics, and problems related to cross-contami-
nation in food, beverage, and pharmaceutical processing. This
last step in the manufacturing process is important both to the
end user and detergent supplier since the performance of an
24 The Aqueous Cleaning Handbook
aqueous-cleaner solvent replacement system is evaluated on
the basis of the drying process. Equipment cost and process-
ing speed are also factors when large volumes of ultrapure rin-
sewater are required to remove small amounts of residue.
There are two basic methods for drying substrates in aque-
ous cleaning: physical drying and chemical drying. Physical
drying consists of evaporation, forceful drying, and absorp-
tion, or a combination of these. Chemical drying includes sol-
ubilization (using a water-soluble solvent to dilute the water)
and displacement (using a surfactant-based solvent that is
insoluble in water). While these are usually faster than physi-
cal methods, they are not inherently environmentally safe. In
addition, proper operation must be followed to realize cost
savings and ensure health and safety.
Removing water by evaporation is the oldest and simplest
physical drying process. Convection ovens do just that. Wet
parts are placed into an oven and heat is applied to remove the
water. Two problems are inherent with such drying solutions:
• Convection or microwave ovens are not always applica-
ble due to space and time constraints or lack of automa-
tion.
• Some types of parts are heat sensitive and others may be
too big or too dense, requiring large amounts of energy,
to be efficiently dried by convection oven.
Mechanical systems for physical drying may be classified
by the following types:
• Vacuum drying—similar to convection drying—requires
a negative pressure to be applied. This causes a decrease
in the water’s boiling point in order to “suck” away the
moisture. This method is ideal for removing trapped
water from blind holes and crevices but may also deform
the part. Also, shorter drying times are balanced out by
higher energy requirements. As with evaporation drying,
an important consideration is that any contamination
contained in the water will be left behind on a cleaned
surface. Multiple rinsing chambers with hot ultrapure
water may not be sufficient to remove these residues and
would add significantly to the time and cost involved.
Aqueous Cleaning Processes 25
 • Forced-air, or blow-drying—a relatively old concept for
removing water. A more advanced method is the use of
an “air knife” that forces clean, dry air through a long,
narrow chamber onto the substrate. Parts on a conveyor
system pass under this intense stream of air and the
water is simply blown off. Parts, however, must be
angled just right for water-soluble residues to be
removed and streaking to be avoided. Complex geome-
tries, nestled parts, and high production volumes are
also difficult problems, and noise may also be of con-
cern. Large volumes of clean and dry air are required for
drying to be successful. Automation may be easily
accomplished, but batch processing is more difficult for
this type of drying system.
• Centrifugal drying—uses gravitational forces to remove
water. Large volumes of parts and blind holes are han-
dled easily; however, this approach is difficult to auto-
mate and delicate parts may be damaged.
• Forced or filtered hot gas—combines convection heat-
ing with an air knife and offers the advantages of evapo-
rative and blow-drying actions. In humid situations,
however, moisture can condense on the substrate, result-
ing in wet parts. Forced drying is environmentally safe
and can handle large volumes of work. Air knives dry rel-
atively fast compared to most physical methods of dry-
ing. They can also be economical and allow for automa-
tion.
Forced/filtered gases can be used to effectively dry
parts, particularly in batch process systems where clean-
ing tanks are employed. After a tank is drained it con-
tains wet parts where dry gas (such as dry nitrogen, or
even heated dry nitrogen) is forced through the closed
chamber to dry the parts. This same principal can be
used in a separate drying chamber in which a dry gas is
also used to evaporate the water and sweep any water
vapor away from the parts. Particular attention should
be paid to the quality of the gas being used. Typically, fil-
ters are employed on the incoming gas—with a filter size
appropriate to the size of particulates which must bee
exclude from the surface.
26 The Aqueous Cleaning Handbook
• Absorption—Moisture absorbing materials (corncobs,
drierite) are cheap, simple, environmentally safe, and
reusable for many drying applications. They are usually
tumbled with the cleaned parts to increase contact with
the water. Delicate parts may be damaged during tum-
bling and the drying agents themselves may further cont-
aminate the parts. Also, complex geometries with blind
holes cannot be dried adequately.
The important thing to remember here is that not all dry-
ing processes are applicable in every situation. As with select-
ing an aqueous cleaner, the right drying process must be care-
fully assessed based on the parts being cleaned and manufac-
turing volume.
POSTCLEANING HANDLING
The way in which parts and surfaces are handled after clean-
ing can impact their cleanliness. For this reason it is impor-
tant to consider how parts are handled and stored to ensure
that the purpose of the cleaning process is maintained.
Depending on the environment, it may be advisable to make
provisions for a clean storage place or conditions. It may be
appropriate to determine how long a surface or part will stay
clean while stored to determine if it needs to be re-cleaned
prior to use.
DETERMINING PART DRYNESS
Inspection is probably the most common method for deter-
mining dryness. For most precision cleaners, the observation
of no visual wet spot constitutes a “dry” part. Tapping the
parts on a brown paper towel will immediately indicate if
there is trapped water. If any solvent is present, the wet spot
will disappear very quickly. A more thorough test for measur-
ing remaining water involves using reagents found at any
chemical supply house, solubilizing the water in methanol,
and performing a relatively simple titration.
CLEANING METHODS
There are ten types of mechanical cleaning methods used in
aqueous cleaning and each is employed—sometimes in combi-
Aqueous Cleaning Processes 27
nation—for specific types of substrates, parts, and cleaning
volume factors. They include:
• Manual—Manual cleaning is used to clean small batches
of parts and surfaces. To clean manually, the article to be
cleaned should be wetted either by immersing it in the
detergent solution, or by using a soaking cloth or
sponge. For nonabrasive scouring, undiluted detergent
should be poured onto a wet cloth or sponge for scrub-
bing. A cloth, sponge, brush, or pad can be used for
cleaning. A thorough rinse follows. Protective gloves and
eye protection should be worn if recommended or
required.
• Immersion/Soak—Soaking is used to clean small items
and the insides of larger vessels. It should be used as a
pretreatment to prevent soils from drying onto a part.
Soiled parts can be placed in a soak tank until such time
that they can be washed. Soaking is also effective to
clean or pretreat very difficult, dried-on residues. To
clean by soaking, a detergent recommended for soaking
should be used, and a detergent soak solution made up
according to the directions. The article should be com-
pletely submerged to prevent any deposits or etching at
the air/solution interface. Soils should be soaked until
they are removed; this may take several hours. Some
soils may require additional agitation or wiping in order
to remove them. A thorough rinse follows.
• Clean-in-Place (CIP)—Clean-in-Place is used to clean
pipes, tanks, and filtration systems. Its chief advantage is
that, as its name implies, it assures clean systems with-
out disassembly. It requires, however, good circulation
for effective cleaning.
There are two main clean-in-place methods:
• Circulate clean-in-place—which involves filling a
tank and system with solution and circulating it
through the system.
• Spray clean-in-place—which involves partially fill-
ing the system and circulating the cleaning solution
through spray nozzles.
28 The Aqueous Cleaning Handbook
Of the two methods, spray clean in place uses far less solution
and can be more efficient.
Typically, the cleaning solution is circulated slowly for at
least one-half hour—with several hours required for large sys-
tems. Displace the cleaning solution by pumping in one full
system capacity of water. Then complete rinsing by circulating
and draining at least two times the systems water capacity. For
spray clean-in-place, a low foaming detergent is used, followed
by rinsing and flushing thoroughly.
• Ultrasonic—Ultrasonic cleaning is used for larger num-
bers and repetitive batches of parts. To clean in an ultra-
sonic tank, a solution is made up in a separate container,
the ultrasonic tank filled, and the machine run for sever-
al minutes to degas the solution and allow the heater to
reach the correct temperature. Small articles should be
placed in racks or baskets; irregularly shaped articles
aligned so that the long axis faces the ultrasonic trans-
ducer (usually the bottom); the machine should run 2–10
minutes until parts are clean. A thorough rinse follows.
• Machine—Machine washing is used for cleaning large
quantities of components. The machine’s directions
should be consulted for details on proper use. In general,
the parts are loaded on racks with open ends facing the
spray nozzles. Narrow-necked parts should be placed in
the center of the racks, preferably on specifically
designed spindles with spray nozzles directed into the
necks. Small articles should be grouped in baskets to
prevent dislodging by spray. Avoid loading parts touch-
ing each other where possible. Only low foam detergents
designed for these machines should be used. Typically,
10 g or 10 mL of detergent per liter of hot, wash-cycle
water (approximately 60˚C) is used.
• Power Spray Wand—Commonly called a power washer,
it consists of a pressurized tank with hot water and/or
steam that is connected to a hand-held wand. The wand
will have a trigger to release the hot water or steam and
usually has a detergent metering device or injection
device to meter in detergent during spraying.
Aqueous Cleaning Processes 29
 • Washer/sanitizer—A high temperature washing
machine usually larger than a home dishwasher; it has
racks where devices to be cleaned are placed with very
hot water used during cleaning to give some thermal
sanitation. Versions of these machines that are used in
cleaning medical instruments may even have pressure
seals and use high pressure steam to achieve higher tem-
peratures for higher degrees of disinfection.
• Glassware Washers—Glassware washers are used for
washing laboratory glassware. They are usually available
in small under counter sizes that are approximately the
size and dimension of a home dishwasher, or a variety of
larger floor standing models for cleaning higher volumes
of glassware. As glassware washers, these will often be
connected to a deionized water source in order to be
able to rinse with the deionized water. In laboratory
cleaning it is often critical to have a deionized water
rinse to prevent any residue left from the rinse water.
• Parts washers—Parts washers are a class of washing
machinery used in industrial cleaning that covers a wide
variety of types of cleaners. These vary from ultrasonic
washers which were discussed previously, to immersion
soak tanks, to elaborate agitation machines having
immersion tanks with bubbles running through them or
with some kind of inert media that is vibrated inside
them with a solution, to variations on the washer sanitiz-
ers or glassware washers as discussed above. If you are
dealing with a machine called the parts washer it can be
important to determine which kind of parts washer it is.
If it is a parts washer which relies on spray agitation or
pressurized spray as in a glassware washer or washer
sanitizer, then you need a low-foaming detergent. If it is
a ultrasonic cleaner or an agitation under immersion
cleaner you may be better off with those detergents suit-
able for those kinds of cleaners.
• PC Board Washer—Like glassware washers these typi-
cally come in under counter sizes, and floor standing
models for larger numbers of boards or larger sizes of
boards. These are usually spray wash machines that have
racks mounted inside them with spray nozzles to dis-
30 The Aqueous Cleaning Handbook
pense detergent and rinse water. There is a class of PC
board washer that is called a conveyorized or continuous
washer that has a conveyor belt that carries the boards
past a series of washing spray stations and rinsing sta-
tions.
IMPROVING PERFORMANCE BY
CONTROLLING EFFICIENCY VARIABLES
By choosing an appropriate cleaning method, using the right
rinsing and drying process, then varying the cleaner, concen-
tration, temperature, and time, an optimized aqueous-cleaning
system can be achieved.
Getting the greatest performance in aqueous critical clean-
ing requires controlling the eight important variables that
affect cleaning performance.
1. Precleaning handling
As a general rule, parts and surfaces must be cleaned promptly
after becoming soiled to avoid drying and setting up the dirt
on them. Clean storage conditions for parts, or proper packing
of parts by the parts supplier, can make it easier to successful-
ly clean parts or surfaces.
2. Agitation/cleaning method
Usually the cleaning method is selected first—depending, of
course, upon the practical considerations of your cleaning
problem. The cleaning method, in turn, dictates the type of
agitation available. While very large items or large quantities
of items with less critical throughput requirements may be
handled in large dip tanks, critical items—and their volume—
will determine the type of cleaning procedure.
Examples:
• Small items—Cleaning by hand with cloth, sponge, or
brush agitation may be acceptable for items that are
small in volume and size.
• Important items—You may want to clean in ultrasonic
immersion tanks for items requiring more controlled,
reliable, and reproducible cleaning that is less subject to
human error.
Aqueous Cleaning Processes 31
 • Large quantities—May also dictate the use of ultrasonic
immersion cleaning, batch-parts washers, or mechanical
washers.
• Very large quantities—Parts with rapid throughput
requirements may require conveyor-type spray washers.
3. Rinse procedure
Rinsing methods are usually dictated by practical considera-
tions that are compatible with the cleaning method you have
chosen.
It is also important to use sufficient rinse water to assure
complete soil and detergent removal. For basic crude cleaning,
two volumes of rinse water for every volume of wash water
may be sufficient; for higher level cleaning three or more vol-
umes of rinse water are usually required.
Agitated or running water is always preferable to stagnant
soak rinsing. It is important to choose rinse water that is free
of problem residues.
Be aware that the rinse water is the last thing to touch the
item you are cleaning. Whatever is in the rinse water can end
up on your surface. The substrate and application for your
parts also help determine the type of rinse water.
Examples:
• Electronic components—Use ion-free deionized water
for components that are conductive ion sensitive.
• Pharmaceutical, medical device, optical, and coating
applications—Use organic-free distilled or reverse-
osmosis water for organic, film-sensitive compounds or
parts.
• Manufacturing—Use low calcium/magnesium soft
water, deionized water, or distilled water to avoid calci-
um/magnesium water spot deposits.
If the purified water is expensive to use, you can often get
by with an initial regular tapwater rinse followed by a final,
purified-water rinse. Another way to minimize rinse water
deposits is to dry by a water-removing method rather a water-
evaporating one.
32 The Aqueous Cleaning Handbook
4. Drying method
You can dry by physically removing rinse water or by evapo-
rating rinse water. Physically removing by wiping, blowing,
centrifuging, drying fluids, or other physical removal tech-
niques will remove the rinse water before it has a chance to
evaporate. Such methods avoid precipitating out any impuri-
ties or salts that may be present in the rinse water.
Evaporation drying methods such as air drying, heat dry-
ing, and vacuum drying can potentially deposit any non-
volatile impurities present in the rinse water. Note that vacu-
um drying can evaporate a wide range of impurities that are
nonvolatile at room temperatures.
5. Cleaner type and concentration
Detergents should be compatible with the cleaning method
and effective on the soils you are removing—one that will not
damage the substrate you are cleaning.
Choose a cleaner with the appropriate combination of
cleaning functions for your soil that will perform well with
your cleaning method.
6. Temperature
Changing this variable gives the most dramatic results.
Generally, the higher the temperature, the faster and more effi-
cient the cleaning. For cleaning mechanisms that have first-
order reaction kinetics (such as emulsifying, saponifying, and
dispersing), an increase of 10˚C (18˚F) will double the rate of
cleaning.
High temperatures are particularly important in
machine/spray washing where a droplet of solution only has a
split second to react with the soil before the next droplet of
cleaning solution displaces it from the surface. High tempera-
tures also help remove soils such as wax or silicon oil that typ-
ically can only be softened at temperatures above 170˚F in
conjunction with a high-emulsifying cleaner. It’s important to
note, however, that high temperatures are not always desir-
able. They must be balanced against a commensurate increase
in corrosion.
Aqueous Cleaning Processes 33
 Also, many materials require using only the highest tem-
perature that will cause no harm to a substrate. Examples
include plastics, which often cannot be cleaned above 70˚C
(160˚F), aluminum not above 60˚C (140˚F), and proteins not
above 55˚C (130˚F).
7. Cleaning time and concentration
Above a certain minimum concentration of detergent, dou-
bling the detergent concentration may only give a 10%
increase in ability to remove soil and a 25% increase in bath
life. Beyond a certain minimum cleaning time, doubling the
cleaning time may only give a 10% increase in ability to
remove soil. The minimum concentration and the minimum
length of cleaning time may be around 25% of a typical con-
servative recommendation from a detergent manufacturer.
To optimize your system, bracket the cleaner manufactur-
er’s recommendation and then increase or decrease the time,
temperature, concentration, and agitation according to your
needs, recognizing that decreasing any one of these variables
may require increasing the others. In many cases dropping the
temperature significantly can result in cleaning performance
decreases that cannot be made up for by increasing time, agi-
tation, or cleaner concentration.
8. Postcleaning Handling
Providing for clean storage or clean packaging in which to put
your clean parts or surfaces can help maintain them in a clean
state.
SELECTING A CLEANING METHOD
The choice of cleaning method is determined by the quantity
of parts to be cleaned, their configuration, the cleanliness level
that needs to be achieved, and the budget available for equip-
ment.
Often a cleaning method choice is based on volume, for
example, manual cleaning for small volumes. As the volumes
or quantity of the parts or surfaces being cleaned increases,
immersion cleaning system, possibly even including ultrasonic
agitation, may be indicated. As the parts and volumes increase
further still, some form of high-volume spray cleaning applica-
tion will be required.
34 The Aqueous Cleaning Handbook
Keep in mind, however, switching from an immersion- or
manual-cleaning method to a spray-cleaning method, may
require reconsidering the choice of detergent. This can be
important in a validated cleaning environment—where a
future change in cleaning methods will also add additional
concerns for validation. Therefore, at a smaller volume, it is
often wise to use a cleaning method that can be scaled up to
high-volume manufacturing, if this level of output is anticipat-
ed.
The following are the predominant cleaning methods:
• Manual cleaning—typically chosen for small-volume
batch cleaning. The levels of cleanliness that can be
achieved by manual cleaning are actually very high,
although the operator determines the consistency of
cleanliness. For consistent manual cleaning, rigorous
operator training and retraining needs to be considered.
Well-written cleaning procedures and training proce-
dures should be provided for—even going go so far as to
certify operators in different cleaning methods with peri-
odic recertification.
• Soak cleaning—usually chosen for small quantities of
parts when there is sufficient time in which to clean
them. Soaking is not labor intensive, although it is typi-
cally a slow process. Care should be taken in choosing a
soak method of delicate parts are being cleaned. Due to
the longer times involved in soaking, there is also more
time for corrosion due to interaction between the sur-
face being cleaned and the solution used to clean it. As a
result, soaking is best suited to small volumes of robust
parts where time is not terribly important.
• Ultrasonic cleaning—particularly effective on small
parts with blind holes and crevices that are inaccessible
by spray cleaning. This process is essentially soak clean-
ing enhanced by ultrasonic sound energy. This greatly
accelerates the speed of cleaning and can greatly
improve cleaning in small spaces or crevices. Ultrasound
helps with dispersing and mass transfer of the cleaner
and the replenishing of fresh cleaning solution to the
surface of the parts being cleaned. Ultrasonic cleaning
involves more expensive equipment and is typically suit-
Aqueous Cleaning Processes 35
 able for somewhat larger volume batches where a higher
level of cleaning is required.
• Clean-in-place by circulation system—typically used
for piping or small tank systems where a spray clean in
place system can not used or in filtration systems where
the filters being cleaned can not be accessed by spray
nozzles.
• Spray clean-in-place—typically used in larger tank sys-
tems where the efficiency achieved by less solution usage
warrants the cost of installing the spray system. The
spray cleaning of tanks can also give more reliable, com-
plete coverage of the tank. (Also, an immersion cleaning
system may have difficulty cleaning the top of a tank,
requiring additional manual cleaning.)
One must keep in mind when choosing which method to
use for cleaning tanks that a detergent that performs well for
soak cleaning may not perform as well in spray cleaning.
Therefore, if it is anticipated that a process will ultimately be
scaled up to a spray clean-in-place system, it may be wise to
consider using a spray-cleaning detergent that will also perform
adequately in soaking operations.
The choice of a cleaning machine depends on the batch and
size of the pieces being cleaned. As batch volumes move up
from those that may be best addressed by ultrasonics, it often
makes sense to employ some form of cabinet, under-counter, or
floor standing washer.
For very high-volume parts washing, a conveyorized system,
whereby parts are placed on a conveyor and are cleaned with
spray nozzles as they pass through the conveyor cleaning sys-
tem, may be appropriate.
Spray cleaning systems are very good for parts and surfaces
that are readily accessible to the spray. They are not as good at
dealing with blind holes and small crevices. For instances where
you have higher volumes of parts where it makes sense to use
spray cleaning, you should investigate spray under immersion.
For cleaning very, very large parts (where an operator can
physically move around the part, for example, vehicles or very
large assemblies) it makes sense to use a power spray want or
handheld pressure spray device to clean part exteriors.
36 The Aqueous Cleaning Handbook
BATH-LIFE EXTENSION AND CONTROL
For the highest levels of critical cleaning only freshly made up
solutions should be used for cleaning to avoid any potential for
cross contamination. For industrial critical cleaning applica-
tions high levels of cleaning can still be achieved with extended
bath life. In general, a pH change of 1 pH unit towards neutral
indicates an exhausted cleaning solution. Bath life can also be
extended by physical filtration of particulates and cooling and
settling of sludge and skimming of oils. Bath life can also be
extended by adding one half as much detergent of the initial
load after partially depleting the cleaning life of a bath. Under
frequent daily use, detergent solutions can rarely be used more
than a week even with these bath life extension techniques.
Conductivity, pH and, % solids by refractometer can be used to
control bath detergent concentration.
Free alkalinity titration can also be used to control bath
life of alkaline cleaners where the soil being cleaned depletes
free alkalinity—as is often the case with oily soils. The process:
• Titrate a fresh solution to determine new-solution free-
alkalinity.
• Titrate the used solution to determine the percent drop in
free alkalinity.
• Add more detergent to the bath to bring the free alkalini-
ty back to the new solution free alkalinity. (For example
if the initial solution is made up with 100 ml of cleaner
concentrate and a 25% drop in free alkalinity is
observed, try adding 25 ml of cleaner concentrate to
recharge your solution.)
Perform a new free-alkalinity titration to confirm the
recharge the first few times this recharging method is used to
be sure that the detergent being used is linear with respect to
free alkalinity depletion. This form of bath life extension can-
not run indefinitely, sludge will eventually form. Fresh solu-
tions must be made up periodically.
Bath lives can be controlled to extend them by using con-
ductivity. Most cleaners have conductive salts in their ingredi-
ents, which are detectable by conductivity. By knowing the
conductivity response of the detergent, the depletion of those
conductive salts can be measured.
Aqueous Cleaning Processes 37
 Many cleaner manufacturers can supply the curves of
detergent concentration versus conductivity. By adapting these
curves to your conditions and measuring the conductivity, de-
tergent depletion and dilution by make-up water can be deter-
mined. This determination can be used to figure out how
much detergent to add to the cleaning solution to restore
cleaning performance. Typically this kind of measure and
recharge can be carried out through several iterations.
Keep in mind, however, the bath will ultimately reach a
point where it forms sludge (or where some other failure
mechanism occurs), at which time the bath must be dumped
and a complete batch of new cleaner employed. The time to
dump the bath and start over is often defined as being after a
certain number of parts or length of time as determined using
some sort of cleanliness measurement. The conductivity will
typically not detect the point of cleaning failure, but will only
detect concentration of cleaner present, whether depleted or
not. The following table gives specific examples of concentra-
tion vs. conductivity for some specific Alconox-brand cleaners.
Using the data below one can derive the concentration of
detergent from measured conductivity. Note that conductivity
is very temperature dependant and detergent solutions do not
have the same slope as many default settings on temperature-
correcting conductivity meters. For best results, allow hot
detergent solutions to cool to a consistent temperature for
comparison.
order of importance) use less heat, lower pH detergents, and
shorten cleaning time and agitation.
In general, use the mildest pH detergent to limit metal cor-
rosion. Higher pH detergents may have metasilicate corrosion
inhibitors that often allow it to be used successfully to clean
soft metals such as aluminum. In general, to reduce plastic
corrosion, use less aggres-sive cleaners that have less solvent
or surfactant character or use lower concentrations of those
cleaners, use lower cleaning temperatures, use less contact
time, and finally, use less agitation.
With aqueous cleaning, metal corrosion can occur during
rinsing and drying. Corrosion inhibitors can be added to rinse
water provided that any associated inhibitor residue does not
interfere with the surface being cleaned. Keeping the surfaces
cleaned hot by using hot rinse water and by using rapid heat
or vacuum drying can accelerate drying and minimize metal
corrosion. Forced air drying and air knives that physically
remove rinse water can also minimize corrosion, as well as
drying with hot oxygen-free gas such as nitrogen.
With mild steel one can have “flash rusting” when rinsing
with hot water and drying with hot air. In some instances, low-
ering the water temperature or drying temperature can help
avoid corrosion on mild steel. For instance, in a case where
flash rusting on mild steel had been occurring due to using
150°F rinse water and ambient air drying, it was found that
flash rusting could be avoided by using 120°F rinse water in
place of the 150°F rinse water.

TABLE CONDUCTIVITY (Ms) VS CONCENTRATION OF ALCONOX, INC CLEANERS AT 22 DEG C

Concentration Alconox Alcojet Terg-a-zyme Alcotabs Liquinox Citranox Detergent 8 (uS) Det-o-jet
REFERENCES
0.125% 1.136 1.354 1.184 1.011 0.108 0.195 21.00 0.614 Alconox Cleaning Solutions Newsletter, Vol. 1, Number 3 “Improving
0.250% 2.08 2.51 2.21 1.912 0.213 0.327 29.70 1.275 Performance—Controlling the 6 Big Efficiency Variables.
0.500% 3.83 4.6 4.1 3.48 0.402 0.475 41.60 2.58 Alconox Guide to Critical Cleaning, Cleaning Procedures section.
1.000% 6.99 8.34 7.51 6.36 0.747 0.682 63.30 5.05 Drying Systems, Appropriate Drying Technology Completes Successful
2.000% 12.71 15.02 13.65 11.55 1.38 0.987 87.60 9.68 Cleaning from Precision Cleaning, December 1997, p. 37.
4.000% 22.6 26.6 24.3 20.8 2.63 1.47 106.40 18.17 Variables and Vitals of Metal and Electronics Aqueous Cleaning article
by Malcolm McLaughlin, Precision Cleaning, January 1994.

CORROSION INHIBITION
Corrosion during cleaning is accelerated by the same things RESOURCES
that accelerate cleaning: heat, aggressive chemicals, time, and www.alconox.com
agitation. To reduce metal corrosion concerns (in approximate www.cleanersolutions.org.
www.corrosionsource.com
www.clean.rti.org

38 The Aqueous Cleaning Handbook Aqueous Cleaning Processes 39

 CHAPTER FOUR

Selecting an
Aqueous-Cleaning
Detergent
The major requirement in cleaning electronic parts, assem-
blies, precision parts, and metal surfaces is that there be no
residues that interfere with further use or processing of the
cleaned surfaces. The cleaning method should be noncorrosive
to the component and the detergent chosen should exhibit
exceptional free-rinsing qualities.
Critical cleaning requires careful selection of cleaning
chemistry and methods to ensure adequate performance with-
out sacrificing either worker safety or benign environmental
impact. Current solvent cleaners may have ozone-depleting
potential or Clean-Air-Act-Amendment-regulated volatile
organic compounds (VOCs). Current corrosive mineral acid or
caustic cleaners may present worker exposure hazards and
environmental disposal problems. The use of appropriate
aqueous cleaners can replace the use of volatile organic and
ozone- depleting compounds for cleaning. In addition, suitable
aqueous cleaners can be milder and easier to dispose of than
mineral acid or caustic cleaners.
In practice, it is important to be able to choose from a
range of detergents to find one that performs well with the
cleaning method and is suitable for the soils and surfaces need
ed to be cleaned. (See Table 4A) Key considerations include:

40 The Aqueous Cleaning Handbook Selecting an Aqueous Cleaning Detergent 41

 • Type of substrate—Metal (ferrous/nonferrous), glass,
plastic, rubber. For example, substrates such as magne-
sium, aluminum, and similar metals may be attacked by
some types of chemicals. Stainless steel alloys, on the
other hand, often have a high resistance to both acids
and alkalies.
• Type of soil—What type of soil is it? Heavy or light,
organic or inorganic, oil or particulate matter. This is
perhaps the single most important question to ask when
you are selecting an aqueous detergent. Heavy soils
require heavy-duty detergents or cleaners to re-move
them. The detergent should have a high concentration of
cleaning ingredients to give it a high capacity for remov-
ing soil; typically heavy soils require very aggressive
cleaners. A heavy soil may often be best handled by a
high dispersing cleaner that is able to move bulk quanti-
ties of soil without having to react chemically with each
individual molecule of soil.
Light soils require a detergent that matches the exact
type of soil in order to be able to most completely
remove them. If you have a light soil it is more impor-
tant to know more about what kind of soil it is so that
you can go from a surface that is almost clean to a sur-
face that’s extremely clean or meets your level of cleanli-
ness. For example, many organic soils have limited water
solubility. These oily soils are often best cleaned by a
high emulsifying cleaner. An inorganic soil again may or
may not be water soluble, but if it is not water soluble it
is often able to be removed by chelation using a deter-
gent that has a good dose of chelating agent or it may be
able to be made water soluble by reacting with an acid
cleaner by some of the acid solubilization mechanisms
which have been discussed in the detergent chemistry
chapter. Oils are often readily cleaned by the same types
of cleaners that remove organic soils. Silicon oils are a
special subset of oils that are very difficult to remove.
They require a very high emulsifying cleaner and usually
very high temperatures to be removed. Silicon oils are
found in things such as mold release agents.
42 The Aqueous Cleaning Handbook
Finally, particulate soils are best removed by disper-
sant cleaners that can lift them into solution and form a
suspension. Very small particulates, for example submi-
cron particulates, need to be cleaned by a very high wet-
ting, low surface tension cleaner that has the ability to
lower the boundary layer between the surface and the
solution down to submicron distances to allow the agita-
tion in the cleaning solution to access the submicron
particulate.
• Part complexity—Are there severe undercuts, blind
holes, or numerous part cavities? Higher-powered wet-
ting detergents with low surface tension may be
required.
• Level of cleanliness required—If the part being cleaned
or the manufacturing process does not require excep-
tionally high technical specifications for cleanliness,
harsh, toxic cleaning agents can often be avoided.
• Manufacturing process—For example, if a part arrives
wet at the cleaning station, an aqueous chemistry may
be best.
• Cleaning efficiency—As a rule, cleaning efficiency
increases with time, temperature, and agitation, though
each may affect other important considerations such as
foaming, costs, health, or safety.
• Environmental considerations—The environmental
impact of cleaning operations can often be minimized or
reduced by selecting the most appropriate aqueous
cleaning agent, and appropriate cleaning and/or recy-
cling system.
Selecting an Aqueous Cleaning Detergent 43
 usually loosens all the soil from the surface and then the
TABLE 4A DETERGENT CLEANING APPLICATIONS AND METHODS rinse water needs to sweep it away. In residue-free clean-
Application Recommended
ing it is important to use a nondepositing rinse aid.
Key Concerns Articles Cleaned/Soil Removed Cleaning Method Detergent Many rinse aids are positively charged compounds that
Metalworking Glass, ceramic, porcelain, stainless steel, Manual, Ultrasonic, Soak, C-I-P* Mild alkaline are attracted to a surface that repels the water from the
and Precision plastic, rubber. Oils, chemicals, particulates.
Manufacturing Machine washer, power wash Low-foam alkaline surface. This can leave what appears to be a nice clean
Clean parts, avoid
volatile solvents, Aluminum, brass, copper, and other soft Manual, Ultrasonic, Soak, C-I-P* Mild alkaline surface, but in fact it will be covered with the hydropho-
strong acids, and metal parts. Oils, chemicals, particulates.
other hazardous Parts washer, power wash Inhibited low-foam alkaline bic water repelling rinse aid.
chemicals.
Inorganics, metallic complexes, trace metals Manual, Ultrasonic, Soak, C-I-P* Mild acid 3. Is the detergent recommended for the desired clean-
and oxides, scale, salts, buffing compounds.
Parts washer, power wash Low-foam mild acid ing method? (See previous discussion.)
Silicone oils, mold-release agents, buffing Manual, Ultrasonic, Soak, C-I-P* High-emulsifying, mild alkaline 4. How hazardous is it? For example, is it highly alkaline
compounds.
Parts washer, pressure spray Low-foam alkaline or acidic, presenting a personal health hazard? Is it cor-
Metal oxides, scale, salts. Metal brightening. Manual, Ultrasonic, Soak, C-I-P* Mild acid rosive? Does it present a reactivity hazard with soils? Is
Parts washer spray Low-foam mild acid it a flammable or volatile solvent? These considerations
Electronics Circuit boards, assemblies, screens, parts, Manual, Ultrasonic, Soak Nonmetal-ion, Nonionic can be evaluated by reviewing a Material Safety Data
Avoid conductive conductive residues, resins, rosins, fluxes,
residues, avoid particulates, salts. Machine washer, power spray Low-foam nonmetal-ion, Sheet for the agent. Preferably, it should not contain any
CFCs, pass board and screen washers Nonionic hazardous ingredients listed on the OSHA standard and
cleaning criteria.
Ceramic insulators and components. Manual, Ultrasonic, Soak Mild alkaline Hazardous Substance List 29CFR 1910 subpart Z.
Parts washers Low-foam alkaline
5. Can it be disposed of easily? Any detergent chosen
*Clean-in-Place by circulating, for spray clean-in-place see machine washer detergents.
should be readily disposable and biodegradable, contain-
ing no RCRA Hazard Classification or EPA Priority
DETERGENT SELECTION Pollutants designation. Otherwise, the use of hazardous
Today’s aqueous critical-cleaning detergents are blended for cleaners may require special, expensive waste-handling
specific applications—substrates, degrees of soil load, and treatment.
cleaning process used. Here are a few questions to ask about a 6. Is it environmentally friendly? Considerations include
detergent brand to ensure that it meets your specific cleaning ozone depletion potential and volatile organic compound
needs: (VOC) content regulated by the Clean Air Act
1. Does it have good detergency on the types of soils Amendments. Approval under anticipated future restric-
that you need to remove? A broad range of organic tions should be weighed as well.
and inorganic soils are readily removed by mild-alkaline 7. How economical is it? The detergent should be widely
cleaners that contain a blend of surfactants and seques- available and affordable. For optimal economy, a con-
tering agents. Metallic and inorganic soils are often centrated detergent is typically used at 1:100 dilutions.
readily solubilized by acid cleaners. Proteinaceous soils
are effectively digested by protease enzyme cleaners. In choosing an appropriate detergent, one must consider
2. Is it free-rinsing? Will it rinse away without leaving the equipment it is being used to clean; the level of cleanliness
interfering detergent residue? A properly formulated and residue removal that is necessary; the cleaning method
detergent will contain rinse aids to help the rinse water that is to be used; and the performance of the detergent. Key
remove the detergent and soil solution. Rinsing is a criti- questions to ask about selecting a cleaner are:
cal part of high-performance cleaning. The detergent • Does it have fillers? There are a number of ways to tell

44 The Aqueous Cleaning Handbook Selecting an Aqueous Cleaning Detergent 45

 whether the powder or liquid brand you’re considering MONEY SPENT ON CLEANING AGENTS PER YEAR
contains any excess fillers and is optimally concentrated.
— What are the ingredients?
Powders: When selecting a powdered brand, look at
the label, technical bulletins, and MSDS to see if it
contains any sodium chloride or sodium sulfate com- Under $10,000
pounds which do not perform a useful cleaning func- 46%
tion but merely add to volume and weight (and ship-
ping costs). $10,000-$50,000 Over $50,000
Liquids: With liquid detergents, the most common 35.5% 18.5%
filler is water. It is important, however, that no more
water is used than necessary to ensure a good solu-
tion, maintain stability, and prolong shelf life. Source: Precision Cleaning Magazine, December, 1996.

— What is the concentration?

Powders: It is rare that a detergent will require more
than a 1 percent solution of detergent to water HEALTH/SAFETY CONSIDERATIONS
(1:100). Human health and safety considerations include detergent
toxicity, corrosivity, reactivity, and flammability. These consid-
Liquids: A typical alkaline cleaner should not need to
erations can be evaluated by reviewing a Material Safety Data
be used at a dilution of more than 1:100. And, semi-
Sheet for the solvent, chemical, or detergent with which you
aqueous or solvent-containing cleaners may reason-
intend to clean. The detergent(s) you choose for your applica-
ably need to be used at dilutions of 2:100 or more.
tion preferably should:
• What are the operating costs?
• be formulated to minimize health-safety concerns while
Operating costs for aqueous cleaners are generally low still offering outstanding cleaning performance
since these cleaners are usually concentrated—typically
• not contain any hazardous ingredients listed on the
using only one to five percent of cleaner solution to
OSHA standard and Hazardous Substance List 29CFR
water. Also, aqueous cleaning baths last a relatively long
1910 subpart Z
time without recycling.
• not have flash points or stability hazards.
Strong acid cleaners generally require constant sys-
tem maintenance since their aggressive chemistry can
Many detergents strong enough to remove fingerprints,
attack tank walls, pump components, and other system
can remove oils from skin and, therefore, have the potential to
parts as well as the materials to be cleaned. (Inhibitors
dry out skin and cause “dishpan hands.” This is especially true
can be used to reduce such attack.) Another disadvan-
of detergents designed for machine spray washing which, in
tage of strong acid cleaners stems from soil loading—
order to perform in the limited contact time afforded during
particularly metal loading—which requires frequent
spray cleaning, are considered to be aggressive cleaners.
decanting and bath dumping, leading to relatively high
Protective neoprene, butyl, rubber, or vinyl gloves are recom-
operating costs compared with alkaline cleaners.
mended for any extensive manual cleaning operation. In addi-
In contrast, alkaline cleaners are often more economi- tion, many detergents are potential eye irritants, and should
cal compared to acid chemistries, because they do not not be used without eye protection. See Chapter Eleven,
cause excessive maintenance problems.

46 The Aqueous Cleaning Handbook Selecting an Aqueous Cleaning Detergent 47

“Environmental Health and Safety Considerations,” for further REFERENCES
discussion. Aqueous Cleaning Chemistries, Precision Cleaning, December 1996, p. 22.
Selecting An Aqueous Cleaner by Malcolm McLaughlin, Precision
ENVIRONMENTAL CONSIDERATIONS Cleaning ’97 Proceedings.
Environmental considerations include concern over volatile
solvents with ozone-depleting potential and volatile-organic RESOURCES
compound content that is regulated by The Clean Air Act www.alconox.com
Amendments. Any detergent chosen should be biodegradable www.cleantechcentral.com
and readily disposable, and contain no RCRA Hazard Classifi- www.clean.rti.org
www.cleanersolutions.org
cation or EPA Priority Pollutants.
Surfactants are not generally viewed as a menace to the
environment. Nonetheless, their environmental attributes
often receive as much attention as their technical properties
and economic aspects. One reason may be the mental image
most people have of foaming streams and rivers, formed over
three decades ago, has not faded entirely. This foam resulted
from non- or poorly-biodegradable surfactants which are no
longer used in modern aqueous cleaner formulations.
Then, too, public environmental awareness has increased
markedly in recent years. In fact, environmentalism has tran-
scended from a social attitude to an almost metaphysical level,
or at least to a position that compares with spirituality. A large
portion of the public wants to “do the right thing,” environ-
mentally speaking. To this end, regulations are enacted and
products are being designed and marketed. We have entered
the age of environmental marketing and are forming attitudes
about environmental attributes, sometimes without adequate
comprehension of the scientific disciplines that are required.
Much of the discussion of the environmental acceptability
or preferability of surfactants centers on the standard against
which measurement is made and on the designation of what is
environmentally important.
Both the issues of health and environmental safety are
important and extremely complex. Again, for a more complete
description for health, safety and environmental issues see
Chapter Eleven.

48 The Aqueous Cleaning Handbook Selecting an Aqueous Cleaning Detergent 49

 CHAPTER FIVE

Testing and Selecting

A Detergent and
Cleaning System
T esting and selecting an aqueous cleaning system involves a
seven-step process:
1. Identify the key reason you are developing the system.
2. Select an evaluation method that will allow determi-
nation that key cleaning criteria are satisfied.
3. Select a test cleaning system that includes a cleaning
method, rinse method, and a drying method.
4. Select a test substrate for cleaning.
5. Select a test soil and method for applying the test soil
to the test substrate.
6. Select an aqueous cleaner for evaluation.
7. Perform tests and optimize your selected system.

IDENTIFY REASONS FOR

CHANGING CLEANING SYSTEMS
It is important to identify the key reasons for a new system so
that the selection process satisfies all of the reasons a new sys-
tem is desirable. The following table outlines some of the rea-
sons for setting up new systems and the kinds of parameters
that must be evaluated for each.

50 The Aqueous Cleaning Handbook Testing and Selecting a Detergent and Cleaning System 51
 Information sources—In order to help identify options and
TABLE 5A REASONS FOR NEW CLEANING SYSTEMS
those systems which may work best for you, you may wish to
AND THEIR CORRESPONDING NEEDS FOR EVALUATION
consult some of the following sources of information. These
Reason Key Considerations resources should be used to help narrow your search for types
Waste treatment concerns Estimate quantity and characteristics of discharge, of systems and cleaning chemistries.
reporting status, hazards, permits needed Look for information that correlates with your reasons for
Air pollution concerns Estimate quantity and characteristics of volatile cleaning and the resulting key considerations.
solvents, current and expected regulatory status
Worker safety Review equipment design and chemical characteristics, TABLE 5B
flammability, corrosivity, toxicity, need for protective Internet
devices, ventilation, thresholds (TLVs), worker training Alconox detergent selection
needed and use procedures (www.alconox.com)
Improved detergency Review equipment design, rinsing and drying procedures, Precision Cleaning Web (www.precisioncleaningweb.com)
and cleaner chemical characteristics to see that they
fit the type of soil and substrate being cleaned Parts Cleaning Web (www.partscleaningweb.com)
Improved cleaning speed Review temperature, agitation, chemistry, and drying Toxic Use Reduction Institute (www.cleaningsolutions.org)
conditions Research Triangle Institute (www.clean.rti.org)
Lower cost Review recurring costs of chemistry, waste treatment, US EPA (www.epa.gov)
disposal, safety, regulatory compliance, maintenance, Pollution Prevention Gems (turi.uml.edu/P2GEMS/)
cleaning time labor, utilities, and capital costs Finishing (www.metalfinishing.com)
New process Prioritize and evaluate all of the above, use of existing Waste Reduction (www.owr.ehnr.state.nc.us/ref/00023.htm)
equipment may be desirable
Publications
Organizational considerations—Having identified what is
Cleantech (Witter Publishing, 84 Park Ave,
being cleaned, the contaminants being cleaned, and the rea-
Flemington, NJ 08822)
sons for changing or creating a new cleaning process, we must
908-788-0343
next consider the organizational implications of the new
www.cleantechcentral.com
cleaning system. In short, who and what will be affected by A2C2 (62 Route 101A, Suite 3, Amherst, NH 03031)
the system? Alconox Guide to
It is important to consider production personnel, supervi- Critical Cleaning (Alconox, Inc. 30 Glenn St., White Plains, NY 10603)
sors, engineering, environmental compliance, purchasing,
marketing, public relations, and quality control. It is also help- Conferences
ful in getting a new process adopted to be able to identify key
Cleantech (WPC Expositions, 84 Park Ave,
benefits to each affected group in a manufacturing organiza-
Flemington, NJ 08822)
tion. Forming a team with influential representatives from
908-788-0343
within these groups will help with the ultimate success of the
www.cleantechexpo.com
adoption of the new cleaning process.

52 The Aqueous Cleaning Handbook Testing and Selecting a Detergent and Cleaning System 53
SELECT AN EVALUATION METHOD TABLE 5C MISTAKES TO AVOID IN EVALUATING A
Once the key reasons for testing and evaluating a new cleaning CLEANER AS PART OF CLEANING SYSTEM DEVELOPMENT
system are determined, methods for evaluating the success of
Mistake Result Correction
the new method must be chosen. The literature available
about the cleaner under consideration should be reviewed for Use immersion in small A high emulsifying gentler Use a Water Pik®,
any health, safety, and environmental concerns. tanks or beakers to test cleaner will work best, but circulated or
Cleaning performance must also be evaluated through test cleaners that will be used in will fail in the spray agitation the spray system
cleaning. First, determine a baseline level of cleanliness and a spray cleaning environment system poured cleaning
way of measuring that baseline. (See Chapter Eight for meth- solutions to mimic
ods to measure cleanliness.) Often visual inspection is suffi- spray cleaning
cient for initial development work. A relatively simple gra- Use a higher temperature A milder cleaner will give Match
vimetric analysis involving weighing a clean substrate before than will be available in adequate cleaning that fails temperatures
soiling, after soiling, and after cleaning to determine percent scale-up at lower temp
soil removal is effective as a measure of cleaning performance Clean for a longer time A milder cleaner will give Only use available
as long as the substrate is impervious to the cleaner. Other than will be practical when adequate cleaning that cleaning times
reflective analytical techniques require special equipment to you scale-up fails in shorter time
be used such as Optically Stimulated Electron Emission Use flat substrates when small A system with inadequate Use a substrate to
(OSEE) as well as Grazing Angle Fourier Transform Infrared crevices and blind holes will be agitation will work on flat mimic the scale-up
Spectroscopy (FTIR). present in scale-up surfaces that fails on crevices surface—perhaps
Surface contact-angle of deionized water on a flat surface take flat plates
can be used, along with a variety of methods that involve pressed together
extracting soils from the surface and then performing an Use a soil that does not The wrong cleaner may Try to use similar
analysis of the extract. As a rule of thumb, the simplest represent the real soil be chosen soils for testing
method that will provide suitably sensitive results should be
employed. It is often tempting when evaluating a cleaner to put the
cleaner in a tank or beaker and dump some of the dirty parts in
SELECTING THE TEST CLEANING SYSTEM it to see if simply soaking will achieve a modest amount of
Ideally, testing of a cleaning system should be achieved using cleaning. (Sometimes people also add heat and agitation so
full-scale conditions with actual dirty surfaces. In practice, they can get more cleaning from their system.) This is an
however, this is often impossible. Accordingly, a small, bench- acceptable bench test only when developing an immersion-
scale system which mimics the full-scale system must often be cleaning system. Problems often occur with this approach
created. when the ultimate intent is to use a spray washer or mechani-
In mimicking the actual cleaning conditions for the cal washer in the scaled-up process. The cleaning mechanisms
process cleaning method, a rinsing and a drying method must can be very different in immersion cleaning than from those
be considered. In evaluating a cleaner, it is particularly impor- involved in spray cleaning. A system that cleans by soaking in a
tant to mimic the time, temperature, and agitation that will be beaker may not work in a spray washing machine.
available in the scaled-up cleaning process. The following Immersion cleaning techniques can use cleaners that rely
table outlines some mistakes when evaluating a cleaner using on kinetically slower mechanisms such as emulsifying, enzy-
a benchtop cleaning system. matic hydrolyzing, and dissolving. High-agitation spraying
mechanisms need a cleaner that relies on kinetically faster

54 The Aqueous Cleaning Handbook Testing and Selecting a Detergent and Cleaning System 55
cleaning mechanisms such as alkaline or acid hydrolysis, wet-
ting, penetrating, and dispersing. Spray cleaners need to be
more aggressive and faster acting since they have but a fraction
of a second to do their cleaning before the next droplet of spray
sweeps them from the surface. Immersion cleaning can have
minutes or hours of contact time.
It is possible to test a cleaner that will perform only margin-
ally in immersion cleaning but performs excellently in a spray-
washing environment. It is also very possible (and even likely)
that a cleaner that performs excellently in immersion cleaning
will be very ineffective in a spray washing environment.
In particular, high-foaming cleaners that can work very well
in immersion do not perform well in enclosed spray cabinet
washers where the foam can create a barrier to the mechanical
energy of the spray, and where the foam may burst the seals of
the cabinet (and, possibly, cause cavitation in the circulating
pumps).
There is another more subtle difference in spray cleaning
systems where, in simplified terms, one is dealing with two
major kinds of agitation. There is the high volume/low pressure
method of spray washing and the low volume/high pressure
method of spray washing. The first involves gently spraying a
high volume of cleaning solution over the surface of a substrate,
which results in a cascade of solution running down the surface
to be cleaned. This results in a more nearly laminar flow at the
surface with a smaller boundary layer that allows for a wider
range of cleaning mechanisms and, in particular, the occur-
rence of greater small-particulate dispersion.
It is not unusual for what is called a low-foaming or con-
trolled foaming cleaner to perform well in such high
volume/low pressure washers. In low volume/high pressure
spray washing, there is much greater turbulence and more
mechanical energy with cleaning solution bouncing off the sur-
faces with less cascading and sheeting action down the surface.
In these very high agitation cleaning systems you may need a
nonfoaming cleaner.
A problem that sometimes occurs is when a perfectly suc-
cessful high volume/low pressure cleaning system is changed
into a low volume/high pressure cleaning system in an effort to
get faster cleaning cycle times and the system suddenly stops
cleaning well.
56 The Aqueous Cleaning Handbook
The cleaner may not be appropriate for the higher agitation
system, or the particle sizes of the soil may not be as easily
cleaned in higher-turbulence, higher-boundary layer conditions.
Again, when performing bench-scale testing for spray clean-
ing systems it is important to mimic the characteristics of the
actual cleaning system. For instance, mimic the drenching of a
surface by pouring or gently pumping cleaning solution over a
surface in order to mimic high volume/low pressure cleaning, or
mimic the blasting of a surface using a pump and nozzle or
Water Pik®.
It is important to stress that although ultrasonic cleaning
can result in very high localized agitation from the cavitation
caused by the sound waves, the agitation occurs under immer-
sion where immersion cleaning mechanisms are still effective.
Even spray under immersion can allow for some of the kineti-
cally slower immersion cleaning mechanisms to work, although
there is much more movement in the cleaning solution that
occurs during spray under immersion and, thus, kinetically less
time available for slower immersion cleaning mechanisms.
The following table outlines bench scale cleaning methods
and how they mimic larger-scale cleaning:
TABLE 5D TYPICAL BENCH-SCALE CLEANING SYSTEMS
AND THE SCALE-UP SYSTEMS THEY MIMIC
CLEANING METHODS
Bench-Scale Full-Scale
Manual cleaning with tool Manual cleaning with tool
Immersion in a small tank Immersion in a big tank
Small tank with stirrer A clean-in-place,
agitated big tank
Small ultrasonic tank (be sure to use Bigger ultrasonic tank
same frequencies and power densities)
Gently hosing or pouring High volume/low pressure
washer onto a surface
Power spray onto surface Low volume/high pressure
washer
Testing and Selecting a Detergent and Cleaning System 57
Select rinsing and drying conditions—In any bench-scale can remove a particular soil from a surface.
cleaning system it is also critical to understand how the rins- For bench-scale testing first choose a cleaning system and
ing and drying processes can affect cleaning results. In bench- then go on to test the system with a given cleaner. The follow-
scale cleaning, it may be practical to use copious quantities of ing table shows typical bench-scale cleaning methods that are
running water for rinsing. Often, simply putting cleaned parts used to make up a cleaning system of cleaning, rinsing, and
under running water at a sink will be both acceptable and a drying:
highly effective rinsing technique. The same level of rinsing,
however, must be duplicated in scale-up. TABLE 5E BENCH-SCALE RINSING AND DRYING METHODS
The cleaner loosens all the soils and prepares them to be AND THEIR CORRESPONDING SCALE-UP METHODS
rinsed away. A running water rinse is far more effective than RINSING METHODS
static dip-tank rinsing, or even a slow counterflow cascade
Bench-Scale Scale-Up
rinse tank setup. Rinsing relies on essentially two types of
mechanisms: Static soak static soak
• Mass displacement—where the rinse water physically Overflowing dip tank counter flow cascade tanks
replaces the soil/solution mixture. Running water running water or efficient
• Concentration gradient dissolving—where the high counter flow cascade tank
concentration soil/solution mixture at the surface being series
cleaned dissolves into the rinse water, creating a uniform DRYING METHODS
low-concentration mixture with a resulting low concen- Bench-Scale Scale-Up
tration of soil present near the solution/surface interface. Air dry Air dry
Oven dry Hot air dry
In a running water rinse system, mass displacement is the
dominant rinse mechanism. In a static soak-tank rinse, con- Hair dryer Hot directed forced air
centration gradient dissolving is the dominant rinsing mecha- Compressed air nozzle Air knife
nism. When testing bench-scale rinsing, mimic the rinsing that Volatile solvent rinse Volatile solvent rinse
will be used in scale-up. For example, when using a series of
dip tanks or counterflow-cascade tanks in scale-up, a running SELECT THE TEST SUBSTRATE
water rinse may represent a more effective rinse, one that Once a cleaning method is selected for testing, the next step in
might allow the use of a less free-rinsing cleaner to perform developing a cleaning system is to select a substrate and a soil
adequately in the bench-scale process, but cause failure in the to clean. Ideally, actual parts or surfaces with actual soils that
scale-up process. will be cleaned should be used. Sometimes, of course, this is
It is also desirable to use the same quality of rinse water not possible, in which case similar materials should be
that will be used in scale-up. If lab-grade deionized water is employed.
used for bench-scale rinsing, for example, the same type of Also, small stainless steel coupons or glass slides are often
water should be available for scale-up. (Conversely, it is often used for bench-scale cleaning development. For many soils it
possible to use tap water rinses in bench-scale testing—even is not critical what the substrate is, and for many cleaning
though water spots will result that can be eliminated by using mechanisms “a surface is a surface”—whether it be glass or
deionized water rinses with water removing—as opposed to metal.
water evaporating—drying methods.) Tap water rinses are When cleaning plastics, however, the surface considera-
often sufficient to show in bench-scale that a cleaning system tions are more critical, since some plastics will have particular

58 The Aqueous Cleaning Handbook Testing and Selecting A Detergent and Cleaning System 59
affinity for organic soils. Also, when removing salts or inor-
ganic soils from metals it is often important to use the exact
metal that will be cleaned when a process is scaled-up. The
same is true for porous surfaces—such as gold and some ce-
ramics—which may require use of the same substrate for
bench-scale testing in order to develop a reliable cleaning sys-
tem.
Similarly, it can also be very important to use the same
surface for testing in order to be sure that the cleaning system
will not corrode or damage the surface. This is especially true
for aluminum.
It can be very useful to work with standard clean coupons.
There are several suppliers of standard coupons that are more
commonly used with corrosion testing, but that can be adapt-
ed for use in cleaning testing. Some suppliers include:
Metal Samples Corrosion Monitoring Systems
A Division of Alabama Specialty Products, Inc.
P.O. Box 8, 152 Metal Samples Rd.
Munford, AL 36268
(256) 358-4202
http://www.alspi.com/msc.htm
Metaspec CO
790 West Mayfield Boulevard
San Antonio, TX 78211
(210) 923-5999
Q-PANEL LAB PRODUCTS
800 Canterbury Road
Cleveland, OH 44145
PH: (440) 835-8700
http://www.q-panel.com
SELECT A TEST SOIL
It is often more important to pay attention to the soil than the
surface during cleaning system development—using the same
soil in bench-top testing as in scale-up. Pay careful attention to
how dried-on the soil will be in the actual process. A freshly
applied soil may be very easy to remove in bench-scale
60 The Aqueous Cleaning Handbook
processes, but may become very difficult to remove if it dries
on the surface for several hours. (If possible, it may be wise to
try to avoid allowing soils to dry onto a surface in the actual
cleaning conditions.)
If using the exact soils that will be present during actual
cleaning is not possible, try to match the characteristics of the
soil. Match the particulate sizes, oil viscosities, wax melting
points, chemical character (for example, do not use a natural
oil to mimic a synthetic or petrochemical oil and vice versa).
Try to apply the soil to the surfaces in the same manner and
quantity that will be present under actual cleaning conditions.
(Soiling the substrate on the heavy side can be helpful in de-
signing a robust cleaning system.)
In addition, it may be critical to develop a way of uniform-
ly soiling a surface in order to get significant reproducible
results that are suitable for comparing cleaning systems. One
approach is to create a uniform slurry, paste, or solution of the
soil, possibly employing a volatile solvent carrier to apply the
liquid mixture to surface, then using a glass rod with spacers
to spread a uniform film of soil onto a coupon to achieve uni-
form reproducible soil levels.
If the objective is to find a way to absolutely clean a soil—
rather than compare cleaning systems—simply smearing or
applying some soil to the surface for visual inspection that
some soil is present can suffice.
SELECTING AN AQUEOUS CLEANER
After establishing combinations of cleaning, rinsing, and dry-
ing, try a cleaner at different time, temperature, and detergent
concentrations to determine if the system will work. Review
the information in Chapter Four on Detergent Selection to
make sure you are testing a cleaner that has a reasonable
chance of success. Match the cleaner to the desired cleaning
method, soil, and surface being cleaned.
PERFORM TEST CLEANINGS
It is advisable to perform at least three cleanings using each
set of conditions to help minimize anomalous results. For crit-
ical-cleaning system development, it is desirable to perform at
least six repetitions of each set of conditions.
Testing and Selecting A Detergent and Cleaning System 61
 Whether selecting an aqueous cleaner and cleaning system
TABLE 5F
for a new manufacturing or processing application or switch-
ing to an aqueous cleaner, the process is the same. It is a good
Typical cleaner test conditions
idea to start by using an “overkill” combination of time, tem- Overkill
perature, concentration, and agitation than might typically be Double the recommended dilution of detergent
required in a bench-test scenario to first prove that the system Maximum practical temperature
you are using is capable of delivering the cleanliness required. Maximum practical cleaning time
Minimum
Finding the minimums—Having proven that the system can
20% of the recommended detergent dilution
work, the next step is to try a combination of what one might
guess is slightly less than minimum time, temperature, con- Room temperature
centration, and agitation to get some idea of where the system Very short cleaning time
starts to fail. A good, less-than-minimum starting point might Optimized
be 20% of a conservative recommendation from the cleaner’s Recommended dilution
manufacturer. For example, if a cleaner is recommended for 120˚F (50˚C) for immersion or manual cleaning methods, 140˚F(60˚C) for spray
use at 1% in water, 60˚C (140˚F) with a 10-minute soak, one clean systems
might try and see how badly it fails at 0.2%, 40˚C (105˚F) and Practical cleaning times
a two-minute soak. This may provide a sense for how robust-
ness of the cleaning process. One can then choose some com-
Once you have determined an “overkill” system that will work
bination of time, temperature, and concentration above the
and a “minimal” system that probably partially fails, an opti-
minimum based on how poorly the system failed to perform.
mum system can be identified. Decide when to stop bench-
Based on these results, try a combination based on a guess
scale optimizing and when to move on to pilot-scale or full-
of what might be slightly above the minimum requirements.
scale use of the cleaning system.
One can then optimize the paramaters by successive iterations
of cleaning performance testing by going halfway between the
last combination of variables that worked (and the last combi- REFERENCES
nation that failed) until satisfied that the system has been suf- Guidebook of Part Cleaning Alternatives, Karen Thomas Massachusetts
Toxics Use Reduction Institute. John LaPlante, Alan Buckley
ficiently optimized for the specific cleaning needs. Massachusetts Office of Technical Assistance, March 1997.
One can also hold any one or more variables constant, Developing a System, from Alconox Cleaning Solutions, Vol 1, Number 3.
such as a maximum practical length of time, or a maximum
safe cleaning temperature while optimizing the other vari-
ables. For example, if one needs to be able to clean a batch of RESOURCES
parts in two minutes, then vary the temperature and concen- www.alconox.com
tration within the two-minute time constraint. www.clean.rti.org
www.cleanersolutions.org

62 The Aqueous Cleaning Handbook Testing and Selecting A Detergent and Cleaning System 63
 CHAPTER SIX

Industrial
Cleaning Applications
T oday, new applications for aqueous cleaning are found in a
wide range of industries—laboratory science, healthcare, phar-
maceuticals, food-and-beverage processing, metalworking,
and precision manufacturing of glass, plastic, and metal com-
ponents.
This chapter describes key considerations in aqueous
cleaning for each of these industries.

HEALTHCARE
The ultimate goals of healthcare cleaning procedures are to
keep instruments and equipment clean and sterile, prolong their
working life, minimize cross-contamination, and reduce med-
ical waste. The ideal detergent for getting reusable items clean
has a neutral-range pH, in order to prevent corrosion or other
surface degradation. When proteinaceous soils from blood or
body fluids must be cleaned, adding enzymes to a cleaner
means the instruments will come clean with soaking and gentle
cleaning rather than abrasive scrubbing—thus prolonging their
working life and decreasing the chance of cross-contamination.
Cleaning in a healthcare setting often means preparing a
surface for sterilization. It is very important to have a clean sur-
face with no dirt on it so that when a sterilization process is car-
ried out you do not wind up sterilizing the dirt—leaving unster-
ilized surfaces beneath the dirt. In short, effective sterilization
requires effective cleaning.
Although healthcare instruments themselves are often
made up of robust plastics or stainless steel, the trays they are

64 The Aqueous Cleaning Handbook Industrial Cleaning Applications 65

handled in as instrument kits and are cleaned in are often
made of light-duty plastics or aluminum. Therefore, the clean-
ing agents chosen must not damage the light-duty plastic or
aluminum instrument-handling trays.
TABLE 6A DETERGENT SELECTION GUIDE FOR HEALTHCARE CLEANING
Application
Key Concerns Articles Cleaned/Soil Removed Cleaning Method
Healthcare Surgical, anaesthetic, and examin- Manual, Ultrasonic, Soak
Effective prepara- ing instruments and equipment. Machine washer,
tion for steriliza- Catheters and tubes. sani-sterilizer
tion, longer instru-
ment life. Minimize Difficult proteinaceous soils, blood Manual, Ultrasonic, Soak
cross-contamina- and other body fluids, tissue on Machine washer,
tion. Reduce waste. instruments. sani-sterilizer
Healthcare instruments that are cleaned are usually exam-
ining instruments of one kind or another. Most healthcare
instruments that come into contact with blood or body fluids
are disposed of so as to completely eliminate, or substantially
reduce, the risk of cross-contamination from blood-born
pathogens. Some reusable examining and probing instruments
(such as endoscopes) actually come in contact with blood or
body fluids and must be cleaned very carefully.
Cleaning healthcare instruments varies from cleaning
small groups of instruments—such as what may be found in
an individual doctor’s office or clinic—that are handled in
small soak trays and sometimes cleaned ultrasonically, to
large-scale central cleaning found in hospitals and large med-
ical centers. In control cleaning, the instruments in the entire
facility are grouped in trays and sent to a central cleaning or
central sterilization facility. These facilities will typically use
large batch washer/sterilizers to perform their cleaning.
PHARMACEUTICAL
Pharmaceutical process equipment cleaning includes every-
thing from bench scale lab production for trial use to full scale
manufacturing of bulk pharmaceuticals. All share the need to
clean and document to government regulated standards. These
standards are commonly called GMP (good manufacturing
practice) or the update as cGMP (current good manufacturing
practice). There are regulations that need to be complied with
66 The Aqueous Cleaning Handbook
from the US FDA, the EU (European Union), and the Interna-
tional Conference on Harmonization (ICH), to name a few.
For a discussion of the cleaning validations required under
these regulations see the chapter 8 on cleaning validation. For
examples of the types of standard operating procedures
(SOPs) used in pharmaceutical process equipment cleaning
Recommended
see the Chapter 7 on cleaning procedures.
Detergent The types of residues that need to be cleaned range from
Mild alkaline easy to clean water-soluble excipients to difficult
Inhibited low-
foam alkaline petrolatum/metal oxide mixtures. To simplify regulatory com-
Enzyme pliance, it is desirable to use as few cleaners as you can to
Inhibited low-
foam alkaline remove the entire range of residues encountered. It is also
desirable for these cleaners to be effective on a wide range of
residues used in a wide range of cleaning techniques, from
manual, soak and ultrasonic cleaning to clean-in-place spray
systems.
The materials of construction that typically need to be
cleaned are glass, 316L stainless steel, Teflon, polypropylene,
and silicon elastomers used in seals. In some cases, pharma-
ceutical manufacturers will use disposable seals, pipes and fil-
ters to avoid having to validate their cleaning. It can be safer
and more cost effective to use some equipment once rather
than clean it.
There is no more demanding application for precision
cleaning than pharmaceutical manufacturing—where cross-
contamination can be costly in lost product and the creation
of risk to human and animal health.
Today many leading drug companies, as well as firms that
manufacture medical devices, are finding that aqueous clean-
ers provide the same kind of scrupulous cleaning required for
processing healthcare products. Examples:
• Capsules and tablets—Some pharmaceutical ingredi-
ents resist going into solution, making tablet presses and
dies difficult to clean. Even stubborn, sustained-release
product residues come clean quickly with appropriate
aqueous cleaners.
• Suspensions—Aqueous cleaners also eliminate intensive
scrubbing and human contact in cleaning large stainless
steel tanks (even 2,000 gal) used in manufacturing liquid
suspensions.
Industrial Cleaning Applications 67
 • Intermediates—Aqueous cleaners are ideal for cleaning
glass-lined chemical reactors used in processing pharma-
ceutical intermediates such as powders, fillers, binding
agents, and other chemicals.
TABLE 6B DETERGENT SELECTION GUIDE FOR PHARMACEUTICAL CLEANING
Application
Key Concerns Articles Cleaned/Soil Removed
Pharmaceutical Product-contact surfaces.
Passing cleaning
validation for FDA
good manufactur-
ing practices.
Inorganic residues, salts, metallics,
pigments.
Protein/ferment residues. R/O, U/F
membranes.
*Clean-in-Place by circulating, for spray clean-in-place see machine washer detergents.
In research and development, aqueous cleaners have long
been used in cleaning metal, glass, plastic, and polymer com-
ponents for benchtop labware as well as for difficult-to-clean
pilot processing equipment such as bioreactors and fermenta-
tion systems.
Controlling Pyrogens—One of the considerations in phar-
maceutical process equipment for parenteral product cleaning
is controlling pyrogens. Pyrogens are endotoxins or cellular
debris that can cause fevers if people are internally exposed.
Pyrogens are often controlled using heat. The cleaner
Liqui-nox (Alconox, Inc. catalog number 1201) and Alconox
(Alconox, Inc. catalog number 1104) are used to depyrogenate
heat sensitive surfaces (as well as those treated by standard
heat treatment). As standard cleaning with 1% 120 deg F (50
deg C) Liqui-nox by manual, soak, or ultrasonic agitation fol-
lowed by a thorough rinse with WFI (pyrogen free water—
water for injection) and post cleaning handling in a pyrogen
controlled environment or packaging can give adequate pyro-
gen control. Stoppers for injectables are cleaned using Alconox
powdered detergent solutions.
A recent article (Hallie Forcinio, Pyrogen Control, March
2001 Pharmaceutical Technology p38) made reference to con-
trolling pyrogens with the following:
68
Pyrogens on packaging materials can be controlled by
heating alone or in combination with alkali or strong oxi-
dizing solutions or by washing with detergent
(1)...Pharmaceutical makers can render plastic containers
pyrogen-free by washing the containers with an alkaline (ie
pH 9-10) cleaning agent on a machine integrated with the
filling line. When washing is the pyrogen-removal method
of choice, any cleaning agent residue must be adequately
removed...The favored method of removing pyrogens form
Recommended stoppers is washing... many stopper makers now offer pre-
Cleaning Method Detergent washed stopers, which are treated to reduce endotoxin lev-
Manual, Ultrasonic, Soak, Mild alkaline els by 3 logs. 1
C-I-P*
Machine washer, Low-foam alkaline
power wash Liqui-nox is certainly a detergent that is used in pyrogen
Manual, Ultrasonic, Soak, Mild acid
C-I-P* control. Most laboratories that do LAL testing for pyrogens
Manual, Ultrasonic, Soak, Enzyme use Liqui-nox to clean their glassware and testing equipment.
C-I-P*
Stainless Steel Cleaning—Since stainless steel and glass
are common substrates cleaned, it is worth taking a closer
look at some of their surface properties and how that effects
cleaning and how to optimize thermodynamics of cleaning by
controlling the pH of the cleaning solution.
In aqueous critical cleaning there are numerous well-
understood factors in detergency affected by pH. Far less well
known, however, is the role pH can play in harnessing electro-
static affects to improve cleaning efficiency. Since like charges
repel, choosing a cleaner of appropriate pH relative to the iso-
electric point of the surface and the pKa (inverse log of the
acid dissociation constant, see table 1) of the residue makes
cleaning far more efficient—especially when cleaning residues
such as acids, bases, and amphoteric proteins, all of which can
have their electrical charges manipulated by pH.
The isoelectric point of a surface is the pH at which the
surface’s electric charge is neutral with regard to its acid/base
and electron donor-acceptor reactions. Moving to a higher or
lower in pH will shift the effective surface charge or electron
density in a negative or positive direction. Examples:
• Steel—typically has an isoelectric point of 8.5 associated
with the reactivity of the oxygen in the oxides Fe2O3,
Fe3O4, and Cr2O3 on the surface of the metal and the
hydrates and hydroxides formed in aqueous solutions.
1
W.A. Jenkins and K R Osborn, Packaging Drugs and Pharmaceuticals, Technomic Publishing
Co, Lancaster PA, 1993, p 28.
The Aqueous Cleaning Handbook Industrial Cleaning Applications 69
 • Glass—has an isoelectric point of 2.5 associated with the
SiO2.
Raising the cleaner solution pH (past the isoelectric point),
causes the surface takes on a more negatively charged charac-
ter. If the residue to be remove also has a negative charge at
that pH, then the negative surface will repel the negatively
charged residue.
In addition to material surfaces, many residues can also
undergo a change in electrical charge due to a simple change
in their pH. For most acids, the pKa indicates the pH at which
the hydronium ions and conjugate base are present in equal
concentrations. Moving higher in pH shifts the equilibrium
toward the right, thereby increasing the concentration of the
negative conjugate base. Thus, when cleaning acids it is desir-
able to use a cleaning solution with a pH above the isoelectric
point and the pKa of the acid. This results in an increase in
the concentration of the negative conjugate base, with a pH
above the isoelectric point of the surface where the surface
will take on a repelling negative character.
TABLE 1 RELATIONSHIP OF pKA, CONJUGATE BASE
AND HYDRONIUM ION CONCENTRATION
HA + H2O ➔ H3O+ + A-
[HA] = acid concentration H2O = water H3O+] = hydronium [A-] = conjugate base
concentration concentration
pKa = –log [H O+ ][A-]/[HA]
3
For example, with stearic acid (C17H35COOH), the conjugate
base is the negatively charged stearate ion (C17H35COO-). The pKa
is about 5. This means that at a pH of 5 and above, we begin to
drive the reaction toward the right, thereby converting stearic acid
to negatively charged stearate ion.
If the stearate ion is a residue on steel and the pH is as high as
8.5 and above, then not only do we have negatively charged
stearate ions due to being above the pH of 5, but also steel surfaces
that are negative in character by virtue of their being at a pH above
the isoelectric point. The steel and the stearate ions repel each
other, facilitating cleaning.
As in table 2, for basic residues, these condition would be
70 The Aqueous Cleaning Handbook
reversed to be below the pH at the pKa and the isoelectric point of
the surface being cleaned in order to achieve a positive-positive
repulsion, or at least a neutral residue and a positive-character sur-
face without attraction.
TABLE 2 OPTIMIZING THERMODYNAMIC CLEANING CONDITIONS
FOR SURFACE/RESIDUE ELECTROSTATIC REPULSION
Acidic residues pH > pKa and isoelectric point of surface
Akaline or basic residues pH < pKa and isoelectric point of surface
For any cleaning, however, it is important to also consider the
corrosive effect of pH on the surface being cleaned. Typically, it is
desirable to choose a cleaner with a pH that will not etch or cor-
rode the surface—for stainless steel, within the limits of passiva-
tion, and for glass, within the limits of etching. (It is important to
note that the addition of corrosion inhibitors can also extend the
acceptable pH range.)
Clean-in-place (CIP) Cleaning—As pharmaceutical processes
go from R&D to pilot scale to manufacturing, the cleaning tech-
niques and equipment can change to fit the needs of the scale of
manufacturing. A bench scale system can often be adequately
cleaned by manual and soak cleaning procedures. As systems
become larger it can be worthwhile to install clean-in-place (CIP)
systems. Parts of the following discussion on CIP cleaning is para-
phrased from the website operated by Dale Seiberling—the self
proclaimed CIP Evangelist (www.seiberling4cip.com).
CIP cleaning can be accomplished by the action of a cleaning
solutions with spray or recirculation under pressure of the initial
flush, wash, and rinse solutions by controlling time, temperature
and cleaner concentration.
• Piping Systems can be effectively cleaned via recirculation
of flush, wash, and rinse solutions at flow rates which will
produce a velocity of 5 feet per second or more in the largest
diameter piping in the CIP circuit.
• Mixers, tanks and blenders can be effectively cleaned by
distributing flush, wash and rinse solutions on the uppers
surfaces at pumping rates equivalent to 2.0-2.5 Gpm per foot
of circumference for vertical vessels, or at 0.2-0.3 Gpm per
square foot of internal surface for horizontal and rectangular
tanks.
Industrial Cleaning Applications 71
 • Integrated CIP Design may be applied to combine the clean-
ing of vessels and piping in one pass in which flush, wash
and rinse solutions to the sprays, and providing for solution
return to the CIP system. This concept can accomplish CIP at
the minimal capital cost and is highly effective in reducing
the post CIP recontamination that often follows conventional
cleaning of lines and vessels in separate circuits.
A CIP monitoring and control system can be installed to ensure
that the CIP system works reliably, rendering the process vessels
and piping molecularly spotless after every product run—or alarm
loudly if it fails. The CIP monitoring and control system can docu-
ment the system’s operation and history, and archive this informa-
tion for regulatory compliance. One way to set up a monitoring
system is to first circulate and flush water through the CIP system
with the control system monitoring the valves and pressure to
assure and record proper operation; proceed to the wash cycle,
possibly using conductivity control to measure and record proper
addition of cleaner solution; flush out the cleaner solutions and
proceed to neutralization and rinsing steps. Final rinses can be cir-
culated to equilibration for rinse water sampling if desired.
GMP Washing Machines—Equipment that is disassem-
bled for cleaning, manufacturing tools, and bench scale pro-
duction equipment that can be loaded into racks can often be
best cleaned in a washer that can do validated cleaning.
GMP Washer/dryer design—within the pharmaceutical
industry there has been, and continues to be, a struggle for a
clear definition of mechanical washer/dryer to properly
address the requirements of GMP applications. Within the
GMP regs there exists several specifications (Part 133.4, 1963,
and part 211.67, 1978) that attempt to bring some clarity to
the design concept. Unfortunately, these regulations leave
many areas open for interpretation with respect to specific
construction criteria for a GMP Washer. With no clear defini-
tion, many variations of “lab style” washers have been adapted
for this arena with their limitations not evident until long after
the purchase and installation.
There are inherent design criteria required for washer/dry-
ers that will clean parts, glassware, plasticware and tooling
used in pharmaceutical production adhering to GMP compli-
72 The Aqueous Cleaning Handbook
ance. The overall scope of the design criteria is to follow FDA’s
rationale that cleaning equipment should “prevent contamina-
tion or adulteration of drug products.”
Structural Flexibility—The design of the GMP washer
has evolved over the past 10 years from a modified laboratory
washer manufactured in a common production line, to a spe-
cific product division within the most up to date manufactur-
ers. Complete separation of tooling and superior welder quali-
fications are requirements for this range of products as quality
control and documentation of the entire construction process
is closely recorded and provided as a deliverable in the final
documents. The washer/dryer must be able to perform a multi-
use task while taking into consideration effective utility and
floor plan consumption. Effective use of the chassis must
allow for service and technician access as well.
For the outer shell of the washer, materials of construction
should be 316L so as to allow for integration into the clean
suite arena and be able to withstand the cleaning chemicals
used in this arena. Service panels should be able to be
designed to allow for access to the critical components
through mechanical chases or locations that the design of the
facility allows. Many times, the washer must adapt to the par-
ticular features of the room that requires the positioning of
the internal components to be accessed by the facilities or vali-
dation teams during and after the installation and calibration
process. Temperature and monitoring instrumentation should
be able to be removed from their ports via tri-clamped connec-
tion and have enough coil length to be able to be placed on a
metrology cart outside of the structure of the washer. This will
allow for easy calibration and verification during validation.
Freestanding or recessed models must be available to give
the facility the product flow characteristics required for their
process.
Chamber Flexibility—for faster cycle times, effective use
of the chamber will allow for a minimization of cycles and a
higher throughput of the washer/dryer during the production
day.
Chamber design should allow for minimal water retention.
Chamber corners should carry a minimum of 1” radius and all
surfaces should be sloped to the drain. Internal structures of
Industrial Cleaning Applications 73
the chamber should feature rounded edges with no threads or
entrapment areas. 316L stainless steel finished to a uniform 25
Ra should be a baseline for these washers.
Care should be taken with respect to the mating of the
inventory systems to the hydraulic circuit. There should be no
mechanical attachment required for the accessory racks.
Spray headers should be positioned at the top and the bottom
of the basin to aid in the cleaning of the parts positioned In
keeping with design criteria of utility savings and GMP con-
struction, the chamber volume should be sized to match the
load configuration required for a specific facility.
Care should also be taken to match the items to be cleaned
so that an effective load and unload pattern can be established
that minimizes operator errors. Multiple level loading configu-
rations will allow for maximum utilization of the chamber vol-
ume while minimizing the consumption of WFI.
Effective use of Teflon and stainless will allow racks and
baskets to mate to the chamber of the washer. (Threaded con-
nections are to be avoided as they are entrapment areas for
water and particulate that could lead to cross contamination
of the products being cleaned.)
Since loads for GMP cleaning can range from glass to plas-
tic to stainless parts, the design of a loading surface should
allow for the weight associated with these components. Two
types of doors are typically available for this application:
• Vertical doors—These allow for easy access to the items
to be cleaned but make it difficult to provide for a seal to
the chamber and require the use of loading trolleys, thus
adding to the number of accessories in the clean suite.
Vertical doors typically have a window built in that has
become popular with lab-style washers but have no func-
tionality in GMP. (Internal lights required for their use
need gaskets that have maintenance issues and the doors
are prone to leakage and service maintenance that may
not be possible during a production run. )
• Horizontal drop-down doors—These provide for an
effective loading table that also serve as an effective con-
tainment structure for the chamber. Gaskets can be
matched to GMP requirements that will allow for com-
plete sealing of the chamber thus allowing for no partic-
74 The Aqueous Cleaning Handbook
ulate migration into or out of the chamber. The door in
the down position provides an effective loading table for
the operators to easily access three sides of the rack to
place components to be cleaned. Heavy parts can be
placed on the door without having to reach into the
chamber of the washer. Teflon wheels on the racks can
provide for a smooth transition into the chamber.
Component Selection—Internal components must be
compliant to GMP requirements. Sanitary diaphragm valves
should be available for all areas that come into contact with
process fluid. Plumbing should utilize orbital welds wherever
possible and be finished to a minimum of 25 Ra. Dead legs
should be kept to a minimum of 6 pipe diameters. 316L stain-
less steel should be the material of choice for all metallic
areas. Cold rolled steel, copper, and other forms of stainless
(except 304L for the frame) should be avoided at all times.
Special attention should be placed with the chemical deliv-
ery system. This has been an overlooked area of GMP washer
design due to the difficulty and expense of providing for an
effective solution. Delivery systems must allow for the addition
of precise amounts of additives (caustic detergents and acid
based products) and must withstand to the harsh nature of the
ingredients that is being delivered. Many times, a commercial
laundry chemical system is used only to be the source of fail-
ure months after qualification, resulting in costly down time
of the production facility.
Drying systems should provide complete coverage to all
aspects of the load. Additionally, the washer itself should be
dried entirely and prepared for the next validated cycle. Non-
shedding materials should be used throughout the drying cir-
cuit. High temperature rated HEPA filters should be the final
point for the air entering the basin or accessories so as to pro-
vide for a clean, particulate free drying process. DOP challenge
ports should be provided so that the integrity of the HEPA’s
can be challenged on a regular interval. Separate circuits for
the basin and the hydraulic circuit (including the internal
parts for the loading accessories) will provide for the fastest
and most effective cycles. This design is inherently more
expensive but can be justified quickly.
Industrial Cleaning Applications 75
 Inventory Systems—As important as the construction of
the chamber, chassis, and internal components are to the over-
all performance of the washer, the inventory is often the most
overlooked aspect part of the project. Most often, manufactur-
ers are criticized for the mating of the inventory system to the
chamber and to the parts to be cleaned. This aspect of the pro-
ject involves a complete inventory of the components to be
cleaned, their dimensional information, weight and specific
cleaning requirements. Once this information is assembled the
parts need to be grouped together in the loads that are
required by the facility to be cleaned and an idea can then be
formulated as to the chamber volume required to complete the
task. Ergonomics should be reviewed so as to not overload the
operator and to maximize the parts/run in order to minimize
the utility consumption of the facility.
Documentation Requirements—The final part of the
package for a GMP washer is the associated documentation
that will give the validation teams the information whereby a
complete qualification of all aspects of the system can be
implemented.
The documentation package should contain (as a mini-
mum) the following components:
• User’s manual
• Maintenance manual
• Instrument list
• Electrical diagram
• Piping and instrumentation diagram
• Spare parts list
• Exploded view
• Welding report and welder certificate
• Source codes are provided in the form of a written copy,
a floppy disc, and a spare E-prom
• Passivation report
• As built drawings
• IQ/OQ documentation
Cleaning of components utilized in a GMP environment
presents obstacles that are not found in generic washing of
76 The Aqueous Cleaning Handbook
glassware or parts for the lab or research function. Additional
challenges such as materials of construction, soiling of active
pharmaceuticals, load configurations, and regulatory con-
straints add to the difficulty of this operation. However, when
properly managed, this task can be easily transitioned and
implemented. A typical procedure for the understanding and
evaluation of a wash protocol would include the following:
A. A clear understanding of the items to be cleaned. This
definition is paramount to the success of a validated
system in that the operator must load and unload in
specific steps so as to maintain the validation of the
cycle. Ergonomics of the load and rack must be
addressed at this point so as to make the additional
design and steelwork feasible.
B. An understanding of the soiling that will be on the parts
to be cleaned. Any active pharmaceuticals must be
addressed and evaluated as to their abilities to be
cleaned within the limits of time/temperature/chemi-
cal/agitation.
C. Load patterns must then be addressed. In many applica-
tions specific components must be kept together during
the cleaning phase so as to maintain their validated sta-
tus in the scope of the process. This challenge requires
that the design function of the inventory systems for the
GMP washer have a full understanding of the materials
that will be cleaned as well as their dimensional aspects.
Parts can then be arranged on a CAD drawing to illus-
trate the functionality of the rack and determine if there
are going to be any load/unload problems to overcome.
It is this point that a clear definition of the cleaning
cycle parameters can begin to come into focus.
D. Programming aspects of the PLC or microprocessor can
then take into account the requirements of the washer
to perform the task to clean the items in the chamber.
System monitoring and data transfer to other monitor-
ing locations will occur at this point and will play a part
in the design.
With these considerations, it is possible to successfully use
a GMP washer to clean pharmaceutical equipment.
Industrial Cleaning Applications 77
BIOTECHNOLOGY
When biotechnology goes into production for biopharmaceuti-
cals and gene-therapy products, the cleaning requirements can
be very similar to pharmaceutical needs. The residues that
need to be cleaned are often complex mixtures resulting from
fermentation and cell culture. The cleaners used must not
leave interfering residues that inhibit culture growth or unac-
ceptable levels of batch-to-batch contamination. As in pharma-
ceutical process equipment cleaning, disposable single use
items may be used for piping, seals, and filters. When pharma-
ceuticals are manufactured, even at R&D pilot scale for trials,
GMP procedures must be followed. The GMP washers
described in the preceding section are often used for biophar-
maceutical cleaning. See chapter 8 on cleaning validation and
Chapter 7 on standard operating procedures, particularly the
example given on cleaning fermentation equipment.
MEDICAL DEVICE MANUFACTURING
The cleaning done during medical device manufacturing is
performed in preparation for sterilizing and sterile packaging
of medical devices. When selecting a detergent, careful consid-
eration must be given to the materials from which these
devices are composed. Usually medical devices are made of
fairly robust materials that can withstand corrosive blood and
body fluids. In some instances, one portion of the device is
intended to come into contact with skin, blood, or body fluids.
Other parts of the device are exterior to the human body and
may be made of less sturdy plastics or aluminum. If these less
sturdy materials are present, a milder detergent should be
selected.
Medical devices are usually assembled under fairly clean
conditions. As a result, a light-duty cleaner is usually selected
to remove light quantities and types of soils.
Good medical device design entails creating devices that
do not have small crevices, cracks, and difficult-to-clean or
reach places. Often, medical devices are manufactured in
modest quantities, lending themselves to batch-cleaning oper-
ations. Ultrasonic cleaning is a common cleaning method in
medical device manufacturing. This, coupled with the fact that
cleaning operations typically remove only light oils from
78 The Aqueous Cleaning Handbook
processes—or small particulates that are present in the rela-
tively clean manufacturing environment—requires selecting
extremely free-rinsing detergents suitable for immersion
cleaning.
For parenteral medical devices designed to be implanted
inside the body, a key consideration is that there be no endo-
toxins or pyrogens present on the surface. Endotoxins or pyro-
gens are fever-causing cell debris or cell-waste products widely
present in the environment. Cleaning these pyrogens or endo-
toxins requires the use of a high-emulsifying cleaner combined
with heat, followed by rinsing with pyrogen-free or endotoxin-
free water. This type of water is often called water for injection
(WFI). WFI is very high purity water derived from high-purity
water filtration systems.
LABORATORY CLEANING
Despite the increasing use of disposable plastics in the laboratory,
reusable glass labware is still widely employed. This is due to envi-
ronmental concerns (recycling issues and disposal problems asso-
ciated with plastics), and because the vast majority of procedures
require glass. In addition, there are instruments and equipment,
which for scientific or economic reasons, must be reused.
The principal concern for any scientist or technician working
with laboratory glassware, instruments, and equipment is that they
be free of interfering residues. These often unseen residues can
cause invalid analytical results. For example, they can erroneously
accelerate or decelerate rate dependent experiments by causing
localized high concentrations of reactants inside micelles. They can
inhibit culture growth, cross-contaminate batches, and cause non-
reproducible results.
To solve these problems, equipment must be cleaned thorough-
ly and any interfering residues removed. This requires that an
appropriate laboratory detergent be selected and an effective clean-
ing method used (Table 6C).
Industrial Cleaning Applications 79

TABLE 6C DETERGENT SELECTION GUIDE FOR LABORATORY CLEANING
Application
Key Concerns Articles Cleaned/Soil Removed
Laboratory Glass, metal, plastic labware, ceramics, tis-Manual, Ultrasonic, Soak, C-I-P*
Reproducible sue culture, porcelain, clean rooms, animal
results, no interfer- cages, bioreactors, tubing, benches, safety
ing residues, equipment.
extending equip-
ment life. Keep lab- Tubes, reusable pipets.
oratory accredita-
Water and environmental sampling.
tion. Laboratory Phosphate-sensitive labware. EPA procedures. Machine washer, labware washer
safety.
Radioactive equipment/contaminants.
Stopcock grease.
Trace metals, metal oxides, scale.
Proteinaceous soils, bio-wastes, tissue, blood Manual, Ultrasonic, Soak, C-I-P*
and other body fluids, fermentation residues Glassware washer
*Clean-in-Place by circulating, for spray clean-in-place see machine washer detergents.
The following are common laboratory-cleaning procedures,
along with guidelines for eliminating interfering residues.
1. Soaking is used to clean small items and the insides of
larger vessels. It should be used as a pretreatment to prevent
soils from drying onto labware. A soak tank should be kept
at the laboratory bench for immersing used labware until
such time that it can be washed. Soaking is also effective to
clean or pretreat very difficult, dried-on residues. To clean
by soaking, a detergent recommended for soaking should be
used, and a detergent soak solution made up according to
the directions. The article should be completely submerged
to prevent any deposits or etching at the air/solution inter-
face. Soils should be soaked until they are removed; this
may take several hours. Some soils may require additional
agitation or wiping in order to remove them. A thorough
rinse follows.
2. Manual cleaning is used to clean small batches of labware
equipment and benches. It is the most commonly used labo-
ratory cleaning method. To clean manually, the article to be
cleaned should be wet either by immersing it in the deter-
gent solution, or by using a soaked cloth or sponge. For
nonabrasive scouring, un-diluted detergent should be
poured onto a wet cloth or sponge for scrubbing. A cloth,
sponge, brush, or pad can be used for cleaning. A thorough
rinse follows. Protective gloves and eye protection should be
worn if recommended or required.
80
Cleaning Method
Machine, powerspray, labware
washer, washer-sterilizer, cage-
washers
Siphon-type washer-rinsers
Manual, Ultrasonic, Soak, C-I-P*
Manual, Ultrasonic, Soak, C-I-P*
Machine washer, warewasher
Manual, Ultrasonic, Soak, C-I-P*
The Aqueous Cleaning Handbook
3. Ultrasonic cleaning is used for larger numbers and repeti-
tive batches of labware cleaning. To clean in an ultrasonic
Recommended
Detergent tank, a solution is made up in a separate container, the ultra-
Mild alkaline sonic tank filled, and the machine run for several minutes to
Low-foaming alkaline degas the solution and allow the heater to reach the correct
temperature. Small articles should be placed in racks or bas-
Tablet
kets; irregularly shaped articles aligned so that the long axis
Mild alkaline
faces the ultrasonic transducer (usually the bottom); and the
Phosphate-free, low foam
High emulsifying, mild alkaline ma-chine should run 2–10 minutes until parts are clean. A
Low-foaming alkaline,
high emulsifying, alkaline
thorough rinse follows.
Mild acid 4. Automatic syphon washing is an effective way to clean
Enzyme Cleaner
reusable pipets. The pipets should be placed completely cov-
Low-foaming alkaline
ered in a detergent soak solution as soon as is practical after
use. This prevents soils from drying onto the pipes. When
ready to clean, the pipets are placed in a holder; an efferves-
cent tablet cleaner is dropped into the washer; the pipets are
placed in a holder over the tablet; and the cold or warm
water is turned on at a rate that will fill the washer to cover
all of the pipets and allow them to drain thoroughly. This
may take as long as an hour. For analytical use, a final rinse
in deionized or distilled water may be required.
5. Machine washing is used in laboratories for cleaning
large quantities of reusable labware. The machine’s direc-
tions should be consulted for details on its proper use. In
general, the labware is loaded on racks with open ends fac-
ing the spray nozzles. Narrownecked flasks should be placed
in the center of the racks, preferably on specially designed
spindles with spray nozzles directed into the necks.
Handling of the labware in the racks should be kept to a
minimum. Small articles should be grouped in baskets to
prevent dislodging by spray. Only low-foaming detergents
designed for these machines should be used. Typically, 10
mL of detergent per liter of hot, wash-cycle water (approxi-
mately 60˚C) is used.
6. Rinsing is an often overlooked and very important part of
laboratory cleaning. A thorough running water rinse that
contacts all surfaces of an article for at least ten seconds per
surface may be required. Filling and emptying small vessels
with rinse water at least three times is a good rinse proce-
dure. For machine cleaning, there should be at least three
Industrial Cleaning Applications 81
 rinse cycles after cleaning. Final or all rinses in water of should follow to assure that there is no such cross-contamination:
suitable purity should be used for analytical labware to 1. Use a laboratory-grade cleaner that does not contain any of the
remove any tap water residues. For tissue culture and gener- types of ingredients that can be analyzed to eliminate the pos-
al analytical ware, a deionized or distilled water final rinse sibility of any detergent residue that can cause cross-contami-
should be used. Trace organic analytical ware should be nation.
rinsed in distilled or organic-free water. Trace inorganic ana- 2. Perform equipment “blanks” by cleaning glassware or handling
lytical ware should be rinsed in deionized water. and sampling equipment and then performing an analysis on
Pharmaceutical and clinical research labware may require the glassware or equipment to determine whether it has any
sterile, pyrogen-free, or injectable water rinsing, depending contaminants. For example, a U.S. Environmental Protection
on the work being done. Agency protocol calls for the use of phosphate-free laboratory
grade detergents such as Alconox or Liqui-Nox. Phosphate-free
Following these procedures diligently may help to ensure that cleaners are specified because in water analysis, where one is
one’s research is not fraught with the problems associated with inter- often testing for the presence of phosphates, this procedure
fering residues on the surfaces of reusable labware, instruments, or eliminates the potential risk of cross-contamination from phos-
equipment. phates. (Note: Alconox is a phosphate-containing detergent. It
has been used for cleaning phosphate analysis labware for
ENVIRONMENTAL AND WATER TESTING many years. When rinsed thoroughly, it will not leave phos-
Typically trace analyses—usually for trace organics—are conducted phate residues.)
for pesticides, known carcinogens, and known toxic organic com-
pounds. (The EPA can provide a list of types of organic compounds FOOD AND BEVERAGE PROCESSING
which might reasonably be testing for.) Other trace analyses focus on In food and beverage processing one is faced with hard surfaces that
inorganic compounds—typically trace metals due to their toxicity are fairly robust and can stand up to the corrosive environments typi-
including metals such as mercury, cadmium, and zinc. cal of this industry. Even meat that contains blood can be fairly cor-
rosive, orange juice is fairly acidic, while other foods have their own
TABLE 6D DETERGENT SELECTION GUIDE FOR ENVIRONMENTAL CLEANING tendencies to attack hard surfaces.
Application Recommended
Key Concerns Articles Cleaned/Soil Removed Cleaning Method Detergent
Environmental Bailers, samplers, augers, Manual, Ultrasonic, Soak, Phosphate free, mild TABLE 6E DETERGENT SELECTION GUIDE FOR FOOD AND BEVERAGE CLEANING
No interfering containers, tubing, teflon, glass, C-I-P* alkaline Application Recommended
residues. rubber, stainless steel. Machine wash, Low-foam, phos- Key Concerns Articles Cleaned/Soil Removed Cleaning Method Detergent
Phosphate free. pressure spray phate free, alkaline
Food & Beverage Stainless steel, food-contact Manual, Ultrasonic, Soak, Mild alkaline
*Clean-in-Place by circulating, for spray clean-in-place see machine washer detergents. Avoid interfering equipment. C-I-P*
residues on food- Machine wash, pressure Low-foam alkaline
contact equipment. washers
In some instances, such as with soil or water testing the purpose Oxides, scale, trace metals, salts, Manual, Ultrasonic, Soak, Mild acid
of the test is to determine general water quality. In such cases, milkstone. C-I-P*
Filter membranes. Proteinaceous Manual, Ultrasonic, Soak, Enzyme
trace analysis is often performed for toxins. Quantitative soils. C-I-P*
analysis is used for drinking water as well as in determining *Clean-in-Place by circulating, for spray clean-in-place see machine washer detergents.

soil quality for farming or gardening.

The key consideration for cleaning is to make sure all sampling Good process design should eliminate the cracks and
and handling equipment as well as glassware that comes into contact crevices and difficult-to-clean places in a properly designed
with the soil or water does not have any cross-contamination from food or beverage processing plant. In food-and-beverage pro-
the any previous soil or water tests. There are two procedures one cessing, manual cleaning is often employed for benches, coun-

82 The Aqueous Cleaning Handbook Industrial Cleaning Applications 83

ters, mixers, extruders, and processing equipment. This calls degrading it and the performance of the vacuum part. This type of
for cleaners that are effective in immersion cleaning. To clean cleaning requires a thorough understanding of the soils present on
these, you need high-emulsifying cleaners where there is a signifi- the part in order to choose a detergent that will be effective
cant amount of organic food residue. .
In meat or poultry processing plants where proteins are present it TABLE 6F DETERGENT SELECTION GUIDE FOR ELECTRONICS CLEANING
is advisable to use an enzyme cleaner. The types of hard surfaces Application Recommended
Key Concerns Articles Cleaned/Soil Removed Cleaning Method Detergent
found in these environments are typically stainless steel or robust
Electronics Circuit boards, assemblies, Manual, Ultrasonic, Soak, Ion-free
plastics such as high density polyethylene, or even ceramic surfaces. Avoid conductive screens, parts, conductive Machine wash, power spray, Ion-free,
residues, avoid residues, resins, rosins, fluxes,
One of the unique surfaces found in food or beverage processing CFCs, pass cleaning particulates, salts.
board and screen washers Low-foam

plants are filtration membranes used to filter various process streams
of food or beverage products. Examples include juice and decaffeinat-
ed coffee processing as well as cheese manufacturing. Such processes
often result in highly fouled, difficult-to-clean filter membranes
which are often very expensive filters with high value. Effective clean-
ing maximizes their useful life and returns their performance to high
rates of throughput.
Since the foods being filtered are by definition foods or nutrients,
these membranes are also frequently fouled by biocontamination that
grows on the nutrient value of the food, causing a condition known
as bio-fouling or bio-film. This type of fouling is often effectively
removed by an enzyme-based cleaner. Enzyme-based cleaners are
also desirable because they often can be made with a neutral or near-
neutral pH that won’t damage the membranes.
It is important to note that since some membranes are delicate
and cannot face harsh alkaline or acid cleaners, it is crucial to select
a detergent which will not cause membrane damage.
GENERAL ELECTRONICS CLEANING
Electronic components are usually made of metal due to their con-
ductive nature and their ability to be bonded by soldering. Soldering
involves the use of flux, an undesirable contaminant since it is not
only unsightly but acidic, thus causing corrosion of electronic com-
ponents.
Other types of electronic components are glass or ceramic insula-
tors. It is important to clean the surface completely in order to pre-
serve their insulating properties. Oils or other conductive residues or
particulates must often be removed.
A special consideration in electronics cleaning involves compo-
nents that rely on a vacuum to create an insulator. These include light
bulbs and vacuum tubes where residue can “outgas” into the vacuum,
criteria.
Ceramic insulators and Manual, Ultrasonic, Soak Mild alkaline
components. Parts washers Low-foam alkaline
Additional types of soils encountered in electronics cleaning are
solder flux residues, mold release agents, as well as metal oxides
formed on vacuum components. For example, metal oxides may be
found on frame holders.
While organic residues usually require some type of emulsifier
for their removal, metal oxides are frequently better removed by an
acid cleaner with high chelating or sequestering capacities.
PC BOARDS
A wide variety of contaminants can remain on the completed assem-
bly surface if they are not properly cleaned. These contaminants can
be:
• Ionic—those with an ionic charge, typically salts such as sodi-
um, potassium, and chlorides. These are of particular concern
because they are potentially conductive, mobile residues.
• Polar—having a dipole moment (a molecule with partially
charged, positive or negative ends or poles), in the sense that
“like dissolves like,” which tend to solvate ionic residues lead-
ing to the concerns previously discussed.
• Nonpolar—having no dipole moment, typically an organic
film with insulating and adhesion interfering properties for
bonding or marking.
• Nonionic—organic compounds that have no ionic charge and
are not salts. They may be either polar or nonpolar (as dis-
cussed previously).
Salts such as plating salts, etching salts, and activators are typi-

84 The Aqueous Cleaning Handbook Industrial Cleaning Applications 85

cally ionic. Many of the organic species are nonionic. However,
organic acids such as the rosin acids and organic acids used as acti-
vators are ionic. An organic molecule by definition is one based on
the element carbon.
The most detrimental type of contaminant is the ionic type. If not
cleaned away, ionic species of contaminants can cause serious prob-
lems including leakage currents between traces on a board as well as
severe corrosion. The presence of moisture greatly accelerates the
activity of ionic species since water solvates the ions and enables
them to become mobile. In the presence of an applied voltage across
circuit traces and moisture, dendritic growth can occur. This occurs
when atoms of the circuit trace migrate outward across the bare lam-
inate until they bridge the circuit width, causing an electrical short.
Mobile ionic species speed up this form of growth. Mobile ionic
species are also responsible for corrosion products being formed on
the assembly surface. Military contractors are required to apply a
conformal coating to protect the assembly surface from moisture. A
conformal coating is, of course, a polymeric material such as an
epoxy, polyurethane, or acrylic designed to protect the assembly sur-
face from moisture. In addition, conformal coatings also isolate cont-
aminants and prevent them from migrating or being dislodged during
temperature-moisture cycling, high vibration, shock environments,
etc.
Nonionic contaminants remaining on the assembly surface can
also lead to performance problems. These contaminants can interfere
with electrical bed-of-nails testing by creating electrical “opens.” They
can also lead to adhesion problems if a conformal coating is being
applied.
Ionic materials and some hygroscopic nonionic materials under
conformal coatings can also lead to blistering during
temperature/humidity cycling. This phenomenon is also called meal-
ing or vesication, and it takes place because no conformal coating is
100% effective against moisture penetration. In fact, the presence of
ionic material or hygroscopic material on the surface under the con-
formal coating actually acts to promote water penetration since such
contamination attracts water. Once the contaminant becomes hydrat-
ed, it builds up osmotic pressure which causes a lifting of the confor-
mal coating thus leading to the blister or vesicle. This type of phe-
nomenon must be considered detrimental to the finished assembly.
Finally, there is the phenomenon of white residue (WR). White
86 The Aqueous Cleaning Handbook
residue is not always white. It can be gray, tan, beige, or amber in
color. There are several possible causes. In some instances the assem-
bly butter coat is removed, thus revealing the glass weave intersec-
tions. This is known as measling. This can result if too harsh a sol-
vent is used for cleaning. Another instance of white residue is when
activator materials are left behind on the assembly surface. This can
come about if the solvent used for defluxing has become depleted of
alcohol (this is especially true of solvents based on trichlorotribluo-
roethane or CFC-113).
Another cause of white residue is solder paste. Solder paste con-
tains materials known as thickening agents (thixotropic agents or
rheological modifiers). These materials are difficult to remove during
the defluxing operation, especially without the expenditure of
mechanical energy, e.g., sprays. These thickening agent residues are
prone to form a white residue, especially if exposed to alcohol.
Exposure to alcohol can come about either from alcohol in the
defluxing solvent or alcohol in an ionic contamination tester.
However, the principal cause of white residue is due to thermal
degradation of rosin. Rosin readily undergoes degradation and poly-
merization (the molecules bond together to form a much larger mole-
cule). This is especially true when it is heated around 260˚C (500° F)
or higher. The rosin also interacts with tin and lead salts formed dur-
ing the fluxing operation by the activator action on the solder oxides.
The rosin interaction products are termed tin and lead abietates. The
polymerized rosin and/or tin and lead abietates are much more diffi-
cult to remove by a defluxing solvent because of their more insoluble
nature. Typically, the white residue appears after the defluxing opera-
tion after the defluxing solvent has flashed off. Both rosin fluxes and
rosin pastes are prone to form this type of white residue.
If this type of white residue appears, what can be done? First, it
is necessary to ascertain that the flux (or paste) is truly the source of
the white residue and to verify that the white residue does not have
another cause.
PRECISION ELECTRONICS
Aqueous cleaning technology is used to meet the high level cleaning
requirements in precision electronics manufacturing of disk drives,
semiconductors, and electrooptics. These industries use high purity
aqueous cleaners in controlled environment manufacturing settings.
These cleaners are made from high purity ingredients with filtration
Industrial Cleaning Applications 87
and purification steps in their manufacture. The end-user manufac- short contact times, rapid rinsing, and rapid drying to minimize the
turers may further filter the cleaners at the point of use. It is not chance for corrosion to occur. It is also critical to be careful using
unusual for a high-purity cleaner to be made in a clean environment extremely high purity deionized rinse water that can be so “ion hun-
where it is filtered to 5 microns and then have further filtration to gry” that it is corrosive to the metal substrate being rinsed.
levels such as 0.2 microns at the point of use. Delivery of finished
cleaner that is filtered to 0.2 microns or better requires manufactur- PLASTICS
ing, filtering and packaging in a cleanroom environment. Plastics cleaning involves the selection of a mild nondamaging clean-
er that is strong enough to remove the soils you are cleaning. As
PRECISION MANUFACTURING you can see in the table below, many plastics are resistant to
In many of today’s high-tech metalworking applications, surfaces attack by typical mild alkaline aqueous cleaners. For delicate
must be prepared by the removal of debris, oxides, scale, and salts to plastics consult the plastic manufacturer regarding their rec-
achieve extraordinary levels of cleanliness. Cosmetic factors can also ommendations for cleaner compatibility or use one of the spe-
enhance buyer perceptions—with a bright, oxide-free finish serving cially formulated plastic cleaners.
as visual indicator of product quality.
Numerous metalworking and metal finishing businesses are find- PLASTICS COMPATIBILITY WITH CLEANERS
ing that aqueous detergents perform as well as or better than solvent Generally acceptable with mild aqueous cleaners
cleaners in removing residues but without their harmful environmen-
tal side effects. Polyethylene (LLDPE, LDPE, PE)
Polypropylene (PP)
Among new, high-tech applications for aqueous cleaners are:
Polyallomer (PA)
• Anodized parts—An anodizing shop which produces anodic Polymethylpentene (PMP, TPX)
coatings on aluminum substrate caps for mounting personal Fluoroethylenes (FEP, TFE, PFA, ECTFA, ETFE, TEFLON®)
computer IC chips with no conductive tail-end residues and no Polysulfones (PSF)
introduction of toxicity or flammability. Polyvinylchloride (PVC)
• Computer parts—A major manufacturer of thermocouples Polystyrene (PS)
and wafers used in computers and medical devices must clean Polyvinyl fluorides (PVDF)
Polyeurethane
ceramics and copper paste in heated (150˚F) ultrasonic baths
Ethylene Propylene (EPM)
prior to nickel plating.
Buna N rubber
• Aluminum—A manufacturer of heat sinks for cooling com- Nordel®
puter chips in NASA space shuttles uses aqueous detergents to Viton®
remove oil and organic debris to eliminate any chance of non- Noryl®
condensable gas formation. Ryton®
Epoxy
In general, precision manufacturing with metals involves prepar- Clean with caution even with mild aqueous cleaners
ing the surface for bonding, coating, or exposure to an environment Polycarbonates (PC)
such as a vacuum or a semiconductor that cannot tolerate interfer- Acetal polyoxymethylene (ACL)
ence from residues. Thus it is important to make sure that the metal Nylon®
will not be attacked by the cleaning, rinsing, or drying process. Polymethylmethacrylate (PMC)
Unfortunately, corrosion inhibitors that leave deposits often cannot
be used for precision cleaning, so it is important to use mild cleaners,

88 The Aqueous Cleaning Handbook Industrial Cleaning Applications 89

 For more delicate plastics, a mild alkaline cleaner can
TABLE 6G DETERGENT SELECTION GUIDE FOR PRECISION MANUFACTURING
often be used at modest temperatures, low concentration, and Application Recommended
short contact times. The most challenging plastic to clean Key Concerns Articles Cleaned/Soil Removed Cleaning Method Detergent
Metalworking Glass, ceramic, porcelain, stainless Manual, Ultrasonic, Soak, Mild alkaline
without damage is stressed polycarbonate which is prone to and Precision steel, plastic, rubber. Oils, C-I-P*
stress cracking on exposure to low surface tension solutions Manufacturing chemicals, particulates. Machine washer, power wash Low-foam alkaline
Clean parts, avoid
Aluminum, brass, copper, and Manual, Ultrasonic, Soak, Mild alkaline
such as solvents and aqueous cleaners. Very dilute cleaner volatile solvents,
other soft metal parts. Oils, chemi- C-I-P*
strong acids, and
solutions may be needed to clean stressed polycarbonate. other hazardous cals, particulates. Parts washer, power wash Inhibited low-foam
chemicals. alkaline or neutral
Most plastics are organic in character which makes them Inorganics, metallic complexes, Manual, Ultrasonic, Soak, Mild acid
attractive to organic film residues. A high emulsifying cleaner trace metals and oxides, scale, C-I-P*
salts, buffing compounds. Parts washer, power wash Low-foam alkaline
is often required to remove organic films from cleaners.
Silicone oils, mold-release agents, Manual, Ultrasonic, Soak, High-emulsifying,
buffing compounds. C-I-P* mild alkaline
GLASS AND CERAMICS Metal oxides, scale, salts. Metal
Parts washer, pressure spray
Manual, Ultrasonic, Soak,
Low-foam alkaline
Mild acid
Glass and ceramic have excellent insulating, transparency, and brightening. C-I-P*
*Clean-in-Place by circulating, for spray clean-in-place see machine washer detergents.
dimensional characteristics that make them a desirable mater-
ial for many high-tech manufacturing applications. OPTICS
Since these are inorganic matrix materials, they often Aqueous detergents have also found application in the manu-
attract and hold inorganic soils such as salts and ions. facturing of scientific as well as consumer optics such as con-
Aqueous cleaners having good chelating properties or acidic tact lenses. For example, one manufacturer uses machining
pH are often effective at removing such inorganic soils. oils and heavy waxes to grind and polish its scientific optics to
Examples of the use of aqueous cleaners in glass and ceramic exacting tolerances. These must be removed from the surface
precision manufacturing include: of the finished product. The company’s technicians have found
• Ceramic crucibles—used in semiconductor-grade labs that an alkaline detergent—normally used in lab washers and
and in manufacturing need to be cleaned of any mobile ultrasonic cleaning systems—was ideal for removing such
ion residues prior to sales to semiconductor customers. wax. (They use a separate, pH-neutral cleaner to brighten the
Aggressive immersion cleaning using heated ultrasonics copper and copper alloys that surround these optics.)
with high wetting, high emulsifying cleaners has been On the consumer-product side, contact lens manufacturing
successful in providing suitable surfaces. also employs pH-neutral aqueous cleaners to remove the wax
used to secure silicon/acrylic copolymer lenses to collets for
CNC machine forming of the all-important base curve layer
which ensure proper fit and wearer comfort. The detergent
has also found application in removing the compounds used
in grinding rigid gas permeable (RGP) contact lenses.
Aqueous cleaners have been widely adopted in solvent-
reduction programs by metalworking and parts-washing oper-
ations. Often, the level of cleanliness required is either for
appearance only or for suitability for painting, bonding or
coating. It is critical to choose a detergent that is compatible
with the type of parts washer being used.

90 The Aqueous Cleaning Handbook Industrial Cleaning Applications 91

 For example, high-agitation cleaning solution machines NUCLEAR
such as bubble/air agitated immersion, spray wand, spray Few industries use more exotic alloys, nor have more stringent
booth, and conveyorized spray machines require the use of quality-control requirements in manufacturing, than precision
low-foaming cleaners. Circulated, static, and ultrasonic manufacturing of nuclear equipment. Components such as
immersion cleaning can be accomplished with high emulsify- guide tubes, end fittings, coil springs, grids, and fasteners used
ing, high foaming cleaners. Less rigorous rinsing is often in fuel assemblies for reactor cavities must be absolutely free
acceptable. Tap water may be a sufficient rinse and the traces of oils or other contaminants.
of water spots may be acceptable. One major manufacturer of nuclear fuel assemblies has
For appearance cleaning, however, a “no-rinse” process found that large parts such as 12-foot guide tubes can be effec-
involving merely wiping the parts or air blowing them may be tively cleaned through manual soaking in a 1:100 dilution of a
better when highly dilute cleaner solutions are employed. pH-neutral aqueous detergent and hot tapwater.
In reactor cavity cleaning, a specialty chelate-free aqueous
cleaner brand has been successfully used during outage proce-
TABLE 6H DETERGENT SELECTION GUIDE FOR OPTICS CLEANING
Application Recommended
dures at commercial nuclear-power plants and auxiliary build-
Key Concerns Articles Cleaned/Soil Removed Cleaning Method Detergent ings for radiological decontamination of floors, walls, tools,
Optics Lenses, substrates, mirrors, reflec- Manual, Ultrasonic, Soak Mild alkaline personal safety equipment, and components made of metal
Avoid optical tors, fibers Parts washers, machine Low-foam alkaline
interface washers and plastic—permitting release of cleaned items from con-
trolled areas.
The key consideration with on-site cleaning is that the
COSMETICS detergent contain no chelating agents which can bond chemi-
Cosmetic manufacturing involves many oils, pigments, emol-
cally to radioisotopes, It should also contain no fluorides,
lients, and “waterproof” ingredients. Some of the most diffi-
chlorides, or sulfur ingredients which might cause surface cor-
cult to clean are titanium dioxide cremes and silicon oil emol-
rosion or intergranular stress corrosion of stainless compo-
lients. Aqueous cleaning detergents are ideal cleaners for sili-
nents.
con, titanium dioxide, and other hard-to-clean residues gener-
ated in cosmetics processing. As with pharmaceutical process-
ing, there can be absolutely no residues that could contami- TABLE 6J DETERGENT SELECTION GUIDE FOR NUCLEAR CLEANING
Application Recommended
nate products and cause eye or skin irritation problems. Key Concerns Articles Cleaned/Soil Removed Cleaning Method Detergent
Silicon emollients can be removed using very high tempera- Nuclear Cavities, floors, tools. Manual, Soak Chelate free, mild
No isotopic exchange. alkaline
tures above 75˚C (170˚F) and double-strength solutions of a Chelation interference. Spray machine Chelate free, low-
high emulsifying cleaner used in a total immersion cleaning foam alkaline
system. Titanium dioxide cremes also often require very high
temperatures and a cleaner with good emulsifying and excel-
lent dispersants. CHEMICAL AND OTHER FLUID PROCESSING
The three main areas of concern in chemical and fluid pro-
cessing cleaning are:
TABLE 6I DETERGENT SELECTION GUIDE FOR COSMETICS CLEANING
Application Recommended • Cleaning chemical process equipment—most notably
Key Concerns Articles Cleaned/Soil Removed Cleaning Method Detergent water or other high-purity chemical delivery systems
Cosmetics Product contact surfaces. Manual, Ultrasonic, Soak, Mild alkaline
Avoid cross- C-I-P* • Oxygen/gas delivery systems—where pipes and tanks
contamination Parts washers, power spray Low-foam alkaline need to be kept extremely clean

92 The Aqueous Cleaning Handbook Industrial Cleaning Applications 93

 • Waste treatment systems—particularly those involving REFERENCES
the use of filter membranes Adams, D. G. and Agaarwal, D. (1990). “CIP System Design and
Installation,” Pharmaceutical Engineering, Vol. 10, No. 6, pp. 9-15.
In piping systems, clean-in-place cleaning is usually Alconox Inc. Guide to Critical Cleaning, Detergent Selection Guide, p. 12.
employed where a cleaning solution is circulated through the Cleaning Printed Wiring Assemblies in Today’s Environment, edited by
pipes and then rinsed thoroughly to the desired level of clean- Les Hymes, published by Van Nostrand Reinhold.
Alconox Cleaning Solutions newsletter, Vol. 1, Number 1, “Drug compa-
liness with an appropriate rinsewater.
nies find aqueous cleaners a sure cure for cross-contamination” and
This is quite similar to the kinds of cleaning done with Vol. 1, Number 2, “How Clean Is Clean?”
oxygen delivery piping systems. In an oxygen delivery piping American Laboratory News edition, June 1992 article “Stopping residue
system it is crucial to have no residues that would be poten- interference on labware and equipment.”
tially oxidizable as this could cause a flammable or explosive Grimes, T. L., Fonner, D. E., Griffin, J. C., Pauli, W. A. and Schadewald,
F. H. (1977). “An Automated System for Cleaning Tanks and Parts
condition. used in the Processing of Pharmaceuticals,” Bulletin of the Parenteral
In waste-treatment filtration, one is often working with Drug Association, 31, No. 4, pp. 179-186.
small to medium sized, in-plant systems where fats, oils, Mahmood, T and John Chu “Cleaning Solutions in the Semiconductor
greases, or process oils from manufacturing processes need to Wafer Manufacturing Process” in Ch 5.4 Handbook for Critical
Cleaning, Kanegsberg, B. Ed., CRC Press Publishers, Boca Raton,
be separated from waste water in order to have an acceptable 2001, 542-561
plant discharge. If this separation is done by a filtration sys- Weitzel, Steven “Strategies for Simplifying Cleaning Validation” referring
tem, the filter membranes need to be cleaned with a high- Dr. M. E. Labib, presented at Cleaning Validation and Cleaning
emulsifying and or high-dispersing cleaner to rejuvenate the Processes, Jan 14-15, Philadelphia, PA USA (2002)
membranes. Often a high-emulsifying cleaner is used first to
remove the oils and greases, followed by the use of an acid RESOURCES
cleaner to remove particulates such as organic soils and silt. www.alconox.com
cleantechcentral.com
TABLE 6K DETERGENT SELECTION GUIDE FOR CHEMICAL www.metalfinising.com
AND FLUID PROCESSING www.seiberling4cip.com
Application Recommended
Key Concerns Articles Cleaned/Soil Removed Cleaning Method Detergent
Chemical and Pipes, tanks. Manual, Soak, Mild alkaline
Fluid Processing Spray, C-I-P* Low-foam alkaline
No interfering
residues. Filters, membranes, proteins, Circulate, Soak, C-I-P* Enzyme cleaner
bio-fouling.
Filters, membranes, silicate. Circulate, Soak, C-I-P* Mild acid
Filters, membranes, grease, oil. Circulate, Soak, C-I-P* Mild alkaline
*Clean-in-Place by circulating, for spray clean-in-place see machine washer detergents.

94 The Aqueous Cleaning Handbook Industrial Cleaning Application 95

 CHAPTER SEVEN

Standard Operating
Procedures
A large part of successful cleaning relies on having a sound,
reproducible procedure. This, of course, aids in making it easi-
er to train operators so that cleaning is consistent. The follow-
ing are sample standard operating procedures for manual
cleaning, ultrasonic cleaning, machine washer cleaning, and
large-tank cleaning.
In some cases, these standard operating procedures were
written for specific detergents and temperatures for specific
soils. As a result, they may need to be adapted to meet specific
applications. However, they provide examples of what should
be included in a standard operating procedure.
The following are lists of the items to consider, including
in different types of standard operating procedures (SOPs),
that can be adapted to the needs of people writing cleaning
procedures.
In general a good SOP should present a list of materials
and people involved, the surface being cleaned should be iden-
tified, and the eight key variables for cleaning effectiveness
should be defined:
1) precleaning handling 5) type of agitation
2) cleaning chemistry/ 6) rinsing conditions
concentration 7) drying conditions
3) time 8) postcleaning handling
4) temperature
Where cleaning solutions are re-used in baths or sumps,
the control parameters and equipment used should be defined
(such as conductivity or pH) the limits should be defined, the

96 The Aqueous Cleaning Handbook Standard Operating Procedures 97

person responsible for monitoring the baths should be
defined, the type of report or logbook entry should be defined,
the trigger points and alert levels should be defined, actions
taken in response to these levels and finally the conditions
under which the bath is dumped should be defined.
ITEMS FOR A MANUAL PARTS OR
MANUAL SURFACE CLEANING SOP
1. List of parts or surfaces being cleaned. Define the scope
of the SOP, the maximum number of parts or surface area
this process is designed to clean. Define any level of training
or certification required to perform this cleaning operation
2. List of Materials
a. Detergent—define full name, manufacturer, manufactur-
er part number, distributor/supplier, and internal part
number as appropriate
b. Water of suitable purity—define tap water, deionized
water, distilled water or water-for-injection as is appro-
priate
c. Brush, absorbent cloth or sponge—whatever is used
d. Container of suitable size for the detergent solution—
define container
e. Any baskets for handling small parts, if used
f. Any rinsing containers, if used
g. Any drying equipment, if used
h. Any required protective equipment, gloves, eye protec-
tion, clothing etc.
3. List any requirements for handling prior to cleaning.
The type of things you could optionally list as they apply
would be:
a. Parts to be cleaned within 4 hours of being processed to
remove grime—if you knew that the grime had a tenden-
cy to dry onto the parts and become more difficult to
clean, or
b. Tank to be cleaned within 3 days of last use—if you had
validated that the tank could be successfully allowed to
sit dirty for 3 days and still be cleaned by this manual
procedure, or
98 The Aqueous Cleaning Handbook
c. Do not remove parts from shipping containers prior to
being ready to clean them promptly—if you know that
unpacking the parts increases the risk of new contami-
nants, or
d. Handle all parts with finger cots to avoid adding finger-
prints to surfaces – if you do not want to add any new
fingerprints to a surface where you are using a cleaning
process that is only designed to remove particulates
e. Presoak the parts in a defined detergent solution at a
defined temperature and time prior to cleaning – for
example presoak parts completely immersed in 1% Terg-
a-zyme detergent (1.25 ounces Terg-a-zyme in 1 gallon
of water) at 120 deg F for 20 minutes prior to cleaning—
if you know your parts have dried on protein soils that
are difficult to clean without presoaking
4. Directions for making up the detergent solution: Make
up detergent solution diluted in water of suitable purity
according to directions in a container of suitable size at a
given temperature.
a. For example: Mix 1.25 ounces of Alconox powdered
detergent in 1 gallon of 120 deg F hot tap water in a 2.5
gallon bucket. Use cleaning solution within 15 minutes
before the temperature drops below 120 deg F.
5. Manual cleaning description:
a. Wet part or surface with solution by
i. Dunking the part in the solution, or
ii. Wiping the part with a solution soaked brush,
absorbent cloth or sponge
b. Clean by scrubbing with the brush, absorbent cloth or
sponge –
i. define any particular cleaning or scrubbing actions
required such as: brush all surfaces vigorously, but
particularly be sure to use brush vigorously on the
inside of the port for at least 30 seconds
6. Rinse Procedure:
a. For example: place parts in basket and run them under
running tap water for 20 seconds while moving basket to
assure all parts are exposed to running water, or
Standard Operating Procedures 99
 b. Hose down all surfaces with running water assuring that
all parts of surface are rinsed for at least 10 seconds, or
c. Dip part in bucket of rinse water for initial rinse, dip in
second bucket of rinse water for second rinse, and then
place under running water at the sink for 10 seconds as
a final rinse.
7. Drying procedure
a. Such as, place parts on rack and allow to air dry, or
b. Place parts on tray and place in 210 deg F drying oven
for 40 minutes, or
c. Open all ports in tank and allow tank to air dry
8. Any post cleaning handling procedures, such as:
a. Define any inspection actions such as: take 10 parts
from the batch and inspect for particulates and visible
smudges with a 10X magnifying glass. Record results in
batch record. Reject entire lot if there are any failures.
Or,
b. Mark tank with “clean tags” recording time, date, and
operator who performed cleaning. The next day after the
tank has dried, close the ports to keep out dust. Or,
c. Dispose of used detergent solution down the drain.
An example of a manual cleaning SOP written for manual
cleaning of a bench top fermentation reactor adapted from
“Fundamentals of Fermentation: Techniques For Benchtop
Fermentors Part I - E. coli” which was prepared by the R & D
Lab, New Brunswick Scientific Co., Inc. is:
1. Scope
a. For cleaning bench top fermentation reactors
b. Operator training a qualification required
2. Materials
a. Liqui-nox Detergent (Alconox, Inc. Catalog Number
1201)
b. Water
c. Kimwipes®
d. pH 7 buffer
e. chemical resistant gloves
f. glycerine
100 The Aqueous Cleaning Handbook
g. sponge
h. non-abrassive pad
3. Precleaning requirements and procedures:
a. When the fermentation run is complete, it is necessary
to carefully shut the process down. First all operating
parameters (agitation, temperature, dissolved oxygen
(D.O.) level, pH, and gas feed) must be set from their
current control modes (such as “PID”, “D.O.”, “Base”) to
the “Off” mode. Note that the manual air valve on the
side of the unit should also be closed as well.
Additionally, if a supplemental oxygen feed was used, it
will be necessary to close the gas tank valve and the
lines leading from it to the unit. If a recirculating chiller
is in use, it should be shut off when the temperature
control is shut off. Feed lines from any addition bottles
which have been used should be clamped off prior to
detaching them from the vessel, and should then be
removed.
i. The next step is to disconnect the vessel from the
unit. The temperature probe needs to be removed
from the thermowell. Remove the motor and place
the protective cap over the agitation shaft. Always
disconnect the water lines by disconnecting the
incoming lines prior to the outgoing lines. The air
line must be disconnected from the sparger.
Disconnect the pH and D.O. probes from the unit
and replace their protective caps. The D.O. probe
presents an easy removal as you simply unscrew
the thread and gently pull it out. It should be
immediately rinsed off and then wiped dry gently,
always remembering to avoid touching the mem-
brane at the tip. Some runs will result in an accu-
mulation of biomaterial on the probe and it may be
necessary to wipe the probe down more vigorously
but in no case should the tip be touched. After
cleaning the D.O. probe the tip can be visually
inspected for damage. The probe should then be
stored in a clean area in such a way as to protect
the sensitive tip. Removing the pH probe is usually
not as difficult a process as inserting it because the
Standard Operating Procedures 101
 shaft will be wet and thus should be relatively easy
to remove. However the danger of probe breakage
is still very real and extreme care must be taken
when removing it. It is still necessary to use two
hands with one hand at the top of the port acting as
a guide to ensure proper removal. A gentle pace for
this is required. If at any point in this process the
probe jams, it is essential to avoid trying to force it.
It may be necessary to reinsert it part way and
apply a lubricant such as glycerin to the shaft and
port in order to effect the probes' removal. In
extreme cases it may be necessary to remove the
headplate with the probe still inside so that you can
approach the problem from both ends. In this case,
it is critical to remove the headplate very carefully.
(We recommend that you have a spare probe avail-
able at all times, in case of breakage.) Once the pH
probe has been removed, it should be immediately
washed off with warm water. If biomaterial has
accumulated on the probe, using a sponge (or an
equivalent that will not scratch glass) and gentle
pressure to clean the surface. The very tip of the
probe should be handled with extreme care and a
Kimwipe® should be used to gently dry it off after
washing. The probe should be stored with the tip
immersed in either electrolyte or pH 7 buffer. This
electrolyte/buffer can be reused, but it should
always be inspected prior to each use for precipita-
tion or contamination.
4. Manual cleaning, rinsing and drying description
a. Now that the vessel is detached from the unit, it can be
cleaned. To do this it will be necessary to remove any
remaining cotton and foil covering the ports. The rub-
ber bulb on the sampler should be removed and rinsed
separately. The glass wool can be removed at this point
as well. The sampling tube is detached and washed sep-
arately. The valve on the sampling port and all clamps
on all tubing connected to ports will need to be open for
proper washing. (Note that the media will need to be
removed prior to unclamping any tubing that is below
102 The Aqueous Cleaning Handbook
the liquid level, as is the case with a side harvest line).
The headplate should be detached by loosening and
then removing the clamps that hold it to the rest of the
vessel. Those clamps may require rinsing. The remain-
ing culture broth should be sterilized or emptied into a
bucket and disinfected by using bleach or other accept-
ed disinfectant prior to disposal. Note that some media
may be incompatible with this procedure, in which case
the media can be placed into another container for ster-
ilization prior to disposal. The headplate should be
washed thoroughly with warm water and then de-ion-
ized (DI) water. It may be necessary to scrub accumula-
tions of biomaterial off. A pad that won't scratch the
steel is required for this. The agitation shaft, the ther-
mowell, harvest and sparger tubes and the short beveled
tips of the interior portion of the base-type addition
ports will often require special attention. All tubes and
shafts must be cleaned. Note that there may be some
residual base or acid left in those lines, so extreme cau-
tion and the use of chemically-resistant gloves is recom-
mended for this procedure. It is often necessary to hand
wipe surfaces with a paper towel in order to fully
remove residual traces of small particulate debris.
b. The washing of the bottom portion of the vessel
requires the same procedures as the headplate. Note
that the sides of the vessel, particularly where the baffle
was adjacent to it, and side ports (plugged or
unplugged) may require special attention.
c. The vessel can now be cleaned by washing with deter-
gent, or by using a cleaning solution. If the vessel is to
be sterilized, all standard precautions must be taken.
Note that for this purpose, the vessel does not need to be
sealed except for those previously cited valves and tub-
ing which run under the liquid level. It will be necessary
to use water in the vessel. We recommend the use of DI
water, and the fill should be at least as high as your stan-
dard level for a run. Unless you have already specifically
wiped the residual grease off the top of the glass cylin-
der, there should be enough so that the headplate can be
clamped to the lower portion of the vessel. Note that it is
Standard Operating Procedures 103
 neither necessary nor desirable to fasten these clamps
with the same force used for attaching the headplate
prior to a run, as this could lead to vessel damage.
Instead, the lightest possible pressure should be used.
The advantage to sterilization is that not only are resid-
ual viable organisms killed, but residual debris will
loosen and become removable by washing after the ves-
sel has cooled. If a cleaning solution is required, use a
1% dilution of Liqui-nox cleaning solution (Alconox, Inc.
catalog number 1201). Alternatively, if you are using the
vessel for consecutive runs with the same media, a rins-
ing of it with warm tap water and the DI water may suf-
fice. Note that if water will run over a vessel surface that
has grease on it, the grease should be removed by wiping
it off with a wet paper towel.
d. In cases where the vessel must be decontaminated prior
to cleaning, add water so that the liquid level reaches
the maximum working volume of the vessel. This will
help prevent biological materials from adhering.
e. Allow vessel to air dry after thorough rinsing
5. Post cleaning procedure
a. Store vessel in a clean area.
b. Inspect visually prior rinsing and sterilization for next
use.
ITEMS FOR A ULTRASONIC CLEANING SOP
1. List of parts the process is intended to clean. Define the
maximum number of parts to put into a batch to be
cleaned. Define any level of training or certification
required to perform this cleaning operation.
2. List of Materials
a. Detergent—define full name, manufacturer, manufactur-
er part number, distributor/supplier, and internal part
number as appropriate
b. Water of suitable purity—define tap water, deionized
water, distilled water or water-for-injection as is appro-
priate
c. Ultrasonic cleaning tank—define size, frequency, config-
uration, manufacturer, and identifying specifications
104 The Aqueous Cleaning Handbook
d. Baskets for handling small parts, if used
e. Any rinsing containers or equipment
f. Any drying equipment, if used
g. Any required protective equipment, gloves, eye protec-
tion, clothing etc.
3. List any requirements for handling prior to cleaning.
The type of things you could optionally list as they apply
would be:
a. Degas solution for 10 minutes to remove dissolved
gasses that will dissipate cavitation energy and decrease
cleaning performance
b. Turn on heaters and preheat the tank to 120 deg F (50
deg C)
c. Parts to be cleaned within 4 hours of being processed to
remove grime – if you knew that the grime had a tenden-
cy to dry onto the parts and become more difficult to
clean, or
d. Do not remove parts from shipping containers prior to
being ready to clean them promptly – if you know that
unpacking the parts increases the risk of new contami-
nants, or
e. Handle all parts with finger cots to avoid adding finger-
prints to surfaces – if you do not want to add any new
fingerprints to a surface where you are using a cleaning
process that is only designed to remove particulates
f. Presoak the parts in a defined detergent solution at a
defined temperature and time prior to cleaning – for
example presoak parts completely immersed in 1% Terg-
a-zyme detergent (1.25 ounces Terg-a-zyme in 1 gallon of
water) at 120 deg F for 20 minutes prior to cleaning – if
you know your parts have dried on protein soils that are
difficult to clean without presoaking
4. Directions for making up the detergent solution: Make up
detergent solution diluted in water of suitable purity according
to directions in a container of suitable size at a given tempera-
ture.
a. For example: Mix 1.25 ounces of Alconox powdered deter-
gent in 1 gallon of 120 deg F (50 deg C) hot tap water which
will fill to tank to within 1 inch of the top of the tank
Standard Operating Procedures 105
 b. For another example: Fill the tank within 1 inch of top
and turn on heaters. Make up 1% Alconox solution in a
beaker (20 g Alconox in 200 ml water in a 250 ml
beaker). Place beaker of Alconox solution in a beaker
tray with the beaker immersed in the heated water. Fill 3
other beakers with deionized water for rinsing and place
them in the beaker tray.
c. Degas solution for 10 minutes to remove dissolved
gasses that will dissipate cavitation energy and decrease
cleaning performance. This is particularly important for
freshly made up solutions.
d. Turn on heaters and preheat the tank to 120 deg F (50
deg C)
5. Ultrasonic cleaning steps:
a. Never place parts or receptacles directly on the bottom
of the unit. It can cause the unit to fail because the parts
will reflect the ultrasonic energy back into the transduc-
er. Always allow at least one inch between the tank bot-
tom and the beaker or receptacle for adequate cavita-
tion. Keep solution within one inch of the top of the unit
when a beaker or tray is in place.
b. If using a tray or basket to lower the parts into the solu-
tion, it is better to use a holder that is of open construc-
tion, either an open mesh basket or an insert tray, that is
adequately perforated for drainage. This also permits
free access of the sound waves to the parts.
c. Clean the parts to be cleaned in the solution by
i. Placing them in basket and immersing them in the
ultrasonic tank for 10 minutes
ii. After 10 minutes lift basket and allow it to drip off
for 1 minute to reduce dragout
iii. Cover ultrasonic tank after removing and draining
basket
6. Rinse Procedure:
a. For example: take basket and run them under running
tap water for 20 seconds while moving basket to assure
all parts are exposed to running water, do a final rinse
by immersing in a second ultrasonic tank filled with
106 The Aqueous Cleaning Handbook
deionized water – change rinse water when it reaches 50
Kohms resistance.
7. Drying procedure
a. Place parts on rack and allow to air dry, or
b. Place parts on tray and place in 210 deg F drying oven
for 40 minutes, or
8. Any post cleaning handling procedures, such as:
a. Define any inspection actions such as: take 10 parts
from the batch and inspect for particulates and visible
smudges with a 10X magnifying glass. Record results in
batch record. Reject entire lot for recleaning if there are
any failures. Or,
b. Dispose of used detergent solution down the drain.
An example of an ultrasonic cleaning procedure adapted
from a manufacturer of small stainless steel and aluminum
parts is:
1. Scope
a. For the cleaning of small stainless steel and aluminum
parts
b. To be carried out by trained and qualified operators
2. List of Materials
a. Alcojet powdered detergent (Alconox, Inc. catalog num-
ber 1450)
b. Drain rack with mounting pins to mount connectors on
for cleaning operation
c. Ultrasonic cleaning tanks
d. Ultrasonic rinsing tanks
e. Air knife, filtered hot air dryers
f. Deionized water
g. Drying ovens
h. 10X magnifying glass
i. alkaline resistant rubber gloves
3. Flow chart showing handling, cleaning, rinsing, drying,
control and post cleaning handling
a. (see chart on pages 107-108)
Standard Operating Procedures 107
CLEANING PROCESS FLOW FOR PARTS CLEANING PROCESS FLOW FOR PARTS
STEP STEP CHEMICAL WATER BATH CHANGE CONTROLS/ Specified Temperature Check Control Check/ Trigger Alert Trigger
NUMBER DESCRIPTION USED USED AGITATION TIME (MIN.) NO PARTS. PARAMETERS Limits (Degree C) Frequency By Chart Equipment Points Level Actions

Incoming DI water Resistivity >2 Megohms R/ T Once/Day Technician Trend Cond meter <5Megohms 1 Change DI
column

pH 5.5-8.0 Once/Day Technician Trend pH meter Out of spec 1

Incoming Inspect Visual As required All IQC tech Insp report 10 x Glass 1% failure 1 Inform
Customer

Material input Qty/load 500pcs/holder

1 Initial Presoak Alcojet Manually 3 min 100K Concentration 1% R/ T

Rinse(water jet) Water Manually 1min R/ T

2 1st Ultrasonic Clean Alcojet DI water Ultrasonic 5±1min 100k Concentration 3% 60-70 Control Box 65±5 Concentration

(40KHZ) pH 10.4-11.4 Once/Day Technician log bk pH meter Out of spec 1 Increase/Dilute

Rinse(water jet) DI Water Manually 1 min Pressure 2-4kg/c R/ T

3 2nd Ultrasonic Clean Alcojet DI water Ultrasonic 5±1min 100k Concentration 3% 60-70 Control Box 64±5 Concentration

(40KHZ) pH 10.4-11.4 Once/Day Technician log bk pH meter Out of spec 1 Increase/Dilute

Rinse(water jet) DI Water Manually 1 min Pressure 2-4kg/c R/ T

Rinse(DI water jet) DI Water Manually 1min Resistivity >2 Megohms R/ T

8 DI rinse (immersion) DI water Air 5min Resistivity >2 Megohms R/ T

9 Final DI rinse DI water Ultrasonic 2min Resistivity > 2 Megohms

(immersion)

(40KHZ) 55+5 Once/Day Technician Control Box 50-60

11 Spin initial dry Machine 2 min Technician Spin Machine 1

12 Dryer Hot air 10min 90±10_ Technician Control Box 95±5 1 Check temp
probe

13 Oven Dry Hot air 45min Every Lot 150±10_ Technician Control Box 150±5 1 Check temp
probe

Outgoing inspect Visual 0.1% fail QC tech Insp report Microscope10 1 Sorting
100

Performance test DI water 4h Every Lot Visual Corrosion 95+5_ 3pcs/lot Technician Insp report Visual No Corrosion 1 Rework

Packing Plastic tray/bag As Required

Storage As Required

ALERT LEVEL: 1. INFORM SUPERVISOR OR QC/ENGINEERING/PRODUCT MANAGER

108 The Aqueous Cleaning Handbook Standard Operating Procedures 109

ALUMINUM FOIL
ULTRASONIC CLEANER TEST PROCEDURE
In working with ultrasonics, it is sometimes useful to be able
to test the performance of your ultrasonic washer. The follow-
ing aluminum foil test adapted from a Brooks Airforce Base
procedure (http://www.brooks.af.mil/dis/ic guidelines/
attach2.htm) can be useful.
1. Prepare an aluminum foil sample. Obtain a roll of standard
lightweight household aluminum foil. Unroll a piece of foil
measuring approximately one (1) inch greater than the
depth of the tank by approximately the width (long dimen-
sion) of the tank. For example: A tank with dimensions of 9
inches long by 5 inches wide by 4 inches deep would require
a foil sample measuring 9 inches by 5 inches. Use scissors to
cut the foil. Do not tear.
2. Prepare a fresh solution of ultrasonic cleaning solution
according to the manufacturer’s instructions and fill the
ultrasonic tank to one inch of the brim.
3. If heaters are supplied with the cleaner, turn them off for
the remainder of the test. Also, if the unit is supplied with a
HI/LO switch, or intensity, it should be set in the highest
position.
4. Before placing the foil in the tank, turn the ultrasonic clean-
er on for five (5) minutes using the timer located on the
cleaner. Be sure to turn the timer to 20 minutes, then back
to the 5 minutes setting for maximum time accuracy if it is
an analog timer. Digital timers can be set directly.
5. Place foil sample which was prepared in Step 1 into the
tank in a vertical position. The foil long dimension should
be positioned with the long tank dimension. The foil should
extend downward, but should not touch the tank bottom.
6. Hold the foil, approximately centered front to back, as
steady as possible. Turn the ultrasonic cleaner on for exactly
20 seconds.
7. Turn the cleaner off and remove the foil sample. Shake the
foil sample dry of any water droplets. Allow foil to air dry,
being careful not to wrinkle the foil.
8. Properly functioning units will result in foil surfaces that
are uniformly “peppered” (covered with a tiny pebbling
110 The Aqueous Cleaning Handbook
effect), over the entire surface. If areas greater than _ inch
square show no pebbling, there may be a problem with the
unit. Retest with new foil to substantiate the failure. The
unit, along with its latest foil record, should be returned to
your service center for service, if both samples fail. Foil
samples may be retained for future comparison. If future
tests show marked changes over time you may need to ser-
vice your unit. Foil samples may be sent with units returned
to the manufacturer for service.
CLEAN-OUT-OF-PLACE IN RACK LOADED
SPRAY-IN-AIR WASHER
Standard Operating Procedures for the wash cycle in a
machine washer, which does not include the scope and list of
materials is:
1. Precleaning is only required to remove bulk ingredients
from the items to be washed and should be accomplished by
a thorough rinsing. Handling of the items to be washed
must be done according to manufacturers recommenda-
tions. All safety regulations of your company should be fol-
lowed in handling and transporting the items to be washed.
2. Cleaning chemistry and concentrations of the cleaning
chemicals is specific to the soiling on the items to be
washed. The GMP Washer should utilize precise dosing
pumps to deliver chemicals to the wash chamber. The dos-
ing time will determine the amount of chemical delivered to
the fixed volume of water in the wash chamber.
3. Temperatures in the GMP washer should be user program-
mable up to 95 degrees Centigrade.
4. Exposure time of the cleaning chemistry at setpoint temper-
ature will account for proper cleaning. GMP Washers vali-
date exposure time through continual monitoring of all
parameters.
5. Purified Water rinsing (i.e. WFI, USP) is performed to
ensure removal of all cleaning chemicals at the end of the
wash cycle. Conductivity measurement of final rinse water
can be taken to validate rinsing efficiency.
Standard Operating Procedures 111
6. On Drying models, a drying step with temperatures up to Function Possibility Prog. 11
110 degrees Centigrade can be performed. All drying air is
HEPA filtered. COLD W.F.I RINSE 1 0 to 30 min
7. Postcleaning handling of the washed items must be per-
COLD W.F.I RINSE 2 0 to 30 min
formed in compliance with internal company procedures
that assure cGMP compliance.
COLD W.F.I RINSE 3 0 to 30 min
COLD W.F.I RINSE 4 0 to 30 min
POSSIBLE SETTINGS FOR WASHER CYCLES
Function Possibility Prog. 11 HOT W.F.I RINSE 0 to 30 min
HOT W.F.I TEMPERATURE up to to 95° C
PREWASH 1 PERIOD 0 to 30 min
During the inspection and qualification of the GMP
PREWASH 1 TEMPERATURE up to to 95° C Washer, verification of the effectiveness of the inventory sys-
PREWASH 1 DETERGENT 0 to 6 min tem as described above must be demonstrated. Testing proto-
cols must be established. An example is as follows:
PREWASH 2 PERIOD 0 to 30 min
PREWASH 2 TEMPERATURE up to to 95° C One test protocol for establishing cGMP washer operation
that can be used can be done by the riboflavin U.V test:
PREWASH 2 DETERGENT 0 to 6 min
Soil the parts with a Riboflavin solution.
Let them dry for 2 hours and then soil them again.
PREWASH 3 PERIOD 0 to 30 min Let them dry overnight.
PREWASH 3 TEMPERATURE up to to 95° C Perform the cycle 11 as follows (this cycle must have no
PREWASH 3 DETERGENT 0 to 6 min drying).

After cycle, the wet parts are checked with an U.V lamp.
WASH PERIOD 0 to 30 min
Does Riboflavin remain?
WASH TEMPERATURE up to to 95° C Test 1 Yes / No
WASH DETERGENT 0 to 6 min Test 2 Yes / No

W.F.I RINSE 1 0 to 9 Glassware: Test 1:

Test 2:
Test 3:
ACID RINSE PERIOD 0 to 30 min
ACID INTAKE 0 to 6 min After all of the preparation of the cycle description, load
patterns and testing of the spray coverage is completed, the
W.F.I RINSE 2 0 to 9 operators must be trained to load/unload the racks is an ef-
ficient manner.

112 The Aqueous Cleaning Handbook Standard Operating Procedures 113

CLEAN-IN-PLACE ULTRAFILTRATION
BRINE WATER FILTER SYSTEM CLEANING
1. Scope
a. To clean a large ultrafiltration brine water filter system
b. Operators must be trained and qualified
2. Materials
a. Good quality chlorine-free tap water (total dissolved
solids less than 5,000 mg/l)
b. 316 stainless steel mix tank sized appropriately to the
system (minimum of 3 minute retention time during cir-
culation) with an exhaust fan, mixer, cooling coil, and
temperature indicator
c. 316 stainless steel centrifuge pump sized for appropriate
flow rates
d. 10 micron cartridge prefilter
e. Flow meters
f. Suitable flexible piping, sampling ports and port connec-
tors
g. Terg-a-zyme (Alconox cat no 1350) enzyme cleaner
3. Pre cleaning conditions
a. Filter system suffering from biofouling and/or inorganic
particulate build-up
4. Cleaning, rinsing and drying description
a. In large systems, isolate the 1 block of filter elements to
be cleaned, allowing the rest of the blocks to operate
normally.
b. Flush filter element block with water once through (10
gallons for a typical 4 inch diameter filter element unit –
different sized units would take proportionally more or
less water)
c. In the mix tank, dissolve enough Terg-a-zyme to make a
0.5% solution taking into account the volume of the
tanks and filter element blocks (2.5 gallons for a 4 inch
system).
d. Turn on mixer to dissolve detergent
e. Circulate the cleaning solution through the filter block.
Send the first 20% of the solution to drain via the brine
return valve. Circulate the rest of the cleaning solution
114 The Aqueous Cleaning Handbook
at 4.5 gallons/min at 345-1035 Kpa pressure for a 4 inch
system. Use the chiller to maintain the temperature
below 35 deg C.
f. The cleaning progress can be monitored by observing the
color of the effluent. Circulate continuously or by alter-
nately circulate/soak for 15 minute intervals. Circulate
for at least 2 hours for a 4 inch system. Continue until
the return effluent is no longer badly discolored.
g. When cleaning is completed, stop recirculation, drain
mix tank to waste. Flush residual cleaner with feed
water at 4.5 gallons per minute (for 4 inch systems) at
345-518 Kpa pressure (for 4 inch systems) sending both
brine and product side to drain. Collect sample of efflu-
ent in a small jar, cover, shake and observe foam indicat-
ing the presence of detergent. Rinse jar between uses.
Continue flushing until no foam is observed in the shak-
en sample jar.
5. Post
a. Perform post treatment procedures and return block to
normal operations. Observe pressure and performance
to determine if further treatment with a citric cleaner
such as Citranox (Alconox, White Plains NY USA cat no
1815) may need to be performed to reduce particulate
and inorganic scale buildup.
CLEAN-IN-PLACE LARGE TANK FILL,
SOAK AND AGITATE CLEANING
1. Scope
a. To clean a large stainless steel tank to remove a blended
material that contains a thick high melting wax.
b. Operators must be trained and qualified
2. Materials
a. Detergent
b. Brush
c. Bucket
d. Recirculation pump
e. Hot water hose
3. Precleaning conditions
a. Tank with waxy residue shall be cleaned within 24 hours.
Standard Operating Procedures 115
 b. Tank ports should be kept closed while in holding
4. Cleaning, rinsing and drying description:
a. Fill tank full with hot plant water
b. Add detergent recommended for the type of residue in
the tank (see note)
c. Turn on mixer wipers to agitate
d. Turn on tank heaters to raise temperature above 200 deg
F (see note)
e. Turn on pumps and connect pipes to recirculate through
any lines that need to be cleaned. Note pumps should be
operated with sufficient head or at a slow enough speed
to avoid cavitation due to foam formation.
f. Run for 4 hours. Depending on how well sealed the tank
is, you may need to top up the solution to compensate
for evaporation
g. Open top and manually scrub with a brush dipped in the
hot solution the unexposed top sections of the tank that
were not immersed by the cleaner
h. Drain the tank
i. Fill the tank with hot plant water that had been heated to
200 deg F with the agitation and any recirculation pump
turned on for 10 minutes.
j. Use a hose with hot water to rinse the top part of the
tank above the immersion line
k. Drain the tank
l. Visually inspect the interior of the tank and clean any
known problem areas with a hot bucket of detergent
solution and a brush.
m. Rinse the tank thoroughly with hose of hot plant water
or a spray ball apparatus with hot plant water.
n. Drain the tank.
o. Allow tank to air dry with ports open
5. Postcleaning conditions
a. Tag the tank as clean with a date to allow control for
clean hold times
b. Record cleaning in equipment log, recording date, time,
and operator
116 The Aqueous Cleaning Handbook
Note, adjustment of the recommended 4 hour clean-
ing time may need to be done as experience is gained
with specific soils and tanks. This cleaning regimen is
designed for a wax, which melts around 200 deg F in
mind. Many soils may not require heating to an excess of
200 deg F. Many waxes are melted by 170 deg F and this
procedure could be adapted to use a lower temperature
for lower melting waxes of for residues that did not
require such high temperatures.
The previous sections in this chapter give examples of
standard operating procedures. The types of considerations
and procedures could be adapted to many other kinds of
cleaning. There are many types of cleaning machines, each
would have its own machine specific standard operating pro-
cedure. You could have procedures for a range of machines
such as vibratory washers, oscillating washers, reel-to-reel
washers, spray cabinet washers, and a range of other industri-
al washers. As long as the general topics outlined here are cov-
ered a successful SOP can be written. The machine manufac-
turer should be able to help you understand the proper use of
the machine. You can add your own understanding of your sit-
uation to adapt this to a successful SOP.
REFERENCES
DuPont Company Bulletin 507 “Cleaning Procedures” p 1-4 (1982)
Durkee, JB, The Parts Cleaning Handbook, Gardner Publications,
Cincinnati, 1994
Dollard, R M Keeping Validation Current: Elements of an Effective
Change Control Program, Philadelphia. presented at Cleaning
Validation and Cleaning Processes Jan 14-15 Philadelphia, PA (2002)
James Fry, Private communication regarding Lancer Washers May 2002
RESOURCES
www.alconox.com
www.lancer.com
http://www.brooks.af.mil/dis/icguidelines/attach2.htm
Standard Operating Procedures 117
 CHAPTER EIGHT

Cleaning Validation
Cleaning validation is typically performed for pharmaceutical
and other GMP manufacturing processes. These include phar-
maceutical, bio-pharmaceutical, bulk-pharmaceutical, med-
ical-device, cosmeceutical and clinical-diagnostic manufactur-
ers. The validation is specific to the detergent and method
used for cleaning.
To perform a cleaning validation one needs a validation
master plan. The validation is best done during Installation
Qualification (IQ), Operational Qualification (OQ), and
Performance Qualification (PQ) of manufacturing equipment
and operations. The validation provides documentation and
evidence of reproducible successful cleaning. The validation
consists of a final report and a set of procedures to maintain a
validated state.
The master validation plan would typical dictate that the
final report will have sections such as the following:
• Objective
• Responsibilities
• Equipment/products/ procedures
• Tests Acceptance limits
• Analytical Methods
• Sampling procedures and recovery
• Cleaning process design
• Data analysis
• Assumptions
• Change control/maintenance
• References

The objective of the validation might be to ensure product,

118 The Aqueous Cleaning Handbook Cleaning Validation 119

worker, and environmental safety while controlling the risk of
cross contamination. The people or departments involved in
carrying out the validation with defined responsibilities would
include:
• Validation Specialist—writes, coordinates validation
• Manufacturing—write SOPs, do training
• Quality Assure/Control—approve and do analytical
methods
• Engineering—inform of changes, provide equipment
data
• R&D—recovery, validate methods, transfer methods,
new cleaners
In the course of the validation one can simplify things by
assembling an equipment matrix that defines all shared and
dedicated equipment. Work can be done to justify which
equipment represents worst case hardest to clean equipment
that in turn must have a full validation done to represent the
documented easier to clean equipment.
By the same token, a matrix of residues can be assembled
to classify into residue groups of types that are cleaned by a
given set of conditions and then determine which is hardest to
clean. In this way, a worst-case residue or worst-case for a
residue class can be confirmed. A matrix of cleaning proce-
dures can then be assembled in order to standardize on as few
procedures as is practical to improve execution and training
for these procedures.
It is important to validate a worst case scenario and to jus-
tify the choice of “worst-case.” The worst case is typically cho-
sen based on product solubility in cleaner or detergent, the
toxicity of the products or degredants being cleaned, dose
sizes and size normal therapeutic dose (smaller may be more
critical to validate), hardest to clean equipment/residue, and
worst interactions with the next batch to be cleaned.
The cleaning validation for a specific cleaner involves test-
ing for acceptable residues on pharmaceutical manufacturing
or medical device surfaces. The validation involves:
• Residue identification,
• Residue detection method selection,
120 The Aqueous Cleaning Handbook
• Sampling method selection,
• Setting residue acceptance criteria,
• Methods validation and recovery studies, and finally
• Writing a procedure and training operators.
This procedure is used to document acceptable residues
three or more times and then a rational monitoring program
to maintain a validated state is put in place. If changing any
part of the procedure or cleaner, first clean the new way, col-
lect data and then clean the old way before using any equip-
ment while in the process of validating the new procedure.
Residue identification—in a pharmaceutical manufactur-
ing environment this involves: the cleaner, primary ingredi-
ents, excipients, decomposition products, and preservatives.
This document is intended to help with the cleaner residue
identification.
Residue detection method selection—for cleaners can
involve specific methods for specific cleaner ingredients such
as: high-performance liquid chromatography (HPLC), ion
selective electrodes, flame photometry, derivative UV spec-
troscopy, enzymatic detection and titration. It can also involve
non-specific methods that detect the presence of a blend of
ingredients such as: total organic carbon, pH, and conductivi-
ty. The FDA prefers specific methods, but will accept non-spe-
cific methods with adequate rationales for their use. For inves-
tigations of failures or action levels, a specific method is usual-
ly preferable. (A later section of this chapter lists references to
several methods for each cleaner brand.)
Sampling method selection—for cleaners involves choos-
ing between rinse water sampling, swabbing surfaces, coupon
sampling, or placebo sampling.
Rinse water sampling involves taking a sample of an equi-
librated post-final rinse that has been recirculated over all sur-
faces. Rinse samples should be correlated to a direct measur-
ing technique such as swabbing.
Swabbing involves using wipe or swab that is moistened
with high purity water (WFI) that is typically wiped over a
defined area in a systematic multi-pass way always going from
clean to dirty areas to avoid recontamination – i.e. 10 side by
side strokes vertically, 10 horizontally and 10 each with the
Cleaning Validation 121
flip side of the swab in each diagonal direction. For TOC
analysis very clean low background swabs or wipes and sam-
ple vials such should be used. The Texwipe large Alpha Swab
714A or 761 have been used, these are available in kits with
clean sample containers.
Quartz glass fiber filter papers have been used successfully.
Coupon sampling involves the use of a coupons or an actual
removable piece of pipe that is dipped into high purity water
to extract residues for analysis.
Placebo testing involves using placebo product and analyz-
ing for residues from the previous batch.
Setting residue acceptance criteria—in pharmaceutical
and medical device manufacturing requires setting residue
acceptance levels for potential residues such as the active
drug, excipients, degradation products, cleaning agents,
bioburden and endotoxins. These levels are determined based
on potential pharmacological, safety, toxicity, stability, and
contamination effects on the next product using that surface
or equipment. Limits are typically set for visual, chemical, and
microbiological residues.
The cleaning agent limits are generally covered under
chemical criteria. Chemical limits can be expressed as a maxi-
mum concentration in the next product (ug/ml), amount per
surface area (ug/cm2), amount in a swab sample (ug or ug/ml),
maximum carryover in a train (mg or g), or concentration in
equilabrated rinse water (ug/ml). You should have a calculated
safety based acceptance limit, and you can have a lower inter-
nal action level, and a lower process control level based on
actual manufacturing and measuring experience.
Cleaning agent safety based limits are typically calculated
from a safety factor of an acceptable daily intake (ADI), a
(1/1000 or more) reduction of an LD50 preferably by the same
route of administration, or reproductive hazard levels. If the
calculated limit is found to be higher than a less than 10 ppm
carryover to the next batch, then the limit can be set to the
more stringent 10 ppm carryover level for the safety based
limit.
Calculated safety based limit in mg/cm2 or mg/ml of clean-
er residue on a just cleaned equipment:
122 The Aqueous Cleaning Handbook
Limit (mg/cm2 or L) = ADI carryover – see below (mg) X Smallest Next Batch (kg)
Size of Shared Equipment (cm2 or L) X Biggest Daily Dose or of Next Batch (kg)
ADI carryover (mg) = LD50 by administration route (mg/kg)
X body weight (kg) X (1/ 10,000 or 1/1000*)
Comparison calculation of limit based on no more than 10
ppm carryover:
Limit (mg/cm2) = 10 mg residue on just cleaned surface X Next Batch Size (kg or L)
1 kg of L of next product X Size (cm2 or L) shared equipment
Note that for many residues one can validate a visual
detection limit on the order of 1-4 ug/cm2. It is possible that
the visually clean criteria will be the most stringent criteria.
Example with a cleaner that has an rat oral LD50 of over 5
g/kg, the ADI calculation using a 70 kg person and a safety fac-
tor of 1000 gives a result of 350mg (5 g/kg X 70 kg / 1000 ).
The calculated residual acceptance limit for a 2000 kg mixer
and line where there might be a next smallest batch of 1000
kg, and the area of the mixer and filling equipment which is
all used in the next batch is 100,000 m2 and the daily dose of
the next product is 0.005 kg results in a calculated residual
acceptance criteria of 700 mg/cm2 (350 mg X1000 kg/(100,000
cm2 X 0.005 kg). By comparison, the 10 ppm in next batch
limit gives an acceptance criteria of 100 ug /cm2 (10 mg X
1000 kg/(1 kg X 100,000 cm2) X 1000ug/mg. In this case, it is
likely that you will be able to show that you can visually detect
down to 4 ug/cm2 and since you need to have a visually clean
surface, your most stringent acceptance criteria will be the
visual limit.
Note that in this example you are trying to avoid getting
more than 350 mg of residue in a daily dose of the next prod-
uct. In the case of small final filling equipment such as filling
needles for vials or tablet punches and dies, you might need to
do separate residue studies on the filling needles or punches to
be sure that there was not enough residue just on that equip-
ment to contaminate the first few bottles or tablets of the next
batch with a residue of 350 mg/daily dose.
If the safety based limit in this example is set at 100
ug/cm2. Then this limit can be expressed as a rinse water con-
Cleaning Validation 123
centration of 100 mg/L in a post final rinse using 100 L of
DIRECTORY OF CLEANER RESIDUE DETECTION METHODS
recirculated to equilibrium rinse water (0.1 mg/cm2 X 100,000
FOR EACH ALCONOX DETERGENT
cm2/100 L). This same limit could be expressed as 6.25 ug/ml
or ppm total organic carbon (TOC) in a sample for a residue
that is 10% TOC by weight in a 20 ml swab sample from a 25

Kit

Vis
cm2 swab area where 50% recovery has been established ((25

rate,

y, UV/
C
LC, Tit

y HPL
cm2 X 100 ug/cm2) X 50% recovery) X 10% TOC/20 ml. The

, Assa

IC
C
ion

me or
nt HP

by TO
b
same safety limit can be expressed several different ways.

ctant

Titrat

HPLC

y GC
ay
rfacta

by Fla
arbon
y Ass
Surfa

her b
The methods validation and recovery study—is the use of

te by

id by
V/Vis

ivity
nic Su

yme b

anic C

assium

col Et
nionic

ospha

ric Ac
nduct
ect U
the sampling and detection method on known spiked surfaces

A. Anio

E. Enz

F. Org

J. Gly
C. Dir

H. Cit
B. No

D. Ph

G. Co

I. Pot
at representative levels, typically spiked at 50%, 100% and
150% of the acceptable limit and at lower expected actual lev- ALCONOX® • • • • •

els to show linearity with documented % recovery as analyzed LIQUI-NOX® • • • • • •

and to determine the limit of detection and limit of quantita- TERG-A-ZYME ®

• • • • • •
tion. Ideally the expected values and limits should be multiples ALCOJET® • • •
of the limits of quantitation. The % recovery is used to corre- ALCOTABS ®
• • • •
late amount detected with amount assumed to be on the sur- DET-O-JET® • • • •
face as an acceptable residue. This is a good time to consider DETERGENT 8 ®
• •
wipe or rinse sample storage conditions and time limits to get CITRANOX® • • • • • •
the sample analyzed. Rinseability profiles showing the com-
LUMINOX® • •
plete rinsing of the individual detergent ingredients should be
CITRAJET® • •
undertaken if the solubility of any detergent ingredients or the
rinseability after drying is in doubt. In some cases
There are some things that are unique to the cleaner being
bioburden/endotoxin levels may need to be validated. It is rec-
tested. As and example, the following is excerpts from the
ommended that this process be done separately from the
Alconox Cleaning Validation References for cleaners made by
cleaning process so that the cleaning validation can be com-
Alconox, Inc. show a variety of residue detection methods for
pleted while the lengthier biobuden/endotoxin evaluation is
these cleaners (see the directory table). As discussed under
done.
methods validation, different analytical methods will require
The written procedure and training of operators—involves
different procedures for validation. The FDA, the International
writing out assigned responsibilities, protective clothing
Conference on Harmonization (ICH), and European Union
needs, equipment disassembly needs, monitoring procedures,
(EU) have all defined validation requirements for analytical
documentation needs, labeling of in process and cleaned
methods used in manufacturing pharmaceuticals. The United
equipment with cleaning expiration date, post cleaning inspec-
States Pharmocopeia (USP) gives method validation guide-
tion procedures, storage conditions, and inspection required
lines in Chapter 1225. Residue detection methods can vary
before next use. The operators then need to be trained and cer-
from non-specific methods such as total organic carbon (TOC)
tified in the procedures.
to selective methods that have been shown to be specific at a
95% confidence level in the conditions of use without signifi-
cant bias or interference from impurities, degredants, excipi-
ents, and other ingredients. The FDA often prefers the use of

124 The Aqueous Cleaning Handbook Cleaning Validation 125

selective methods that have been shown to be specific, particu- the new process with monitoring to prove that the new
larly for investigations. process gives the same validated results as the old process.
Non-specific methods such as TOC are commonly used The final section of the final validation report would have
where the limits of detection and quantitation are well below the references to any standard methods, journal articles, or
residue acceptance limits. TOC also detects virtually all organ- government documents.
ic residues, in ways making it superior at showing overall In selecting an aqueous cleaner for cGMP manufacturing
cleanliness. The following table reviews method validation where a cleaning validation is required, consider both the effi-
requirements: cacy of the cleaner and the ability of the cleaner manufacturer
to support validation efforts.
TABLE: ANALYTICAL METHODS VALIDATION CONDITIONS Things one should look for from a cleaner supplier
Method Accuracy Precision Linearity Reproducibility Selectivity Specificity LOD LOQ Ruggedness include:
(Repeatability)
• Lot traceability of the cleaners
HPLC X X X X X X X X X
• Certificates of Analysis for the cleaners
GC X X X X X X X X X
• Consistent manufacturing
TLCX X X X X X X X X
• Ingredient disclosures under confidentiality
IC X X X X X X X X
• Cooperation with audits and quality questionnaires
Wet Methods X X X X X X X X X
UV-vis X X X X X X X X X
• Ingredient toxicity data
TOC X X X X X X • Ingredient reactivity information to help determine
HPLC- high performance liquid chromatography, GC – gas chromatography, TLC – thin layer chromatography, IC ion chro- degredations and interactions
matography, UV-vis – ultraviolet visible spectroscopy, TOC- total organic carbon, Wet methods- titrations/assays • Cleaner shelf life information
• Residue detection method information
In the final report the next section would deal with clean-
• Residue sampling information
ing process design with references to standard operating pro-
cedures and how they were evaluated. This would be followed • Acceptance limits information
by a section of data analysis with statistical justification for • Recovery information
the conclusions reached. A defined procedure for changing • Residue detection methods validation information
validated processes is needed. This should address the level of • Assistance with written cleaning procedures
approval and review needed for specific changes. Provisions
for emergency changes should be considered. There should be To discuss the specifics of these validations with the exam-
a list of assumptions made that would need to be reviewed ples given with Alconox detergents, contact Malcolm
whenever anything is changed. McLaughlin at 914-948-4040, ext. 160, or write mmclaugh-
It also makes sense to include a review of validated lin@alconox.com
processes during the annual product review (APR) to see that
the interim period of small changes has not cumulatively
made large changes that exceed the assumptions made (ie.
hardest to clean, or most toxic) that would require revalida-
tion. Typically changing a cleaner would require revalidation.
For some kinds of changes it is appropriate to continue opera-
tions the old way while simultaneously and sequentially doing

126 The Aqueous Cleaning Handbook Cleaning Validation 127

REFERENCES CHAPTER NINE
21 CFR 211 and Proposed Revisions
Brewer, Rebecca Designing and Documenting Your Cleaning Validation
Program to Meet FDA Requirements, Washington Group
International , Philadelphia. presented at Cleaning Validation and
Cleaning Processes Feb 1-2 Philadelphia, PA (2001)
Cooper, “Using Swabs for Cleaning Validation: A Review” Cleaning
Validation, IVT, p 74-89 (1996)
FDA “Biotechnology Inspection Guide” (1991) Wastewater Treatment
FDA “Guide to Inspection of Bulk Pharmaceuticals Chemicals” (1991)
FDA “Guide to Inspection of Cleaning Validation” (1993)
ourman and Mullen, “Determining Cleaning Validation Acceptance
Limits for Pharmaceutical Manufacturing” Pharm Technol. 17 (4), 54-
and Cleaner Recycling
60 (1993)
Leblanc, “Establishing Scientifically Justified Acceptance Criteria for
Cleaning Validation of Finished Drug Products,” Pharm Technol 22
Wastewater treatment is imperative for reducing the level of
contamination present in the water from a cleaning system,
(10), 136-148 (1998) which may include insoluble oils, emulsified oils, other dis-
Mowafak, Nassani, PhD, “Qualification of Quality Control in solved organics, suspended solids, and dissolved inorganic
Laboratories,” Journal of Validation Technology, Vol 8, No 3, 260-272
(May 2002) solids such as chlorides, nitrates, phosphates, and metals.
Treatment requirements before discharge to the local
sewer vary from state to state, and municipality to municipali-
RESOURCES ty. Most local governing authorities enforce acceptable criteria
www.alconox.com for pH, biological oxygen demand (BOD), and chemical oxy-
www.ivthome.com
www.cleaningvalidation.com gen demand (COD). Specific discharge criteria will be noted
www.fda.gov.com on your discharge permit.
www.fdainfo.com A typical wastewater treatment system involves a few com-
mon operations, including pretreatment, which is designed to
reduce the volume of solids and wastewater.

TYPES OF CONTAMINANTS
• Solids—Acid conditions are used to enhance breakup of
the oil-water emulsion. The water layer is pumped to a
chamber, where a polymer flocculent is added. The
wastewater is then pumped to a clarifier, where much of
the oil condenses into a floc, which settles to the bottom
of the chamber.
Flocculated solids are transferred to a filter press,
where they are dried in preparation for disposal. The
supernatant liquid is pumped to a process tank where
the pH is raised in order to promote precipitate metals.
Flocculation of the metals is achieved upon addition of a
polymer.

128 The Aqueous Cleaning Handbook Wastewater Treatment and Cleaner Recycling 129
 • Oils—Capability to remove trace quantities of floating oil
in a cleaning bath not only improves cleaner perfor-
mance, but extends bath life. Further, upon filtering out
any particulates or fines, oils collected may be evaluated
for reuse, rather than destined for disposal.
Traditional mechanical separation of oil from waste-
water involves the use of skimmers, tank overflow, and
decanting methods. Such out-of-process, post-produc-
tion, end-of-pipe wastewater treatment approaches tend
to perform less efficiently in a continuous manufactur-
ing operation and contribute to disposal problems.
EQUIPMENT OPTIONS
• Evaporators—Evaporation is commonly used to reduce
the volume of water for further treatment. The contami-
nants then become concentrated within the bottom
sludge and the water is transferred to a holding tank,
where it is allowed to cool to room temperature. The
water is either discharged to drain (with the necessary
permits and approvals in place), or undergoes further
treatment.
• Separators—Gravity separation of nonemulsified oil in
wastewater can occur in the clarification tank. The influ-
ent and effluent flow rates are optimized to allow effi-
cient separation of the lighter oil layer from the water.
An inclined plate can be used to direct the flow of the oil
layer away from the wastewater.
A current method of oil-water separation applies
Bernoulli’s principle, whereby the wastewater is split
into two laminar flows. Oil is continuously collected and
concentrated in a second chamber, which is separated by
a baffle from the primary chamber and a reduced-pres-
sure area below. The reduced pressure directs the flow of
water down, away from the second chamber.
The oil is recovered from the top of the concentrated
layer, when the layer reaches a designed thickness. Higher-
quality oil is recovered this way, and is able to be reused.
• Activated carbon—Suspended organic materials can be
removed from the waste stream with the application of
130 The Aqueous Cleaning Handbook
an activated carbon filter, capable of absorbing material
many times its own weight within its extensive pore net-
work.
However, activated carbon is used for organic materi-
als only. Metal contaminants and other inorganic materi-
als will remain dissolved or suspended in the wastewater.
An activated carbon filter can be used as one of the last
stages before discharge or recycling, in order to assure
cleanliness. Filters can be arranged in series or parallel.
A parallel arrangement allows for change-out of one fil-
ter while the others remain operational.
• UV Systems—Ultraviolet (UV) light is an effective means
to destroy biological organisms. A UV-oxidation system
can be employed, as necessary, to reduce the BOD of the
wastewater.
SELECTION CONSIDERATIONS
The following are basic guidelines for selection of a waste-
water treatment system:
• Treatment options should be studied by an engineer to
assess process alternatives. The system should be opti-
mized for proper flow rates, filter capacities, through-
puts, etc.
• Design, maintenance, and operations should have con-
tingencies for downtime.
• Capital and operating costs may justify the recycling of
wastewater in a closed-loop system.
CLEANER RECYCLING
As numerous ozone-depleting compounds became legislated
out of use, a large number of companies chose aqueous clean-
ing solutions as replacement alternatives to solvent degreasing.
In the early transitional days, many process and manufac-
turing engineers were concerned that aqueous processes
would reduce part quality and throughput while creating addi-
tional waste and wastewater treatment problems and costs.
Some alternatives to aqueous cleaning systems include
“drop-in” semi-aqueous or solvent-based cleaning systems.
However, these are not without their own problems, namely
Wastewater Treatment and Cleaner Recycling 131
employee health concerns, flash points (flammability), and
possible worker discomfort due to odors.
One public lab where solvent replacement work has been
done is The University of Massachusetts at Lowell’s Toxics Use
Reduction Institute. The Institute has shown the viability of
aqueous cleaning in industrial settings. Aqueous cleaning has
provided a sound alternative to vapor degreasing in as many
as four out of five applications that the Institute reviews on a
laboratory scale for industry clients.
Modern closed-loop aqueous cleaning systems remove
contaminants from both the cleaning bath and rinse water,
and compared to solvent cleaning systems, may be relatively
inexpensive to install.
Recycling can help reduce or eliminate liquid waste by
trading dilute liquid waste for more easily disposed solid
waste in the form of spent filters or concentrated sludge.
Recycling can also help reduce detergent consumption in
order to get more parts clean per pound or gallon. It may also
save time and increase throughput while reducing system set-
up requirements.
The first place to install recycling equipment is in the rinse
water portion of the cleaning system. In sequential tank clean-
ing this is accomplished by using a series of countercurrent
cascading rinse tanks with each tank’s water being progres-
sively reused. This type of system minimizes water usage while
ensuring that the final rinse stages contain the cleanest water.
(Because less water is used, recycling is also easier and less
expensive to install.)
In addition, it is easier to recycle the detergent solution
separately from the rinse water because the equipment used is
merely separating soils, not trying to create high-purity water,
for which you need activated carbon, deionizing resins or
reverse-osmosis. Treating cleaning solutions can be accom-
plished through one or more of the following procedures:
• Physical filtration—uses gravity or low-pressure pump
cartridges at one to 100 micron levels of filtration to
remove suspended particulates.
• Microfiltration—uses low-pressure pumps, dead-end, or
cross-flow filter membranes to realize 0.1 to 1.0 micron
levels of particulate filtration (used to break and remove
132 The Aqueous Cleaning Handbook
very fine suspensions of particulates).
• Physical separation—such as cooling and skimming,
settling, and emulsion breakup. Cooling solutions allow
emulsions and suspensions to break. Settling allows
water-insoluble materials to separate by density; heavy
sludge will generally settle to the bottom when a suspen-
sion breaks. In emulsion breakup, light oils will general-
ly rise to the surface and the overflow can be physically
skimmed off with oleophilic wicks or cycling bands of
oleophilic material, leaving reusable cleaning solution.
• Solution recharge—is when a detergent solution life can
be extended by using the detergent to exhaustion, and
then adding some amount of additional detergent (for
example, 50 percent of the original dose). The concentra-
tion of useable detergent will then be sufficiently raised
to a level where effective cleaning will occur.
• Ultrafiltration—is when multiplex membrane filters are
packaged into a variety of cartridge configurations and
integrated into the cleaning process. A feed solution is
pumped through the filters’ cartridge and split into a
permeate or filtrate (material retained by the membrane)
and retentate (fluid retained by the membrane). The soil-
free permeate stream is then recycled back to the parts
washer.
FILTER SELECTION
Today, many kinds of filters are available for ultrafiltration
due to advances in membrane types and the continued evolu-
tion of systems with better temperature and chemical stability.
For example, extremely hydrophilic (water-absorbing and oil-
repellent) polymeric membranes have been developed to resist
fouling by free oils, emulsions, and other hydrophobic solutes
in order to achieve efficient filtration rates over extended peri-
ods.
Filters can be either symmetric, with fairly uniform pore
diameters throughout the membrane, or asymmetric, consist-
ing of a thin “selective” layer over a thick, porous substructure.
Membrane selection is critical to the effectiveness of any
recycling system. Before deciding on a system, users should
ask the following questions:
Wastewater Treatment and Cleaner Recycling 133
 • Surface chemistry—Has the membrane been engi-
neered for easy cleaning or to resist fouling by free-float-
ing and emulsified oils?
• Stability—Is it physically and chemically stable toward a
broad range of pH and aggressive chemicals?
• Pore size—Has it been designed to ensure complete pas-
sage of all cleaner components while sufficiently retain-
ing the oils?
• Temperature tolerance—What is the membrane’s tem-
perature tolerance?
While not all aqueous cleaning applications require the use
of membrane-based filtration, their use can be especially help-
ful in achieving steady conditions, desirable for maintaining
quality control in high-production applications. Detergents
must be selected for their compatibility with the specific mem-
brane employed, and vice versa.
CLOSING THE LOOP ON AQUEOUS CLEANING AND RINSING
There are a number of methods for removing contaminants
from aqueous-cleaner solutions. These are selected for particu-
lar applications based on the size of the contaminants.
Particulates may be removed using settling tanks, chip bas-
kets, media filtration, or canister filters. Oils are collected
using skimmers and coalescers. Most of the remaining conta-
minants can be removed using micro- and ultrafiltration.
Usually you have separate rinse water recycling and cleaner
solution recycling. Cleaners are recycled using physical filters,
oil separators, ultrafiltration, and microfiltration.
Microfiltration uses a membrane with pore sizes from 0.1
to 1.0 microns, while ultrafiltration pore sizes range from
0.0005 to 0.1 microns.
Ultrafiltration membrane pore sizes are also specified by
molecular weight cutoffs (MWCOs). Contaminants with a
diameter greater than the membrane’s MWCO are thus filtered
out.
It is important to keep in mind that both micro- and ultra-
filtration are pressure-driven processes. Neither will reject
salts, which can adversely affect its performance and make dis-
posal necessary. It is therefore important to monitor the salt
134 The Aqueous Cleaning Handbook
content of both the recycled bath and the rinse water used.
In a separate system, rinse water must be purified. The
rinsing recycle systems can be designed to deliver water to a
level that leaves parts able to meet required cleanliness stan-
dards.
In addition to particle, micro- and ultrafiltration, these
recycling systems may also use reverse osmosis (RO) in con-
junction with microfiltration in order to protect the filter
membrane. Activated carbon may be used for the removal of
the majority of organic contaminants. Ion exchange is another
type of system that uses specially designed resins to capture
cations and anions such as chlorine, heavy metals, calcium,
and magnesium. Since these types of cations and anions may
be considered hazardous waste, they must be shipped back to
suppliers for regeneration.
MONITORING AND CONTROLLING CLEANING BATHS
In order to extend bath life or recycle solutions, the cleaning
bath should be monitored to determine when the solution can
be recharged with detergent and when it is spent, mandating a
fresh batch. There are numerous sophisticated analytical
chemistry techniques, such as FTIR (Fourier Transform
Infrared Spectroscopy), HPLC (high pressure liquid chro-
matography), COD (chemical oxygen demand) and TOC (total
organic carbon), for analyzing recycled cleaner. Free
Alkalinity, a process which measures unreacted builder in the
cleaner, can also be used, as well as Total Alkalinity, which
measures total alkalinity as well as the alkalinity consumed in
the cleaning process due to sludge formation or hydrolysis of
animal or vegetable-based oils. Neither Free Alkalinity nor
Total Alkalinity, however, measure the level of surfactants, ren-
dering them inappropriate in procedures which depend on the
removal of soil.
Some very simple, yet effective, techniques can be used to
monitor bath life, including:
• Conductivity—The measurement of ionic content of the
cleaning solution using electrodes connected to a con-
ductivity meter. This is a useful technique for figuring
out when to add more detergent to a cleaning solution
with high ionic content, such as those based on salts
Wastewater Treatment and Cleaner Recycling 135
 (potassium hydroxide or sodium metasilicate, for exam-
ple). Conductivity will drop as soils react with the salts.
This is not a useful technique for monitoring high emul-
sifying cleaners that rely on surfactants for a significant
part of the cleaning mechanism.
• Refractometry—The indirect measure of the concentra-
tion of dissolved components which influence the refrac-
tive index of a sample of solution using a simple hand-
held refractometer. It can be used to monitor the build
up of soils and concentration of a solution due to water
evaporation. Empirical observations of cleaning solu-
tions in use compared with recorded measurements can
be used to derive appropriate times to recharge or dis-
card solutions.
• Foam Height—Observation of the foam height of a vol-
ume sample of cleaning solution in a vigorously-agitated,
stoppered test tube will show a decrease in foam height
and foam stability with the build up of oils. As foam
height decreases, cleaning solution should be recharged
or discarded. Observations must be made at the same
temperatures.
• pH—Measurement of the acidity or alkalinity of a solu-
tion on a scale of 0–14, expressed as the negative log of
the hydrogen ion concentration, which is measured
using electrodes dipped in the solution connected to a
pH meter. Note that pH paper should not be used with
surfactant-containing cleaners, because they commonly
interfere with accurate readings. A given brand of deter-
gent will have a typical pH. If the soils are acidic, inor-
ganic, or saponifiable natural oils, the pH will drop as
the cleaning solution is used up. Typically, as pH drops
0.5 pH units, the detergent should be recharged. Then
the solution can be used to exhaustion as it drops one
full pH unit.
Each of the above methods has its application, based on
the type of detergent used and the soils that need to be
removed. When using an ionic cleaner to remove nonionic
soils, for example, conductivity can be used to monitor dilu-
tion, dragout, and loss of detergent. When using a high-emulsi-
136 The Aqueous Cleaning Handbook
fying or dispersing detergent to remove oils or particulate types
of soils, refractometry can be an effective means of measure-
ment and control. Foam height is most applicable to cleaners
based on foaming surfactants that rely on emulsification of
oily soils for their removal. When cleaning with an alkaline
detergent and the soil is either acidic or neutralizing in charac-
ter (as most soils are), pH can be used as a control measure.
TABLE 7A BASIC MONITORING AND CONTROL TECHNIQUE
SELECTION BASED ON TYPE OF DETERGENT USED
Conductivity Ionic cleaner removing nonionic soil such as a high
alkaline cleaner used for degreasing
Refractometry High emulsifying and dispersing cleaner used on
mixed particulate and oily soil
Foam height High-foaming cleaner used to clean oily soils
pH decrease Alkaline cleaner used to clean acidic or hydrolyzable
soils that react with the cleaner (most soils are acidic
or hydrolyzable)
pH increase Acidic cleaner used to clean an alkaline or neutral soil
ECONOMIC FACTORS
One must keep in mind that where detergent recycling is con-
cerned, it is possible to be penny-wise and pound-foolish. It
may not be worth risking inadequate, or even uncontrolled,
cleaning simply to get every last penny of performance from a
detergent solution.
The cost of installing recycling and reuse equipment and
procedures must be weighed against the cost of disposal and
solution use. The value of the parts being cleaned, the
increased risk of cleaning failure with each new part cleaned
and the chance of cleaner exhaustion or soil redeposition must
all be considered.
One question that needs to be asked and answered is:
Is it cheaper and better to send partially used cleaner to
drain and make up a fresh batch of cleaner?
With nonhazardous detergents and wastes, probably
cheaper and better to send to drain and make fresh solution.
With easily treated hazardous wastes, perhaps not. Where reg-
Wastewater Treatment and Cleaner Recycling 137
ulatory compliance costs are prohibitive or no drain is avail-
able, the answer is, in all probability, better to recycle.
Another factor to consider is the volume of your cleaning
system. In high-volume, high-performance cleaning applica-
tions with quality control inspection or low fault-tolerance
parts such as electronic components and optical parts, recy-
cling may well be worth it. But in low-volume, extreme-clean-
ing performance applications such as pharmaceutical process
equipment, medical devices and high-priced, soil-sensitive
equipment, recycling the detergent may not be.
Also, before considering recycling as an option, an evalua-
tion and determination must be undertaken as to whether the
EPA needs to be involved, including the completion of a SARA
report of discharge quantities of any listed chemical that is
either in the soil or detergent discharge.
The following additional parameters must also be fully
reviewed:
• Toxicity—by TCLP (Toxicity Characteristic Leaching
Procedure)
• Corrosivity—pH below 2 or higher than 12.5
• Ignitability—flash point below 60˚C (140˚F) ignitable
In addition, compressed gases and oxidizers as well as
reactivity of the waste stream should be reviewed to determine
if RCRA regulations apply as covered in 40 CFR 261.21-.24, as
well as any applicable state and local discharge regulations.
PROVEN TECHNOLOGIES
There are numerous suppliers of closed-loop aqueous-cleaning
systems designed to increase process efficiency by decreasing
the generation of waste. Implementing such systems should
not be based solely on short-term economic evaluation, but
must also include a careful review of environmental and regu-
latory considerations. The benefits of sophisticated closed-
loop systems must be weighed against the costs of maintaining
those systems (for example, membrane systems need periodic
cleaning or may need to be replaced).
In the long run, recycling may be more economically bene-
ficial than constantly playing catch-up with the evolving regu-
lations surrounding industrial parts cleaning.
138 The Aqueous Cleaning Handbook
It is important to note, however, that manufacturers
already using aqueous-cleaning solutions don’t need a closed-
loop system to begin recycling today. In fact, recycling can be
as simple as making up a large soak tank for continuous use
throughout the manufacturing process, saving time and
money merely by recycling wash-tank water through a skim-
mer, then recharging with detergent at midweek intervals. This
will allow you to avoid downtime during draining, refilling,
recharging with detergent, and reheating the tank.
REFERENCES
Alkaline Cleaner Recycle Handbook, Membrex, Inc., Fairfield, NJ 1994, p.
5.
Precision Cleaning, June 1997, article “Closed-Loop Cleaner Recycling by
Malcolm McLaughlin, p. 17–24.
Personal interview, University of Massachusetts at Lowell, Toxics Use
Reduction Institute.
Alkaline Cleaner Recycle Handbook, Membrex, Inc., Fairfield, NJ 1994, p.
5.
Ibid., pp. 4–5.
Ibid., pp. 3–5.
Closed-Loop Aqueous Cleaning, University of Massachusetts, Toxics Use
Reduction Institute, Lowell, MA, 1995, p. 6.
Ibid, p. 10.
Precision Cleaning, December 1997 issue, article “Wastewater
Treatment,” p. 50.
Precision Cleaning, December 1997 issue, article “Filtration Systems,” p.
38.
Precision Cleaning, November 1996, article “Aqueous Cleaning System
Design: Recycling, p. 36–42.
Precision Cleaning, December 1997, article “Sifting Through Filtration
Options,” p. 16–23.
Precision Cleaning, October 1996, article “Aqueous Cleaning Technology:
How long is a Cleaning Bath Really Effective?”, p. 21–27.
RESOURCES
www.alconox.com
Wastewater Treatment and Cleaner Recycling 139
 CHAPTER 10

Measuring Cleanliness
M easuring cleanliness can be done at different levels depend-
ing on the technique employed. Processes which detect clean-
liness at levels as low as 0.01 grams per square centimeter in-
clude:
• Visual inspection
• Low power microscope inspection
• Wiping and visual inspecting
• Water break tests
• Atomizer tests
• Nonvolatile residue inspection
• Surface UV Fluorescence detection
• Tape test.

The next level of cleanliness measurements detects soils at

the 0.01 to .001 gram per sq. cm level—a level of detection is
suitable for aerospace, electrical, automotive and many sur-
face preparation applications. This level of detection can be
achieved through Millipore filter measurement techniques
• Optical microscopy
• Extraction
• Oil evaporation
• Oil soluble fluorescence
• Gravimetric analysis
• Surface Energy tests
• Contact angle measurement
• Particle counting

140 The Aqueous Cleaning Handbook Measuring Cleanliness 141

 The highest level of cleanliness measurement—where lev-
els below 1 microgram per sq. cm. can be detected—are suit-
able for use in semiconductor, disk drive, and medical device
applications. The kinds of techniques that are used for this
level of precise cleanliness measurement are:
• Carbon coulometry
• Electron spectroscopy for chemical analysis (ESCA)
• Fourier transform infrared (FTIR)
• Gas chromatography/mass spectrophotometry (GC/MS)
• Ion chromatography (IC)
• Optically stimulated electronic emissions (OSEE)
• Particle counting, scanning electron microscopy (SEM)
• Secondary ion mass spectroscopy (SIMS)
The following are summaries of these various cleanliness
measuring techniques as appropriate to each of the three lev-
els of cleanliness required.
CLEANLINESS DETECTION AT 0.01 GRAMS PER SQ. CM
• Visual inspection—is best used to detect residues of
contrasting color or texture. Good lighting can enhance
visual inspection, fiber optic lights providing light across
a surface improve detection, and magnification of course
improves detection.
• Low-power microscope inspection—This is an excel-
lent way to quickly and efficiently verify cleanliness of
residual oils and greases, flux residues, particles and sur-
faces.
• Wiping and visual inspecting—Wiping a surface with a
white wipe will provide a contrasting surface with which
to detect dark residues (the white glove test).
• Water-break test—Use running water and let it sheet
across the surface. Observe if any breaks in the water
occur due to hydrophobic (water-fearing) residues. (See
“The Hydrophobic Surface Film by the Water Break
Test,” ASTM Method F 22-65—found at www.astm.org.)
The water break test is a fairly crude test which is suit-
able for detecting films of process oils and heavy finger-
142 The Aqueous Cleaning Handbook
prints. It will not readily detect non-hydrophobic
residues. This test is often used for parts washing; it may
not always be suitable for precision cleaning applica-
tions.
• Atomizer test—A variation of the water-break test, this
requires observing whether a gently sprayed water mist
deposits uniformly or whether water repulsion occurs
(usually due to a hydrophobic soil). The atomizer test is
slightly more sensitive to hydrophobic soils than the
water break test. In the water break test the kinetic ener-
gy of the flowing water may overcome a hydrophobic
residue where in the atomizer test you may be able to
see the results of a little droplet of water being repelled
by a hydrophobic contaminant.
• Nonvolatile Residue Inspection (NVR)—The NVR test
involves extraction of soil from a dirty surface into a sol-
vent, just as is done with the extraction method above.
The solvent is then evaporated onto a coupon of known
weight and after the solvent is evaporated off any residue
is deposited on the coupon. When the coupon is re-
weighed, any increase in weight is recorded as the non-
volatile residue. Many solvents can be used for this pur-
pose. It is important to use a solvent that can dissolve
the soil being detected. (Isopropyl alcohol, methalyne
chloride, acetone and other solvents have been used for
this purpose.)
• Surface Ultraviolet Florescence (UV)—Many organic
and some inorganic contaminants will fluoresce under
UV light. Shining a UV light on the surface will cause the
residues to easily be seen, particularly in a slightly dark-
ened or dark room. The higher the intensity of the light
used, the lower the level of contaminants which can be
easily detected. Note, however, that the typical black
light found in novelty or specialty gift stores may not be
strong enough to cause much residue to fluoresce. More
powerful UV lights available from scientific supply hous-
es or industrial suppliers will give far higher levels of
detection. The test is performed by shining the light on
the surface and observing a fluorescent, typically a yel-
low, orange or green, sometimes red, color which glows
Measuring Cleanliness 143
 under the light and is easily seen.
• Tape Test—The Tape Test is a simple method for aiding
visual inspection and is well suited to determining the
cleanliness of smooth metal and plastic parts. It involves
attaching transparent adhesive tape to the surface being
measured, firmly pressing it down, carefully removing it
and then placing it on a sheet of clean white paper.
Comparing the sample with an adjacent piece of white
paper provides a fast, easy way to visually monitor par-
ticulates and sometimes even film residues.
CLEANLINESS DETECTION AT
0.01 TO .001 GRAMS PER SQ. CM
• Millipore Filter Measurement—The Millipore Test—
also known as the “patch” test—involves spraying sam-
ples of parts with filtered hexane, isopropyl alcohol, or
trichlorethylene at pressures of 60 to 80 psi through a
1.2-micron filter membrane inside a jet nozzle. The
spray is collected, vacuum-filtered onto a clean filter
membrane followed by microscope inspection for any
particle-per-micron contaminants. (The membrane can
also be weighed to determine total contaminants in mil-
ligrams.)
• Optical Microscopy—High-power compound micro-
scopes can also be used (typically on circuit boards),
however, these are more delicate and more expensive
than simple, low-power microscopes and generally
require greater operator skill and training.
• Extraction—a particularly useful method for detecting
detergent residues, this measurement technique employs
a solvent-soaked glass filter paper, or high purity swabs
to wipe surfaces. The filter paper or swab is then extract-
ed or digested and trace analysis performed on the
extract. This procedure can be quantitative if one wipes
a known area.
Extraction methods can be highly sensitive to a wide
range of possible soils and residues. The limitations on
this method, however, is that an appropriate solvent
must be used to extract any soils. When performing trace
144 The Aqueous Cleaning Handbook
analysis for detergent residues it is advisable to use
water as the solvent. (The sensitivity of an extraction test
depends on the method of trace analysis.)
The types of trace analyses most often used are UV
visible spectrophotometry, total organic carbon (TOC)
analysis, high performance liquid chromatography
(HPLC), atomic absorption (AA) or inorganic residues,
and liquid chromatography (LC). (These techniques are
discussed separately in this chapter under “Detection
below 1 microgram per sq. cm.”)
• Oil Evaporation—For filmy residues, a few drops of
organic solvent can be deposited on the surface and then
removed via pipette and placed on a watch glass. If any
filmy residues are present, one should observe a charac-
teristic ring of organic-material deposits.
• Oil Soluble Fluorescence—Involves immersing a part
in a fluorescent oil soluble penetrant dye and then
observing under fluorescent light to see if any dye pene-
trates or adheres indicating the presence of oil. This
method is outlined in ASTM F601-98 “Standard Practice
for Fluorescent Penetrant Inspection of Metallic Surgical
Implants.” Of course cleaning procedures need to be
established to remove the dye after testing.
• Gravimetric Analysis—With small parts of known
weight, the amount of excess weight indicated the
amount of soil present.
After cleaning if the part returns to it’s clean weight
one can conclude that the part is clean. Gravimetric
analysis is also very useful as a screening tool in lab
cleaning situations where a coupon is weighed before
soiling, after soiling with an artificial soil, and then
weighed again after cleaning to derive percent of soil
removed.
• Surface energy—Any hard, flat material has a character-
istic surface energy. As a result, a deposit of a known vol-
ume of pure liquid (typically deionized water) will form
a droplet of predictable size based on the amount of that
energy. Measuring droplet size will determine surface
cleanliness. Generally, hydrophobic soils create smaller
Measuring Cleanliness 145
 droplets; hydrophilic soils, larger ones. The surface-ener-
gy test is far more sensitive than the atomizer or water-
break test and has the advantage of being able to detect
both hydrophilic and hydrophobic soils. The problem
with the surface energy test is it only tests the surface
directly underneath the droplet where you are measur-
ing. If you have a broad, large surface where measuring
one little area of it would be representative of the level of
the cleaning that went on the entire surface, this can be
an excellent and highly sensitive method. If you have a
part that has lots of cracks and crevices and holes, the
surfaces that are accessible for you to place a droplet of
liquid to measure surface energy may not be representa-
tive of the types of soils that may be hidden in any
cracks, crevices, or blind holes. (For a fuller description
of this measurement technique see “More on water-drop
surface energy test,” which follows this section.)
• Contact angle measurement—A variation of surface
energy testing is contact-angle, defined simply as the
relationship of certain forces when a liquid stabilizes on
a part’s surface. This method can be used to determine
cleanliness since the properties of various contaminated
surfaces are reflected by different contact angles.
Contact-angle measurement is especially suited to manu-
facturing operations such as wire bonding on PCBs or
the application of thin films on quartz glass which
require a cleanliness test that is nondestructive. Vapors
from the process itself, such as vacuum or diffusion
pump oils, various process chemicals, or even human
perspiration, are all contaminants whose presence can
be detected by changes in the contact angle. (For a fuller
description of this measurement technique see “More on
Contact Angle Measurement Methods,” which follows
this section.)
• In-situ Particle Counting (ISPM)—Part cleanliness
becomes critically important as mechanical, optical, and
electronic parts shrink in size and formerly inconsequen-
tial particles grow in comparison. High-technology
cleaning techniques, such as ultrasonic bath cleaning are
widely used. Today’s precision industrial applications
146 The Aqueous Cleaning Handbook
now employ ultrasonic cleaning baths as well.
In-situ particle monitoring (ISPM) provides a tool to
observe particle removal behavior in the ultrasonic cleaning
bath process at work and in real time, thus providing the abili-
ty to quickly select, adjust, and optimize the cleaning process.
Once the process is optimized, ISPM can be used to monitor
bath performance, and monitor filtration recycle performance.
ISPM measures particle counts directly during the cleaning
process in both ultrasonic rinse and wash baths.
AN EXAMPLE OF HOW IN SITU PARTICLE MONITORING WORKS
In work done by John Hunt (Pacific Scientific Instruments,
Grants Pass, OR) to optimize a choice or concentration of
cleaning agent, a known amount/type of particle contamina-
tion was deposited on glass slide test coupons. Several clean-
ing agents were tested for their effectiveness in removing the
contamination by monitoring the rate of particle removal in
the bath by recycling the bath through a filtration loop and
detecting particles just before filtration.. For each concentra-
tion and each detergent, various particle sizes were observed
in the bath at the addition of increased concentration of deter-
gent, and then again when the soiled glass plate is added to
the bath. When the soiled plate is added, a number of parti-
cles per ml per minute is determined by integrating the area
under the particle size counting curves for a given length of
time for each particle size monitored at each concentration of
each detergent. If you are trying to optimize detergent con-
centrations, be sure to allow any bubble interference to reach
baseline after addition of increased concentration of detergent
prior to placing the soiled plate in the bath. By observing the
shape of the particle counting curve, you will typically see an
initial spike of particles coming off the plate when you add the
soiled plate and then see particles continue to come off over
time. Typically after 10 or 15 minutes no more particles are
observed. This information can be used to optimize cleaning
times in addition to cleaner concentrations. By the same
token, during cleaning, real-time particle counting could be
used to determine when to take the parts out of the bath by
observing when the particle counts had dropped back to base-
line.
Measuring Cleanliness 147
MORE ON WATER DROP SURFACE ENERGY TEST
Surface energy can be indirectly detected by measuring the
size of a droplet of known volume sitting on a surface. Using a
volumetric pipette a drop of typically 0.2 ml of water is placed
carefully onto a surface being investigated. The droplet size is
measured with a micrometer. If the droplet is circular the area
is determined by the pi r squared method. Note that any
machining or scoring will distort droplets, it may be easier to
use a length times width method of estimating droplets – do
not vary area calculations within a set of measurements.
Typically a surface with a hydrophobic oily residue film will
repel the water and cause the droplets to be smaller than are
observed on the clean surface.
This method works well on glass and metal surfaces. It is
better at detecting films on smooth surfaces rather than par-
ticulates. If the surface is scratched during cleaning, the
droplet size will become smaller causing false readings if the
test is used as a before and after test. If a volumentric pipette
is not available, then using an eyedropper to deposit drops and
using a scale sensitive to 0.001 grams, the ratio of droplet
weight to area can be used to detect changes in surface energy.
Again, a rise in this ratio indicated going from a dirty to a
clean surface. It is useful to work with some known cleaned
surface to observe droplet size behavior and known soiled sur-
faces to confirm that the residue will give the observed
changes.
As with other cleanliness verification techniques, special
tips for contact angle measurement, if practiced, will increase
the repeatability and validity of the measurement results. The
following tips from Precision Cleaning magazine, (Oct. 97 p.
23) were helpfully compiled:
• Use gloves when handling the samples to be measured.
Organics, such as finger oils, cosmetics, and other conta-
minants, will skew the contact angle results.
• Note the nature of the droplet after applying it to the sur-
face. Wait until the droplet has ceased its advancement
and no more change in lateral movement has occurred.
Measure this time interval, making sure that you wait
this period of time after every measurement. Retain con-
sistent time intervals between the placement of the
148 The Aqueous Cleaning Handbook
droplet and its measurement.
• Use medical-grade, ultra-purified deionized water from a
laboratory supply house in order to have a consistent
measuring liquid. This will limit the number of measure-
ment variables.
• Use test liquids of larger surface tension than the solid’s
surface energy in order to obtain easy-to-read results.
• Neutralize the effects of static charges on substrates.
Substrates that are electrostatically charged can skew
contact angle readings up to 5 degrees.
• Accurately control liquid droplets so that they are repeat-
edly deposited onto the sample. Gently move the sample
to the liquid droplet formed at the end of the syringe/dis-
penser in order to minimize gravitational effects.
• In the case of very high contact angles, you may find it
difficult to adhere the droplet from the needle to the
solid sample. Use a Teflon-coated needle of a higher
gauge (smaller inner diameter).
• In case of very low contact angles, use the highest possi-
ble needle gauge (smallest inner diameter needle) for
controlling very small droplet volumes onto the sample.
MORE ON CONTACT-ANGLE MEASURING METHODS
Accepted methods of measuring contact angles to determine
surface characteristics include the inverted bubble, Wilhelmy
Plate, and sessile drop techniques. The latter is the most wide-
ly practiced quality control technique, as it is relatively quick
and requires minimal investment in time and financial
resources.
In the sessile drop technique, the specimen to be measured
is loaded onto a specimen holder. A liquid droplet 3 to 4 mm
in diameter is carefully deposited onto the substrate surface. A
tangent line is drawn at the three-phase interface point in
order to determine the contact angle. Alternately, a line is
drawn from the three-phase interface point through the apex.
This angle turns out to be equal to 1/2 of the tangent angle and
is reproducible by different operators.
Several “real world” examples will help illustrate what can
be learned from the use of the contact angle measuring tech-
Measuring Cleanliness 149
nique to determine the existence of impurities on a surface.
LCD (Liquid Crystal Display) panel surfaces contaminated
with organic matter will be less accepting of a variety of films,
such as metals and protective layers, resulting in poor manu-
facturing yields. Sources of such contaminants include the
vapor of process materials, chemicals, and human perspira-
tion. Very thin organic contaminants several monolayers in
thickness (greater than 10 angstroms) can be evaluated using
the contact angle technique.
In fact, it is generally agreed that the wetting behavior
involves only the last layer or two atoms on either side of a
solid’s interface. The water contact angle correlates the “clean-
liness” of the surface to the adhesion of the copper deposited
onto the surface of the LCD.
Water contact angles can be used in various processes to
determine contamination levels, predict cleanliness and adhe-
sive bond strengths, and monitor cleaning operations.
Whether you are checking the moisture effects on silicon
wafers or LCD quartz panel glass metal adhesion, all that is
needed is an understanding of the basic theory involved and
proper measurement techniques.
DETECTION BELOW 1 MICROGRAM PER SQ. CM
• Carbon Coulometry—The technique employs in-situ
direct oxidation of surface carbon to carbon dioxide
(CO2), followed by automatic CO2 coulometric detec-
tion. (For a fuller description of additional in-situ moni-
toring techniques, see the “In-Situ Particulate
Monitoring” section of this chapter.)
• Electron Spectroscopy for Chemical Analysis
(ESCA)—ESCA is an extremely surface-sensitive tech-
nique, which employs the photoelectric effect, for the
detection of elements and determination of elemental
composition. Electrons are ejected from a solid surface
by irradiating the surface with an x-ray monobeam. The
emitted photoelectrons have a kinetic energy equal to
the x-ray less the binding energy of the electron. The
measured kinetic energy of the electrons can therefore
be converted to binding energies, enabling element iden-
tification.
150 The Aqueous Cleaning Handbook
• Fourier Transform Infrared Spectroscopy (FTIR)—
FTIR spectroscopy is used for structural characterization
of organic and inorganic molecules in solids, liquids,
gases, and on surfaces. Spectrometers record the interac-
tion of light energy in the form of infrared radiation with
an experimental sample, measuring the frequencies at
which the sample absorbs the radiation and the intensi-
ties of the absorption. After using an extraction method
or by using a surface scanning machine, by comparing
the unknown spectra to the standard frequency at which
specific molecules are known to absorb light, the sam-
ple’s chemical makeup as well as it’s concentration can
be determined.
• Gas Chromatography/Mass Spectrophotometry
(GC/MS)—GC/MS is used to identify surface contamina-
tion by extracting contaminants into a solvent and ana-
lyzing them. Organic compounds are then separated via
GC and are then identified, based on molecular weight,
by MS.
• Ion Chromatography (IC)—Ion Chromotography is a
form of liquid chromatography of aqueous samples used
to determine ionic contamination on critical compo-
nents. Columns containing ion- exchange resins are
used to separate the atomic or molecular sample ions
based on their partition ratios as they pass through the
columns. It is the only technique that can provide quan-
titative analysis of anions at the ppb level of an extract
that has been swabbed or wiped from a surface and
extracted into solution for analysis.
• Optically Stimulated Electronic Emissions—When
high-energy UV light hits a surface, electrons are emit-
ted, and the reflected current can be measured. A clean
surface will give the highest return current, so any drop
in current represents contamination. This method is
good for determining low levels of contamination (both
ionic and nonionic). However, while optically stimulated
electronic emissions can detect contamination, it cannot
identify it.
Measuring Cleanliness 151
 • Scanning Electron Microscopy (SEM)—By scanning
high energy electrons across a specimen, SEM allows the
study of both morphology and composition of biological
and physical materials. When high energy primary elec-
trons impact the specimen they are deflected or scat-
tered. Those that are deflected at an angle greater than
90o can reenter the vacuum above the specimen and
make up the backscatter signal. The proportion of pri-
mary electrons collected as backscatter electrons (bse)
increases as a function of the atomic number of the sam-
ple specimen, thereby portraying its chemistry. Forward
scattering primary electrons, those that are deflected at
an angle of 90o or less, travel through the specimen
while loosing energy. The atomic electrons gain this lost
energy, allowing them to escape from their atoms. Those
that are very close to the surface (within the escape
depth) may have sufficient energy to escape from the
sample surface back into the vacuum as secondary elec-
trons (SE). Because an incline surface exposes a larger
area to the electron beam, thereby impacting more elec-
trons within the escape depth, production of secondary
electrons is attributable to the specimen being at high
incident angles with the electron probe. The resultant se
image thus reflects the surface topography of the speci-
men.
• Secondary Ion Mass Spectroscopy (SIMS)—SIMS is
an extremely sensitive surface analytical technique used
for chemical determination of surface constituents, both
elemental and molecular, as well as ppb concentrations
of impurities in semiconductors and metals. The materi-
al under investigation is bombarded with primary ions
which, upon impact, cause secondary ions to be ejected
from the sample’s surface. These secondary ions can be
identified by their mass, which is determined by measur-
ing their travel time from surface to analyzer.
152 The Aqueous Cleaning Handbook
REFERENCES
Alconox Cleaning Solutions newsletter, Vol. 1, Number 1 article “How
Clean is Clean?”
ASTM. F-2265, The American Society of Testing Materials.
Carol LeBlanc; Turi, Massachusetts, Toxics Use Reduction Program for
The 22nd Mr. Clean Conference, Oct. 96.
Carrasco, Armando, “Moisture Induced Stress Sensitivity Reduction of
FSRAM 52 Lead PLCC’s,” 1996 Surface Mount International
Conference, p. 607–611.
Cleaning Printed Wiring Assemblies in Today’s Environment, p. 94
“Testing for cleanliness,” and p. 197 “Cleanliness Verification”
Cleantech “Cleanliness Verification,” CleanTech Vol 3, No. 3, S1-S12
(March 2001)
Djennas, Frank, Prack, Edward, and Matsuda, Yushi, , “Investigation of
Plasma Effects on Plastic Packages Delamination and Cracking.”
IEEE Trans. CHMT, 16. 1993, p. 91–924, edited by Les Hymes.
G. Gould and E.A. Irene, “An Inside Study of Aqueous HF Treatment of
Silicon by Contact Angle Measurement and Ellipsometry,” Journal of
The Electrochemical Society, 135 (1988), p. 1535–39.
Geosling, C and Koran, J “Contamination Control and Analytical
Techniques,” in Ch 3.2 Handbook for Critical Cleaning, Kanegsberg, B.
Ed., CRC Press Publishers, Boca Raton, 2001, 431-448
Good, R.J. and Stromberg. R.R., Ed., “Colloid and Surface Science,”
Plenum, Volume 11, New York, 1979.
Hawkins, George, Ganesan. Gans, Lewis, Gary and Berg, Howard. “The
PBGA: A Systematic Study of Moisture Resistance,” The ISHM
Journal of Microcircuits & Electronic Packaging, 18, No. 2, 122–132,
1995.
Herard, Laurent, “Surface Treatment for Plastic Ball Grid Array
Assembly and Its Effect on Package Reliability,” ISHM Workshop on
Flip Chip and Ball Grid Arrays, Berlin, Germany, November 13–15,
1995, p. 1.
Japan, Kuman- Gypta, “Comparative Studies of the Contact Angle as a
Measure of Adherence for Photoresist,” Thin Solid Films, 75 (1981), p.
319–329.
Mittal, K.L., Ed., “Contact Angle, Wettability and Adhesion,” VSP,
Volume 1, the Netherlands. 1993.
Precision Cleaning, October 1997 article “Contact Angles Measure
Component Cleanliness,” p. 21–24.
Toshiaki Matsunaga, J., “Relationship Between Surface Energy and
Surface Contamination,” Physical Chemistry, 71 (1967), p. 4176.
Trent Thompson, “Moisture Absorption and Autoclave Performance
Optimization of Glob Top Ball Grid Array,” 1996 Surface Mount
International Conference, p. 587–592.
Williams, Richard and Goodman, Alvin M., “Wetting of Thin Layers of
SiO2 by Water,” Applied Physics Letters, Volume 25, November 1974,
p. 531–532.
Measuring Cleanliness 153
RESOURCES CHAPTER 11
www.alconox.com
www.astp.com
www.photoemission.com
www.pmeasuring.com

Environmental
Health and Safety
Considerations
T he key environmental health and safety advantages and dis-
advantages of aqueous cleaners both derive from the fact that
they use water for cleaning and rinsing. Water is inherently
environmentally sound and a substantially safe chemical to
work with. Water is a recyclable natural resource. Yet, as pop-
ulations grow, clean surface water will become increasingly
scarce. Water can also be a transport medium for various pol-
luting or hazardous chemicals that may derive from the use of
aqueous cleaning in specific instances.
One way to look at the environmental health and safety of
a cleaning process is to consider:
• How hazardous is the cleaning process?
• How hazardous is the effluent resulting from the clean-
ing process?
• How sustainable—in terms of energy and resources—is
the process?

All critical cleaning is a spectrum that ranges from pollut-

ing hazardous processes to clean and safe processes; clean,
safe, and reduced waste processes; and clean, safe, and sus-
tainable processes. Aqueous cleaning can, in fact, play a role
all along this spectrum.
It is, of course, possible to use aqueous cleaners with haz-
ardous ingredients that are used to clean hazardous soils that

154 The Aqueous Cleaning Handbook Environmental Health and Safety Considerations 155
are then dumped in the environment—resulting in a haz-
ardous, polluting process. But by the same token, industrial
cleaning can also involve the use of an aqueous cleaner that
has no hazardous ingredients used to clean the same haz-
ardous soils whereby the cleaning solutions are treated prior
to discharge—resulting in a clean and relatively safer process.
Improvement in safety can be achieved by eliminating the
source of the hazardous soil in the process. Taking this a step
further one can effect a reduced waste process by incorporat-
ing some degree of soil recycling, cleaning solution recycling,
and rinse water recycling. It is possible to design a so-called
“zero-discharge” system with no fluid effluent, limited volatile
effluent and reduced solid waste by recycling cleaning and
rinsing solutions with filters. In order to move toward a clean,
safe and sustainable process, however, one would need to
eliminate the use of whatever caused the hazardous soil and
replace it with a nonhazardous biodegradable soil. Then, after
the water used in the cleaning and rinsing process has been
recycled sufficiently to create sustainable energy consumption
rates, the now nonhazardous soil in the effluent would not cre-
ate a hazard in the environment. Any water released could
safely be incorporated into the natural water cycle (surface
water to evaporated water to clouds to rain, and finally, once
again returning to surface water).
Most nonaqueous chemical cleaning methods generally
have much greater difficulty in achieving clean, safe, sustain-
able processes. Many nonaqueous cleaners are themselves
health hazards, water pollutants, or air pollutants. Certainly
not all nonaqueous cleaners are hazardous and/or pollutants,
but most do not have a basic natural process such as the
water-cycle to purify and recycle key ingredients. (Of course,
this is an oversimplification; viewed from the standpoint of a
long enough time scale, almost anything can be considered to
have a sustainable natural cycle of synthesis and decay. We are
considering here natural processes that can contribute to sus-
tainable processes achievable in the course of human life-
times.)
One might argue that the carbon cycle, the nitrogen cycle,
the oxygen cycle and many other elemental cycles also become
involved in nonaqueous cleaning processes. In fact, many of
156 The Aqueous Cleaning Handbook
these cycles are relevant to aqueous-cleaning ingredients.
However, all of these cycles involve far more chemical trans-
formations and slower processes with longer residence times
in various long-term forms. For example, one step in the car-
bon cycle involves extensive time spent as geological carbon-
ates—in the same way nitrogen stays for extensive periods as
nitrogen in the air. Oxygen is also tied as geological carbon-
ates. These elements simply do not cycle as rapidly, in a puri-
fying sense, as does water.
ENVIRONMENTAL ISSUES IN AQUEOUS CLEANING
The environmental issues involved in aqueous cleaning are
mostly associated with the ingredients and their ultimate dis-
charge into the environment. Taking a larger view of the envi-
ronmental issues concerning aqueous-cleaning processes it is
reasonable to consider the energy and resources used in mak-
ing the cleaner, and the energy and resources consumed in
using the cleaner.
There are several important factors concerning discharge
of spent cleaning solutions into the environment: biodegrad-
ability, aquatic toxicity, and eutrophication potential.
Historically, early detergent formulations contained poorly
biodegradable surfactants that were capable of causing foam-
ing in surface lakes and rivers when the spent solutions were
discharged to drain. Today, all modern detergent formulations
use biodegradable surfactants that do no buildup and persist
in the environment and cause surface water-foaming prob-
lems.
Aquatic toxicity can come from very high or very low pH
or the toxicity of the ingredients. Where extreme pH cleaning
is required, it is advisable to neutralize or discharge spent
solutions in small enough quantities to avoid problems. The
sur-factants in aqueous cleaners can have aquatic toxicity
associated with them. The use of biodegradable surfactants
and the discharge of limited quantities of cleaning solutions
generally results in no toxic concentration of surfactants in
surface water. Older more highly toxic surfactants are no
longer widely used in aqueous-cleaner formulations.
Eutrophication involves cleaners that contain phosphates.
Phosphorus is an essential nutrient for algae. When significant
Environmental Health and Safety Considerations 157
amounts of phosphorus are discharged into surface water, it
can result in vigorously growing algae blooms. The algae die
and settle to the bottom of the water causing more rapid than
normal filling in of lakes and ponds with silt and organic mat-
ter. Although eutrophication is a normal, natural process, the
acceleration of this process by phosphates is undesirable. The
main source of phosphorous to surface waters is agricultural
run-off from farming. There are no national regulations
restricting the use of phosphates in cleaners, however many
states and municipalities have enacted legislation that restricts
the use of phosphates in household cleaners. There are cur-
rently no restrictions on the use of phosphate containing
cleaners in industrial cleaning applications.
SAFETY ISSUES IN AQUEOUS CLEANING
Worker safety issues with aqueous cleaners can involve skin
exposure, eye exposure, ingestion, inhalation, and chronic sys-
temic exposure. Consult the label and material safety data
sheet on the cleaner for warnings and safety precautions.
When cleaning by hand, it is always good practice to wear
protective gloves. Even the mildest cleaners can sometimes
cause “dishpan-hand” skin irritation. Gloves also afford a
degree of comfort when working manually with hot solutions.
In fact, many highly acidic or alkaline cleaners require the use
of chemical-resistant gloves for worker safety.
Eye exposure is also a concern with many aqueous clean-
ers. Eye tissue is particularly prone to attack by chemically
active aqueous solutions. Accordingly, it is also considered
good industrial practice to wear safety glasses or other eye
protection when working with aqueous-cleaning solutions.
Particularly hazardous aqueous cleaners should have warn-
ings and recommended eye protection on the label.
In addition, inhalation hazards can exist with some aque-
ous cleaners. Because aqueous cleaners generally do not have
volatile solvent ingredients, it is somewhat unusual to find the
need for respiratory protection with such cleaners. However, it
is considered good industrial practice to have some respirato-
ry protection when working with sprays and mists in open-
spray cleaning. Any special ventilation required should be
noted on the material safety data sheet. Some semiaqueous
158 The Aqueous Cleaning Handbook
cleaners may contain volatile solvents that require special ven-
tilation and possibly even flammability controls.
While it is relatively unusual for an aqueous cleaner to
contain any carcinogenic ingredients, a review of the cleaner’s
material safety data sheet should disclose any long-term
chronic exposure concerns relating to carcinogenicity.
Physical safety issues with aqueous cleaners are generally
concern storage and handling to avoid any hazardous reac-
tions with other industrial chemicals. Good industrial practice
usually involves storing acid and alkaline chemicals separately
to avoid any reactions between them and aqueous cleaners in
the event of accidental spills. Some aqueous cleaners contain
bleaches or other oxidizing agents that should be stored away
from reactive chemicals that might undergo hazardous oxida-
tion reactions. As previously mentioned, most completely
aqueous cleaners are usually not flammable. However, some
aqueous cleaners can contain ingredients that can create haz-
ardous chemicals when burned. (It is considered good practice
to wear respiratory protection when fighting any fire involving
industrial chemicals.)
PRACTICAL REGULATORY REVIEW
In today’s manufacturing environments, it is realistic to try to
achieve safe, clean, and reduced waste cleaning processes—
and to continually strive toward achieving ultimately sustain-
able processes. At the very least, processes that comply with
current environmental and health safety regulations should be
used.
The first step in evaluating the environmental health and
safety of an aqueous cleaner is to secure the material safety
data sheet and technical bulletins for the cleaners you plan to
test or use, and to assemble as much information as you can
about the soils you will be removing. A review of this informa-
tion should disclose important environmental and health haz-
ards and regulatory issues.
When performing an initial review of regulatory issues for
an aqueous cleaner, it is important to consider OSHA
(Occupational Safety and Health Administration) regulations,
NPDES (National Pollutant Discharge Elimination System)
discharge permits, DEP (Department of Environmental
Environmental Health and Safety Considerations 159
Protection) sewer connection/extension permits, and any
RCRA (Resource Conservation and Reclamation Act) haz-
ardous waste class or Clean Water Act regulations. State and
local environmental regulations should also be considered.
In the long run, it may be wise to conduct a full scale envi-
ronmental audit no matter what type of cleaning system you
are using. Such an audit may result in changes in the way you
currently manufacture and clean. In fact, after conducting a
Appendix
full-scale environmental audit many companies turn to aque-
I List of Abbreviations
ous cleaning as a means to more easily and safely achieve reg-
ulatory compliance. (A program of regular re-auditing can II Cleaner Types from Alconox, Inc.
assure continued regulatory compliance.) III Detergent Selection Guide
When compared with many of the hazards of nonaqueous IV Glossary of Essential Terms
and semiaqueous cleaners—such as those containing ozone- V Application Case Histories
depleting fluorocarbon solvents, carcinogenic organic sol- VI Index
vents, and flammable components—aqueous cleaners are a
sound choice for safe, environmentally sound cleaning. By
choosing the safest, most environmentally sound aqueous
cleaner that will perform to your cleaning requirements, the
majority of cleaning problems can be solved with more than
acceptable levels of worker safety and environmental impact.

ADDITIONAL READING
Precision Cleaning, December 1995, article “Environmental Auditing:
Learning from Common Pitfalls and Issues”, p. 13–18.
Journal of Surfactants and Detergents, Vol. 1, No. 1, January 1998, article
“Surfactants and the Environment,” by Larry N. Britton.

RESOURCES
www.alconox.com
www.epa.gov
www.osha.gov

160 The Aqueous Cleaning Handbook Appendix 161

APPENDIX I APPENDIX II

LIST OF ABBREVIATIONS CLEANER TYPES FROM ALCONOX, INC.

BOD Biological Oxygen Demand 30 Glenn St., White Plains, NY 10603, ph 877-877-2526, email cleaning@alconox.com, www.alconox.com

CFC Choloro Fluoro Carbon Cleaner Type Cleaning Methods Used Brand
CIP Clean in Place High emulsifying, manual, soak, ALCONOX® powder
COD Chemical Oxygen Demand mild alkaline ultrasonic, circulate CIP LIQUI-NOX® liquid
DEP Department of Environmental Protection Acid cleaner manual, soak, ultrasonic, CITRANOX® liquid
EH&S Environmental Health & Safety circulate CIP
EPA Environmental Protection Agency Low-foaming, alkaline machine washer, pressure ALCOJET® powder
spray, spray CIP
FT-IR Fourrier Transform Infra Red
Low-foaming, machine washer, DET-O-JET® liquid
GWP Global Warming Potential
high alkaline pressure spray, spray CIP
LAS Linear Alkylbenzene Sulfonate
Ion-free, low-foaming machine washer, DETERGENT 8® liquid
LCD Liquid Crystal Display pressure spray, spray CIP,
MSDS Material Safety Data Sheet manual, soak, ultrasonic,
NPDES National Pollution Discharge Elimination Systems circulate CIP
ODP Ozone Depleting Potential Mild alkaline tablet siphon tube and pipete washer ALCOTABS® tablet
ODS Ozone Depleting Substance Neutral, low-foaming machine washer, LUMINOX® liquid
OSHA Occupational Safety and Health Administration pressure spray, spray CIP,
RCRA Resource Conversation and Reclamation Act manual, soak, ultrasonic,
circulate CIP
SARA Superfund Authorization and Reauthorization Act
Enzyme cleaner manual, soak, TERG-A-ZYME® powder
SNAP Significant New Alternatives Policy
ultrasonic, circulate CIP
TCVLP Toxic Chemical Leaching Properties
Low-foaming, acidic machine washer, pressure CITRAJET® liquid
UV Ultra Violet spray, spray
VOC Volatile Organic Compound

162 The Aqueous Cleaning Handbook Appendix 163

APPENDIX III APPENDIX IV

DETERGENT SELECTION GUIDE

Application Recommended

Key Concerns
Healthcare
Effective preparation for
sterilization, longer instru-
ment life. Minimize cross-
contamination. Reduce
Glossary of
Articles Cleaned/Soil Removed Cleaning Method Detergent
Surgical, anaesthetic, and examining instruments Manual, Ultrasonic, Soak ALCONOX, LIQUI-NOX
and equipment. Catheters and tubes. Machine washer, sani-sterilizer ALCOJET, LUMINOX, CITRAJET
Difficult proteinaceous soils, blood and other Manual, Ultrasonic, Soak TERG-A-ZYME
body fluids, tissue on instruments.

Essential Terms
Machine washer, sani-sterilizer ALCOJET, LUMINOX
waste.
Pharmaceutical Product-contact surfaces. Manual, Ultrasonic, Soak, C-I-P* ALCONOX, LIQUI-NOX
Passing cleaning validation Machine washer, power wash ALCOJET, DET-O-JET
for FDA good manufactur- LUMINOX, CITRAJET
ing practices.
Inorganic residues, salts, metallics, pigments Manual, Ultrasonic, Soak, C-I-P* CITRANOX

Machine washer, power wash CITRAJET

Protein/ferment residues. R/O, U/F membranes.
Laboratory
Reproducible results, no
Glass, metal, plastic labware, ceramics, tissue
culture, porcelain, clean rooms, animal cages,
interfering residues,
extending equipment life.
bioreactors, tubing, benches, safety equipment.
Keep laboratory accredita-
tion. Laboratory safety.
Tubes, reusable pipets.
Water and environmental sampling. Phosphate-
sensitive labware. EPA procedures.
Radioactive equipment/contaminants.
Stopcock grease.
Trace metals, metal oxides, scale.
Proteinaceous soils, bio-wastes, tissue, blood
and other body fluids, fermentation residues.
Manual, Ultrasonic, Soak, C-I-P* TERG-A-ZYME 483—the warning letter threaten close from FDA.
Manual, Ultrasonic, Soak, C-I-P*
Machine, power spray, labware washer,
ALCONOX, LIQUI-NOX
ALCOJET, LUMINOX
Acid cleaner—an aqueous cleaner that has a pH significantly below
washer-sterilizer, cage-washers DET-O-JET, CITRAJET 7, typically below a pH of 5.5. Acid cleaners contain acids and often
Siphon-type washer-rinsers
Manual, Ultrasonic, Soak, C-I-P*
ALCOTABS
LIQUI-NOX, CITRANOX
other cleaning ingredients such as surfactants. Acid cleaners are
Machine washer, labware washer DETERGENT 8,, CITRAJET able to clean using the cleaning mechanism of acid solubalization
Manual, Ultrasonic, Soak, C-I-P* ALCONOX (see other definitions) where an acid reacts with a soil molecule to
Machine washer, warewasher
Manual, Ultrasonic, Soak, C-I-P*
ALCOJET
CITRANOX
create a water soluble molecule, and acid hydrolysis (see other defi-
Machine washer, ware washer CITRAJET nitions) where an acid reacts with a soil molecule and breaks it into
Manual, Ultrasonic, Soak, C-I-P* TERG-A-ZYME a smaller water soluble soil.
Glassware washer ALCOJET, DET-O-JET

Metalworking Glass, ceramic, porcelain, stainless steel, plastic, Manual, Ultrasonic, Soak, C-I-P* ALCONOX, LIQUI-NOX Alkaline cleaner—a water based cleaner that contains alkaline
and Precision
Manufacturing
rubber. Oils, chemicals, particulates.
Machine washer, power wash ALCOJET, DET-O-JET ingredients that cause the cleaner to have a significantly high pH. A
Clean parts, avoid volatile
solvents, strong acids,
Aluminum, brass, copper, and other soft metal
parts. Oils, chemicals, particulates.
Manual, Ultrasonic, Soak, C-I-P* ALCONOX, LIQUI-NOX
cleaner with a pH of 8.5–11 can be considered to be a mild alkaline
Parts washer, power wash ALCOJET, LUMINOX
and other hazardous
chemicals. Inorganics, metallic complexes, trace metals and Manual, Ultrasonic, Soak, C-I-P* CITRANOX
cleaner. A cleaner with a pH of 11–12.5 is at least an unqualified
oxides, scale, salts, buffing compounds.
Parts washer, power wash ALCOJET, DET-O-JET, CITRAJET alkaline cleaner. A cleaner with a pH above 12.5 would be a high
Silicone oils, mold-release agents, buffing
compounds.
Manual, Ultrasonic, Soak, C-I-P* ALCONOX alkaline and corrosive cleaner. Alkalinity helps promote saponify-
Parts washer, pressure spray ALCOJET, DET-O-JET
Metal oxides, scale, salts. Metal brightening. Manual, Ultrasonic, Soak, C-I-P* CITRANOX
ing(see other definitions), solubilizing (see other definitions) alka-
Parts washer, pressure spray CITRAJET line soluble soils, and hydrolysis (see other definitions).
Environmental Bailers, samplers, augers, containers, tubing, Manual, Ultrasonic, Soak, C-I-P* LIQUI-NOX, DETERGENT 8
No interfering residues. teflon, glass, rubber, stainless steel. Machine wash, pressure spray DETERGENT 8, LUMINOX
Anionic surfactant—a cleaner ingredient that is a surface active
Phosphate free.
DETERGENT 8, LUMINOX
agent(see other definitions) that has a negative charge on the
Electronics Circuit boards, assemblies, screens, parts, Manual, Ultrasonic, Soak
Avoid conductive residues, conductive residues, resins, rosins, fluxes, Machine washer, power spray
organic portion of the molecule. The charge on the surfactant
particulates, salts. DETERGENT 8, LUMINOX
avoid CFCs, pass cleaning
criteria.
board and screen washers determines the charge of the cleaner or detergent. An anionic deter-
Ceramic insulators and components. Manual, Ultrasonic, Soak ALCONOX, LIQUI-NOX

Food and Dairy
Avoid interfering residues
on food-contact equip-
ment.
Stainless steel, food-contact equipment.
Oxides, scale, trace metals, salts, milkstone.
Filter membranes. Proteinaceous soils.
Parts washers
Manual, Ultrasonic, Soak, C-I-P*
Machine wash, pressure washers
Manual, Ultrasonic, Soak, C-I-P*
Machine wash, pressure washers
Manual, Ultrasonic, Soak, C-I-P*
gent contains anionic surfactants. Anionic surfactants can be and
ALCOJET, DET-O-JET, CITRAJET
usually are emulsifiers (see other definitions) and dispersants(see
ALCONOX, LIQUI-NOX
ALCOJET, DET-O-JET, CITRAJET
other definitions). Typical anionic surfactants include organic sul-
CITRANOX fates, sulfonates and carboxylates. The most common anionic sur-
CITRAJET
factant is sodium dodecylbenzene sulfonate.
TERG-A-ZYME

Cosmetics Product contact surfaces. Manual, Ultrasonic, Soak, C-I-P* ALCONOX, LIQUI-NOX API—active pharmaceutical ingredient.
Avoid cross- CITRANOX, LUMINOX
contamination. Parts washers, power spray ALCOJET, DET-O-JET, Aqueous cleaner—a blend of water soluble chemicals designed to
Optics Lenses, substrates, mirrors, reflectors, fibers. Manual, Ultrasonic, Soak
LUMINOX, CITRAJET
ALCONOX, LIQUI-NOX
remove soils into a water based solution with a water continuous
Avoid optical interference. CITRANOX, LUMINOX phase during cleaning.
Parts washers, machine washers ALCOJET, DET-O-JET,
LUMINOX ARP—annual product review.
Nuclear Reactor cavities, pipes, tools, protective equip- Manual, Soak, Spray DETERGENT 8, LUMINOX,
Avoid waste interference. ment. ALCONOX Bioburden—microbes on the surface.
Builder—a cleaner ingredient that enhances the cleaning ability of
*Clean-in-Place by circulating, for spray clean-in-place see machine washer detergents.
the surfactants in at least one, and usually a combination of the fol-
lowing ways: softens water to prevent water hardness ions from
reacting with the surfactants or soils by chelation, sequestration or

164 The Aqueous Cleaning Handbook Appendix 165

 binding; enhances surface tension lowering of surfactants; adds
alkalinity; buffers a cleaner to maintain alkalinity; emulsifies oils;
disperses particulates; inhibits redeposition of soils; breaks up
clumps of particles by deflocculation; saponifies soils; provides cor-
rosion inhibition; and improve the handling, flowing, and storage
characteristics of the cleaner. A typical builder is sodium polyphos-
phate.
CFR—code of Federal regulations.
cGMP—current good manufacturing practice.
Chelating Agent—a cleaner ingredient that is an chemical with at
least 2 available sites on the molecule to bind with metal ions in a
water based solution to form a ring compound with metal. Typical
examples of chelating agents include sodium polyphosphates and
ethylene diamine tetra acetic acid (EDTA). Many chelating agents
are also sequestering agents (see other definitions).
CIP—clean in place.
Cleaner—a chemical or blend of chemicals designed to clean. These
may be solvents, acids, bases, detergents, and/or water based
blends.
Degreaser—a cleaner that is designed to remove oils and greases.
These are typically heavy duty cleaners that are designed to remove
gross amounts of oil and grease leaving a visually clean surface
rather than light duty fine cleaners that are designed to remove
lower or trace levels of oils that leave a measurably or analytically
clean surface. Most degreasers are either high alkaline aqueous
cleaners or solvent based cleaners.
Detergent—a blend of ingredients intended for cleaning that include
at least a surfactant (see other definitions) to give at least emulsify-
ing or dispersing and a builder (see other definitions) to inhibit
water hardness precipitation from calcium and magnesium salts. In
some industry usage, the word detergent is used when the word
surfactant is meant.
Dispersant—a cleaner ingredient that reacts with water insoluble
particulates to overcome electrostatic attraction by the particulate
to a hard surface to create a liquid solid mixture in the form of a
suspension. A typical dispersant is sodium polyphosphate.
Dissolve—a cleaning mechanism that relies on a cleaning fluid to be
able to form a stable mixture with individual soil molecules. In
aqueous cleaners, one of the cleaning mechanisms is for the water
to dissolve water soluble soils.
Emulsifier—a cleaner ingredient that lowers the interfacial tension
between immiscible liquids such as oil and water thereby allowing
them to mix. A typical mechanism for emulsifying is for the emulsi-
fier to form a micelle, which in the case of oil and water involves a
small droplet of oil surrounded by emulsifier such that the emulsi-
fier is in contact with the water and the entire surrounded droplet
or micelle is dissolved in the water. Emulsifiers are surfactants (see
other definitions).
Excipients—fillers, non-active pharmaceutical ingredients.
GC—gas chromatography
166 The Aqueous Cleaning Handbook
HPLC—high performance liquid chromatography.
Hydrolyze—to break a molecule apart using acid (H+) and hydroxyl
ions (OH -) from water (H 2O). This occurs when a fat or oil is
hydrolyzed to make soap as in saponification (see other definitions)
or when an enzyme breaks down a protein.
IC—ion chromatography.
ICH—International Conference on Harmonization.
Ion-free cleaner—a cleaner that has no metal ion ingredients.
Typically an ion-free cleaner will contain nonionic surfactants and
other ingredients that are not metallic salts. An ion-free cleaner
does not contain sodium or other metal salts.
IQ—installation qualification.
LOD—limit of detection (signal to noise S/N = 3)
LOQ—limit of quantitation (signal to noise S/N = 10)
Micelle—is a sub-microscopic aggregate of molecules. In the context
of cleaners these molecules are surfactants usually arranged in
sphere or rod shapes with the hydrophilic end of the surfactants
facing outwards into the water solution with the hydrophobic ends
of the molecules facing toward the inside of the aggregate. Micelles
are able to hold hydrophobic oil molecules inside them and create
stable emulsions.
Neutral cleaner—a cleaner that has a pH near 7, typically in the
range of 5.5 to 8.5. These cleaners tend to rely more on emulsifying
and dissolving rather than aggressive chemical attack on soils that
are possible with acid or alkaline cleaners.
Nonionic cleaner—a cleaner that contains nonionic surfactants. The
term does not mean an ion-free cleaner. A nonionic cleaner may
easily contain nonionic surfactants blended with many ionic
builders that are sodium salts or other metal ion salts. (see ion-free
cleaner).
Nonionic surfactant—a cleaner ingredient that is a surface active
agent(see other definitions) that has a no charge on the organic
portion of the molecule. The charge on the surfactant determines
the charge of the cleaner or detergent. An nonionic detergent con-
tains nonionic surfactants. A nonionic detergent is not necessarily
ion free (see other definitions). A nonionic detergent may contain
many ionic salts, just the surfactant is not ionic and does not have
an electrical charge. Nonionic surfactants can be and usually are
emulsifiers (see other definitions) and dispersants (see other defini-
tions). Typical nonionic surfactants include organic ethoxylates.
The most common anionic surfactants are alcohol ethoxylates and
alkylphenol ethoxylates.
OQ—operational qualification.
pH—a measure of how acidic or basic a solution is defined as the
inverse log of the hydrogen ion concentration in water. In practical
terms, pH 7 is neutral, below 7 is acidic and above 7 is basic or
alkaline.
ppb—parts per billion (ug/liter, microgram/liter).
ppm—parts per million (mg/liter, milligram/liter).
Appendix 167
PQ—performance qualification. end of the molecule that is hydrophilic (“water loving”). The
RAL—residue acceptance limits. hydrophilic end of the molecule is stable in water and the
Saponifier—a cleaner ingredient that reacts with a natural oil ester, hydrophobic end of the molecule is more stable out of the water
or resin ester such as rosin to split the poorly water soluble ester next to the air, particulate, oil or surface away from the water solu-
into a more water soluble salt (or soap) of an acid. In the case of tion. This means that a surface active agent can act as a wetting
many compounds this converts a water insoluble oil or resin into a agent to allow a cleaner to wet a surface or penetrate into small
water soluble soap that in turn acts as an emulsifier to emulsify any cracks and crevices to perform cleaning. A surface active agent
unreacted oil or resin and assist with cleaning. Typical saponifiers react with a particle to act as a dispersant. A surface active agent
are potassium hydroxide and sodium hydroxide. can act as an emulsifier with oil. Surface active agents are either
anionic, nonionic, cationic, or amphoteric (see other definitions).
Semiaqueous cleaner—a chemical or blend of chemicals or solvents
that are used to clean that rely on a water rinse. These are usually Surfactant—see surface active agent.
either a solvent or blend of water soluble solvents that are used Titrate—wet chemistry test to detect an amount of something.
straight without water as a cleaner followed by a water rinse, or TOC—total organic carbon analysis.
they may be blended with water during use. UV-vis—ultraviolet or visible spectroscopy.
Sequestering agent—a cleaner ingredient that is a chelating agent
(see other definitions) that reacts with metal ions in a water based
cleaner to hold them in solution and bind with them tightly enough
to stop the metal ions from reacting with other chemicals or soils.
A typical sequestering agent is sodium polyphosphate.
Soap—the salt of an acid. A typical example is the sodium salt of
stearic acid (sodium stearate) formed from sodium hydroxide (a
saponifier—see other definitions) and glycerol tristearate (natural
animal fat). Soap is a surfactant (see other definitions) that usually
has good emulsifying properties for the oils or fats from which it is
derived. One issue with soap is that it can react with calcium or
magnesium hardness ions in tap water to form water insoluble cal-
cium or magnesium salts that precipitate out as a soap scum film.
Solubilizing—a cleaning mechanism that involves dissolving a soil
into a single aqueous phase that relies on a “like dissolves like”
principle. In an aqueous cleaner the water acts as a polar solvent to
help solubilize polar soils. The main cleaning mechanism of sol-
vent based cleaners is solubilizing or dissolving.
Solvent cleaner—a cleaner that is made up of one or more organic
chemicals that have some ability to dissolve soils. Typically solvent
cleaners contain volatile organic compounds. Fluorocarbon based
freon cleaners are solvent cleaners. Solvent cleaners do not have a
water continuous phase present during cleaning, in fact there is
usually no water present in their formulations.
SOP—standard operating procedure.
Surface tension—a force that runs parallel to a surface that results
from the attraction of the surface molecules towards the molecules
that are below the surface. This tension acts to minimize surface
areas of a solution.
Surface active agent—or surfactants are an ingredient in most
aqueous cleaners that are chemicals that are active at solution sur-
face interfaces. In the context of cleaners this means chemicals that
lower the surface tension or interfacial tension at liquid-gas, liquid-
liquid, and liquid-solid interfaces. The structure of surface active
agents used in aqueous cleaners are usually oblong with one end of
the molecule that is hydrophobic (“water hating” ) and the other

168 The Aqueous Cleaning Handbook Appendix 169

 APPENDIX V

Application
Case Histories
1. OPTICAL WAX
MORE HEAT FOR FASTER CLEANING
An optical lens manufacturer had been using ALCONOX pow-
dered detergent in a heated ultrasonic bath for years to remove a
wax from the lens during manufacturing. As production grew,
this system was not able to clean fast enough. By increasing the
temperature, adequate cleaning performance and speed were
achieved.

Initial Problem Solution

Time 10 min 5 min
Temp 60 deg C 70 deg C
Agitation ultrasonic ultrasonic
Chemistry 1% ALCONOX 1% ALCONOX
Rinse deionized water deionized water
Dry air air
Problem cleans to slow

170 The Aqueous Cleaning Handbook Appendix 171

2. PRECISION MANUFACTURING PROCESS OILS 3. PHARMACEUTICAL TABLET COATING EQUIPMENT
HIGHER CONCENTRATION INCREASES BATH LIFE SOIL CHANGE CAN REQUIRE CLEANER CHANGE
For years, a metal valve manufacturer had been using LIQUI- A pharmaceutical company had been using a typical high alkaline
NOX liquid detergent in an immersion tank that was made up cleaner for manual cleaning of tablet coating equipment. This
and depleted in one shift to remove process oils from metal worked fine with their standard tablet coatings. When the compa-
valves. As production grew, the number valves and quantity of ny started to make tablets with enteric coatings, they observed
oils to be removed increased. The valve manufacturer observed that their standard cleaner could not even get their coating equip-
that toward the end of the day the tank did not clean as well as at ment visually clean. By changing to an acid cleaner that was
the beginning of the day. By increasing the concentration of effective on the water insoluble inorganic salts used in the enteric
detergent, the manufacturer was able to increase the soil capacity coating they were able to get their equipment clean.
of the solution and thereby extend the bath life to meet his needs.
Initial Problem Solution
Initial Problem Solution Time 10 min 10 min
Time 20 min 20 min Temp 50 deg C 50 deg C
Temp 50 deg C 50 deg C Agitation manual manual
Agitation soak soak Chemistry 1% High Alkaline 2% CITRANOX
Chemistry 1% LIQUI-NOX 1.5% LIQUI-NOX Rinse deionized water deionized water
Rinse deionized water deionized water Dry air air
Dry air air Problem system could not clean enteric coating
Problem tank did not last long enough on tablet coating equipment

172 The Aqueous Cleaning Handbook Appendix 173

4. ARCHITECTURAL GLASS MANUFACTURER SEES SPOTS WHEN 5. WASTE TREATMENT FILTERS
SETTING UP MANUFACTURING IN A SITE WITH HARD WATER ENZYME CLEANER CURES BIOFOULED FILTERS
DEIONIZED WATER STOPS WATER SPOTS A small scale in-house waste treatment filtration plant was being
An architectural glass manufacturer had one plant where they used to remove oils from a waste stream at a manufacturing
used DET-O-JET cleaner to clean glass prior to coating. In their plant. The filter membranes were typically cleaned with a high
existing plant the tap water was soft without much dissolved cal- alkaline cleaner at high heat. Finally bio-fouling began to occur in
cium or magnesium in it. The manufacturer was able to clean the filter and the resulting proteinaceous soils would crosslink
and rinse sheets of glass in a conveyor spray system using tap and become tenacious when exposed to the hot alkaline cleaning
water to rinse prior to air knife drying. When they set up another solution. The filter flow rates and pressures would not recover
plant in another part of the country they kept getting water spots after cleaning. The solution was to treat with TERG-A-ZYME
because the local water at the new plant site was hard water with enzyme cleaner at moderate temperatures to restore the filters to
a lot of dissolved calcium and magnesium in the water. By their normal flow rates and pressures.
switching to a deionized water rinse at the new plant and by beef-
ing up the air knives, spot free drying was achieved. Initial Problem Solution
Time 1 hour 1 hour
Initial Problem Solution
Temp 55 deg C 55 deg C
Time 10 s/ft 10 s/ft
Agitation circulate circulate
Temp 55 deg C 55 deg C
Chemistry high alkaline 1/2% TERG-A-ZYME
Agitation spray spray
Rinse tap water tap water
Chemistry 1/2% DET-O-JET 1/2% DET-O-JET
Dry none needed none needed
Rinse hard tap water deionized water
Problem fouled filter membranes
Dry air knife air
Problem water spots

174 The Aqueous Cleaning Handbook Appendix 175

6. WINE TASTING GLASSES 7. LABORATORY PIPETS FAIL TO DELIVER
ELIMINATING DETERGENT FRAGRANCE RESIDUES INCREASED AGITATION IMPROVES CLEANING
The world renowned wine critic Robert Parker observed in his An analytical laboratory had been using volumetric pipets to pre-
book BORDEAUX, “I can’t begin to tell you how many dinner cisely measure volumes of analytical reagents. When they cali-
parties I have attended where the wonderful, cedary, blackcurrant brated their pipets they found that their old pipets were not as
bouquet of 15- or 20-year-old Pauillac was flawed by the smell of reliable as brand new ones. The problem was traced to incom-
dishwater detergents...” In fact the human palate is very sensitive plete cleaning. The old cleaning process involved soaking the
to fragrances found in many detergents. A major supplier of wine pipets in a static soak bath and then rinsing them in a siphon
tasting glasses found that he was able to satisfy the needs of his pipet rinser before air drying. By adding ALCOTABS tablets to
discerning clientele by suggesting they use free-rinsing, fragrance- the siphon pipet rinser, a concentration of detergent became
free LIQUI-NOX cleaner instead of the depositing fragrance con- available for cleaning during the higher agitation rinse process to
taining household dishwashing detergents they had been using. complete the removal of residues that had been loosened during
soaking. After the ALCOTAB had completely dissolved in the
Initial Problem Solution siphon rinser, rinse water continues to flow and rinsing is
Time 30 sec 30 sec completed.
Temp 50 deg C 50 deg C Initial Problem Solution
Agitation manual manual Time 8 hours 8 hours
Chemistry dish detergent 1% LIQUI-NOX Temp ambient ambient
Rinse tap water tap water Agitation soak soak followed by circulate
Dry air air Chemistry lab detergent lab detergent plus ALCOTABS
Problem Fragrance residues on wineglasses Rinse DI water DI water
interfered with wine bouquet Dry air air
Problem soaking alone could not remove all
reagent residues in pipets

176 The Aqueous Cleaning Handbook Appendix 177

 APPENDIX VI
Index
A 69, 87-93, 95, 127, 131-132,
Absorption, 25, 27, 145, 151, 153
Acid cleaners, 44, 46, 84, 165
Acrylic, 86, 91
Activated carbon, 130-132, 135
Additives, 9, 12, 15-16, 75
ADI carryover, 123
Aggressive, 22-23, 38-39, 42, 46-
47, 56, 90, 134-135, 167
Agitation, 13, 17, 19-20, 22, 23,
28, 30-31, 34, 38, 39, 43, 52, 54,
55, 56, 57, 62, 68, 77, 80, 92,
97, 101, 103, 108, 116, 171-177
Air knife, 26, 59, 107, 174
Air pollution, 52
Air/solution interface, 20, 28, 80
Alkaline, vii, 11-13, 14, 16-18, 37,
44-46, 56, 66, 68-69, 80, 82-85,
89, 90-94, 107, 137, 139, 158,
159, 163, 165-167, 173, 175
Alkaline cleaner, 17, 46, 165
Alkaline salt builders, 11
Aluminum, 34, 39, 42, 44, 60, 66,
78, 88, 91, 107, 110, 164
Aluminum foil, 110
Amphoteric surfactant, 10
Analytical method, 119-120, 125-
126
Anion, 135, 151
Anionic surfactant, 9-10, 125,
165, 167
Anodized part, 88
Anti-redeposition, 9, 15, 20
Aquatic toxicity, 157
Aqueous, iii, vii-x, 1-2, 4-9, 13-
16, 18-20, 23-25, 27, 31, 39, 41-
44, 46, 48-49, 51, 61-62, 65, 67-
178 The Aqueous Cleaning Handbook Appendix
134, 138-139, 151, 153, 155-
160, 165-166, 168
Aqueous cleaner, iii, vii, ix-x, 1-2,
4, 6-9, 13-16, 19-20, 27, 41, 46,
48-49 51, 61-62, 67-68, 87-91,
93, 95, 127, 155-160, 165-166,
168
ASTM, 142, 145, 153
Atomic absorption (AA), 145
Atomizer, 141, 143, 146
Automatic syphon washing, 81
B
Batch cleaning, 35, 78
Bath dumping, 46
Bath life, 14, 34, 37, 130, 135,
172
Bench-scale, 54, 57-60, 63
Bench-scale testing, 57-60
Bioburden, 122, 124, 165
Biodegradable, 14, 45, 48, 156-
157
Biotechnology, 78, 128
Blender, 71
Blood, 65-66, 78, 80, 83, 164
Blood-born pathogens, 66
Blow-drying, 26
BOD, 129, 131, 162
Body fluids, 65-66, 78, 80, 164
Builder, vii, 1, 9, 11-12, 14, 135,
165-167
C
Calcium, 6, 11-13, 15, 24, 32,
135, 166, 168, 174
Carbon, 3-4, 86, 121, 124-126,
179
 130-132, 135, 142, 150
Carbon coulometry, 142, 150
Carcinogens, 82
Cationic surfactants, 10
Cavitation, 56-57, 105-106, 116
Centrifugal drying, 26
Ceramic, 44, 60, 80, 84-85, 88,
90-91, 164
Certificates of Analysis, 21, 127
CFC(s), v, vii, 2-5, 8, 44, 85, 87,
162
Chamber flexibility, 73
Change control/maintenance,
119
Chelating, 9, 11-12, 15, 42, 85,
90, 93, 166, 168
Chelating agent, 9, 11-12, 15, 42,
85, 90, 93, 166, 168
Chemical drying, 25
Chlorocarbon, 3
Chlorofluorocarbon, v, 3-4
Circuit board cleaning, 24
Circulation system, 36
Clean Air Act Amendment, iv, v,
8, 45, 48
Cleaner concentration, 12, 34,
71, 147
Cleaner recycling, iv, 129, 131,
139
Cleaner type, iv, 33, 161, 163
Cleaning efficiency, 43, 69
Cleaning method, 20, 22-23, 27,
31-35, 41, 45, 51, 54, 57, 59, 61,
63, 78-80, 156, 163
Cleaning performance, ix-x, 8,
31, 34, 38, 47, 54, 62, 105-106,
138, 171
Cleaning process, iii, ix, 17, 19,
27, 44, 52, 54, 62, 95, 99, 105,
117, 119, 124, 126, 128, 133,
135, 147, 155, 156, 157, 159,
177
Cleaning process design, 119,
126
Cleaning time, 19, 22-23, 34, 39,
52, 55, 63, 117, 147
180
Cleaning validation, iv, 67, 78,
95, 117, 119, 120, 124-125, 127-
128
Clean-in-place, 22, 28-29, 36, 44,
57, 67-68, 71, 80, 81-82, 91-92,
94, 114-115, 164
Cleanroom, 24, 88
Closed-loop, 18, 131, 132, 138,
139
COD, 129, 135, 162
Computer parts, 88
Concentrated cleaner, 16
Concentration, vi, ix, 12-14, 16,
21, 31, 33-34, 37-39, 42, 46, 58,
61-62, 70-71, 79, 90, 97, 108-
109, 111, 122, 133, 136, 147,
151-152, 157, 167, 172, 177
Concentration gradient dissolv-
ing, 58
Conductive residue, 24, 84
Conductivity, 37-38, 72, 97, 111,
121, 125, 135-137
Contact-angle, 54, 146, 149
Contaminant, 6, 15, 23, 52, 83,
84, 85, 86, 93, 99, 105, 129,
130, 131, 132, 134, 135, 143,
144, 146, 148, 150, 151
Contaminant dispersants, 15
Controlled foaming, 56
Corrosion, 9, 15, 17, 23, 24, 33,
35, 38, 39, 60, 65, 71, 84, 86,
88-89, 93, 109, 166
Corrosion inhibiting agents, 15
Corrosion inhibition, 9, 38, 166
Corrosion inhibitor, 15, 24, 39,
71, 88
Corrosivity, 47, 52, 138
Cosmetic, ix, 88, 92, 148, 164
Counterflow-cascade, 23, 58
Counterflow-cascade rinse, 23
Coupling agent, 16
Coupon sampling, 121, 122
Cross-contamination, 24, 65-67,
82-83, 95
Cycle time, 56, 73
The Aqueous Cleaning Handbook
D Electronics, 24, 39, 44, 84-85, 87,
Deflocculation, 13-14, 166
Defluxing, 87
Deionized water, 23-24, 30, 32,
54, 58, 82, 98, 104, 106-107,
145, 149, 171-174
Detection limit, 123
Detergency, 2, 15-17, 44, 52, 69
Detergent concentration, 21, 34,
37, 38, 61, 147
Detergent solution, 13, 28, 37-38,
68, 80, 98-100, 105, 107, 116,
132-133, 137
Dipole moment, 6-7, 85
Disinfectant, 10, 103
Dispersant, 9-10, 43, 92, 165-167,
169
Dispersing, 13-14, 17, 33, 35, 42,
56, 94, 137, 166
Displacement, 25, 58
Disposable, 45, 48, 67, 78, 79
Disposal, 15, 41, 52, 79, 103, 129-
130, 134, 137
Dissolved inorganic solids, 129
Dissolved organics, 129
Dissolving, 1, 6, 15, 17, 22, 55,
167-168
Distilled water, 6, 23-24, 32, 81-
82, 98, 104
Drying, vi, 19, 24-29, 31, 33, 39,
51-52, 54, 58-59, 61, 75, 80-81,
88-89, 97-98, 100, 102, 105,
107, 112-114, 116, 124, 174,
177
Drying method, 19, 24, 33, 51,
54, 58, 59
E Flammable, 45, 94, 159, 160
Economic factors, 137
Economy, 21, 45
EDTA, 12, 15, 166
Electron spectroscopy, 142, 150
Electronic component, ix, 24, 32,
84, 138
Electronic solder flux cleaning,
20
Appendix
164
Electrostatic repulsion, 71
Emulsification, 13, 137
Emulsified oils, 15, 129, 134
Emulsifier, vii, 1, 9, 11, 13-14,
85, 165-169
Endoscopes, 66
Endotoxin, 68, 79, 122, 124
Environmental and water test-
ing, 82
Environmental considerations,
43, 48
Enzymatic detection, 121
Enzymatic hydrolyzing, 55
Enzyme, 15, 44, 65-66, 68, 80,
84, 94, 114, 125, 163, 167, 175
EPA Priority Pollutants, 45, 48
Equipment "blanks", 83
EU, 67, 125
Eutrophication, 157, 158
Evaluation method, 51, 54
Evaporation, 3, 24, 25, 33, 116,
130, 136, 141, 145
Evaporators, 130
Extenders, 16
Extraction, 141, 143-145, 151
F
FDA, 67-68, 73, 121, 125, 128,
164-165
Ferrous, 42
Filler, 16, 45, 46, 68, 166
Filter, iv, 26, 36, 67, 75, 78, 84,
88, 94, 114, 122, 129, 131-135,
141, 144, 156, 164, 175
Flash point, 47, 132, 138
Flocculent, 129
Flow-through clean-in-place, 22
Fluid processing, 93-94
Foam height, 136-137
Foam suppressing capabilities,
21
Foaming agents, 15, 20
181
Food and beverage processing,
83
Forced-air, 26, 39, 59
Forced-air drying, 39
Free alkalinity, 37, 135
Free-rinsing, 41, 44, 58, 79, 176
FTIR, 54, 135, 142, 151
G 34-36, 55-57, 63, 79, 84, 90, 92,
Gas chromatography, 126, 142,
151, 166
Glass, iv, ix, 42, 44, 59, 61, 65,
67-69, 70-71, 74, 79-80, 82-84,
87, 90-91, 100, 102-103, 107,
122, 144-148, 150, 164, 174
Glassware washer, 30
Global warming, v, 3-5, 162
GMP, 66, 72-78, 111, 113, 119
GMP washing machines, 72
Gravimetric, 54, 141, 145
H In-situ particle counting (ISPM),
Hazardous, vi, vii, 3, 8, 44-45, 47,
91, 135, 137, 155-156, 158-160,
164
Hazardous chemicals, vi, 8, 155,
159
Hazardous substance list, 45, 47
HCFC, v, vii, 2-5, 8
Healthcare, 65-66, 164
HEPA filter, 75
High emulsifying, 20, 42, 55, 90,
92, 136
High volume/low pressure, 56-57
High-agitation spraying, 55
High-foaming cleaners, 56
HPLC, 121, 126, 135, 145, 167
Hydrochlorofluorocarbon, v, 3-5
Hydrogen bonding, 7, 10
Hydrolysis, 13, 16, 17, 56, 135,
165
Hydrolyzed, 17, 167
Hydrophilic, 9, 11, 14, 133, 146,
167, 169
Hydrophobic, 9, 11, 45, 133, 142-
182
143, 145-146, 148, 167-169
Hydrotropes, 16
Hydroxide, 2, 14, 16, 69, 136, 168
I Nuclear, 93, 164
ICH, 67, 125, 167
Ignitability, 138
Immersion, 5, 12-14, 28, 30-32,
116, 172
Immersion cleaning, 13-14, 32,
34, 36, 55-57, 79, 84, 90, 92
Ingredients, 1, 7, 9, 11, 14-16, 21,
37, 42, 45-47, 67, 75, 83, 87, 92-
3, 111, 121, 124-125, 155-159,
165-167
Inhibitor, 15, 24, 39, 46, 71, 88
Inorganic, 6, 9, 11, 14, 17, 42, 44,
60, 82, 90-91, 114-115, 129,
131, 136, 143, 145, 151, 164,
173
Inorganic soil, 9, 42, 44, 60, 90
146
Insoluble oils, 1, 11, 129
Insoluble particles, 14
Installation Qualification (IQ),
119
Interfering detergent residue, 44
Ion chromatography (IC), 142,
151
Ionic, 10, 85, 86, 87, 135-137,
151, 167
Irritants, 47
L Montreal Protocol on Substances
Laboratory cleaning, 30, 79-81
LD50, 122-123
Limonene, 5
Lipophilic, 14
Liquids, ix, 5, 15, 46, 149, 151,
166
Lot number tracking, 21
Low volume/high pressure, 56-57
Low-foaming, 20, 29-30, 56,81,
92, 163
The Aqueous Cleaning Handbook
Low-foaming detergent, 20, 30,
81
Low-power microscope inspec-
tion, 142
M
Machine cleaning, 20, 81
Machine washing, 20, 29, 81
Magnesium, 6, 11, 13, 15, 24, 32,
42, 135, 166, 168, 174
Manual, 20, 22-23, 28, 34-36, 44,
47, 57, 63, 55-67, 68, 71, 76,
80, 82-83, 85, 91-94, 97, 98-102,
163-164, 173, 176
Manual cleaning, 20, 23, 28, 34,
35, 36, 47, 57, 63, 80, 83, 99-
100, 102, 173
Manual surface cleaning, 98
Mass displacement, 58
Mass spectrophotometry, 142
Master validation plan, 119
Material Safety Data Sheet, vi,
45, 47, 158-159, 162
Measuring cleanliness, iv, 141
Mechanical action, 5, 12, 13
Mechanical agitation, 20
Medical device manufacturing,
78, 122
Metal finishing, 88
Micelle, 11-12, 79, 166-167
Microfiltration, 132, 134-135
Millipore filter measurement,
141, 144
Minimal system, 63
Mixer, 71, 84, 114, 116, 123
that Deplete the Ozone Layer, 5
N 92, 133, 164
Neutral, 14, 16-17, 37, 65, 69, 71,
84, 91, 93, 137, 163, 167
Nonferrous, 42
Nonionic, 9-10, 14, 20, 85-86,
136, 137, 151, 167, 169
Nonionic contaminant, 86
Nonionic surfactant, 10, 14, 125,
Appendix
167
Nonpolar, 85
Nonvolatile Residue Inspection
(NVR), 141, 143
O
Oil evaporation, 141, 145
Oil viscosities, 61
Oleophilic, 9, 11, 133
Operating cost, 46, 131
Operational Qualification (OQ),
119, 167
Optical microscopy, 141, 144
Optically stimulated electronic
emission, 142, 151
Optics, 91-92, 164
Organic, v, vi, ix, 1, 3, 4, 5, 6, 8,
9, 10, 11, 13, 15, 32, 41, 42, 44,
45, 48, 60, 82, 84, 85, 86, 88,
90, 94, 121, 124, 125, 126, 129,
130, 131, 135, 143, 145, 150,
151, 158, 160, 162, 165, 167,
168, 169
Organic-free, 82
OSEE, 54, 142
OSHA, 45, 47, 159-160, 162
Outgas, 84
Overkill system, 63
Ozone depletion, 3, 45
P
Parenteral medical device, 79
Particulate, 11, 17, 22, 42-44 56,
61, 74, 75, 85, 91, 103, 114,
115, 132, 137, 150, 164, 166,
169
Parts washer, 30, 32, 44, 85, 91-
Pathogens, 66
PC board, 30-31, 85
PC board washer, 30, 31
Performance Qualification (PQ),
119
Permeate, 133
pH, 10, 14-17, 37, 39, 65, 69-71,
183
 84, 90-91, 93, 97, 100-102, 109,
121, 129, 134, 136-138, 157,
165, 167
Pharmaceutical, iv, 24, 32, 66-69,
71-72, 77, 78, 82, 92, 95, 119-
122, 128, 138, 164-166, 173
Phosphate, 83, 125, 158, 164
Physical drying, 24-26
Physical filtration, 37, 132
Physical separation, 133
Pilot scale, 63, 71, 78
Piping system, 71, 94
pKa, 69, 70, 71
Placebo sampling, 121
Plastic, ix, 34, 39, 42, 59, 65-66,
68, 74, 78-79, 84, 89-90, 93,
144, 153
Plastics compatibility, 89
Polar, 6-7, 10, 85, 168
Polar soil, 6-7, 168
Polar solvent, 6, 168
Polymerized rosin, 87
Porous surface, 60
Postcleaning handling, 19, 27,
34, 97, 112
Powder, 15-16, 46, 163
Power spray wand, 29
Power washer, 29
Precleaning handling, 19, 31, 97
Presoaking, 21-22, 99, 105
Pressurized spray, 30
Protein, 17, 34, 69, 84, 99, 105,
167
Proteinaceous soil, 44, 65-66, 80,
83, 164, 175
Q Sampling method, 120-121
Quality control, 21, 52, 73, 93,
128, 134, 138, 149
R Saponification, 9, 13-14, 167
RCRA, 45, 48, 138, 160, 162
RCRA Hazard Classification, 45
Reactivity, 45, 47, 69, 127, 138
Recycling, iv, 13, 18, 43, 46, 79,
184
129, 131-135, 137-139, 147, 156
Refractometry, 136-137
Regulatory review, 159
Residue, ix, 6, 17, 21, 23-26, 28,
30, 32, 39, 41, 44-45, 67-71, 78-
80, 82-90, 92, 94-95, 115-117,
120-127, 141-145, 148, 164,
168, 176-177
Residue acceptance criteria, 121-
122
Residue detection method selec-
tion, 120-121
Residue identification, 120-121
Residue-free, 45
Retentate, 133
Rinse, 13, 19, 21, 23-24, 28-33,
39, 44-45, 51, 58-59, 68, 71-72,
80-82, 89, 92, 99-100, 106-108,
111-113, 115-116, 121-124, 132,
134-135, 147, 156, 168, 171-177
Rinse aid, 44-45
Rinse procedure, 32, 81, 99, 106
Rinse water sampling, 72, 121
Rinsing, vi, 5, 9, 13, 21, 23-25,
29, 31-32, 39, 41, 44, 52, 54, 58-
59, 61, 72, 79, 81-82, 88-89, 92,
98, 102-107, 111, 114, 116, 124,
134-135, 155-156, 176-177
Rosin, 44, 85-87, 164, 168
Rubber, 4, 42, 47, 82-83, 89, 91,
102, 107, 164
S Solvent, v, vi, vii, ix, 1-8, 13, 15,
Safety based limit, 122, 123
Salt, 1, 11, 14, 15, 17, 24, 33, 37,
60, 68, 83, 85, 87, 88, 90-91, 94,
134, 135, 136, 164, 166, 167,
168, 173
Sampling procedures and recov-
ery, 119
Sanitizer, 30
Saponifier, 2,15, 20, 168
Scale, 16-17, 44, 80, 83, 88, 91,
115, 164
Scale-up, 55, 57-60
The Aqueous Cleaning Handbook
Scanning Electron Microscopy
(SEM), 142, 152
Secondary Ion Mass
Spectroscopy (SIMS), 142, 152
Semiaqueous cleaner, 5, 14, 17,
160, 168
Separator, 130, 134
Sequestering agent, 11-12, 15,
44, 166, 168
Sequestration, 13, 165
Sessile drop technique, 149
Silicates, 14
Skimmer, 130, 134, 139
Soak, 19-20, 22-24, 28, 30, 32,
35-36, 44, 58-59, 62, 66-68, 71,
80-83, 85, 91-93-94, 99, 105,
115, 139, 163-164, 172, 177
Soak cleaning, 22, 35, 36, 71
Soaking, 22, 23, 28, 35-36, 55,
65, 80, 93, 99, 105, 177
Soap, 1-2, 6, 10, 12-16, 20, 167-
168
Soil, 1-3, 5-7, 9, 11-17, 19-23, 28,
32-34, 37, 41-46, 51-52, 54-55,
57-61, 65-66, 68, 78, 80-83, 85,
89-90, 91-94, 97, 99, 105, 113,
117, 132-133, 135-138, 141,
143-146, 155-156, 159, 166-168,
172-173, 175
Solder paste, 87
Solubilization, 13, 25, 42
Solution recharge, 133
25, 27, 39, 41, 44-45, 46-48, 52,
59, 61, 87-88, 90-91, 131-132,
143-145, 151, 158-160, 164,
166, 168
Spray, 12-13, 20, 22-23, 28-36,
44, 47, 55-57, 63, 67-68, 71, 74,
80-83, 85, 91-94, 111, 113, 116-
117, 144, 158, 163-164, 174
Spray agitation, 30, 55
Spray cleaning, 13, 22-23, 34-36,
47, 55-57, 158
Spray clean-in-place, 28-29, 36,
44, 68, 80, 82-83, 91, 94, 164
Stabilizers, 15
Appendix
Stainless steel, 15, 42, 44, 59, 65,
67, 69, 71, 74, 75, 82-84, 91,
107, 114, 115, 164
Stainless steel cleaning, 69
Standard operating procedure,
iv, 67, 78, 97, 111, 117, 126, 168
Steel, 15, 39, 42, 44, 59, 65, 67-
71, 74, 75, 77, 82-84, 91, 103,
107, 114-115, 164
Sterilization, 65-66, 103-104
Sterilizing, 65, 78
Substrate, iv, 1, 3, 12-15, 17, 19-
20, 23-26, 28, 32-34, 42, 44, 51-
52, 54-56, 59-61, 69, 88-89, 92,
149, 164
Surface active agent, 1, 2, 9, 165,
167-169
Surface contact-angle, 54
Surface energy, 141, 145-146,
148-149, 153
Surface tension, 11, 12, 14, 21,
43, 90, 149, 166, 168
Surfactant, vii, 1, 5-6, 9-14, 16,
20, 21, 25, 39, 44, 48, 125, 135,
136, 137, 157, 160, 165-169
Surfactant-free cleaner, 20
Suspended solid, 129
Suspension, 11, 43, 67, 133, 166
Swabbing surface, 121
Synthetic solvent, 2-3
T
Tank, 22-24, 26, 28-31, 36, 46,
55, 57-59, 67, 71, 80-81, 93-95,
97-98, 100-101, 104-107, 110,
114-117, 129-130, 132, 134,
139, 172
Tap water, 11, 23, 24, 58, 82, 92,
98, 99, 104, 105, 106, 114, 168,
174, 175, 176
Tape test, 141, 144
Temperature, 12-15, 17, 19-23,
29-31, 33-34, 38-39, 42-43, 52,
54-55, 61-63, 71, 73, 75, 77, 81,
86, 90, 92, 97, 99, 101, 105,
111-117, 130, 133-134, 136,
171, 175
185
Terpene, 3, 5
Test, 51, 54, 59-61, 119, 141, 144,
148
Test acceptance limit, 119
Test cleaning, 51, 54, 61
Test soil, 51, 60
Test substrate, 51, 59
Testing, 19, 54-55, 57-62, 68, 82-
83, 86, 113, 120, 122, 145-146
Testing, iii, vi, 51, 113, 153
Time, vii, x, 12, 17, 19, 22-23, 25,
28, 31, 34-35, 38-39, 43, 46-47,
52, 54-57, 61-63, 71, 73, 75, 77,
80, 89, 97, 99-100, 105, 110-
111, 114, 116-117, 124, 132,
139, 147-149, 152, 156-157,
171-177
Titration, 27, 37, 121, 125-126
Total alkalinity, 135
Toxicity, 47, 52, 82, 88, 120, 122,
127, 138, 157
Trace analysis, 82, 144-145
Trace metals, 80, 82, 164
U Waxy or oily soils, 22
Ultrafiltration, 18, 114, 133-135
Ultrasonic, 12-13, 20, 22, 29-32,
34-36, 44, 57, 66-68, 78, 80-83,
85, 88, 90-92, 97, 104, 106-108,
110, 146-147, 163-164, 171
Ultrasonic cleaning, 20, 22, 29,
35, 57, 67, 78, 81, 91, 97, 104,
106-107, 110, 147
Ultrasonically agitated rinsing,
23
USP, 111, 125
UV, v, 121, 126, 131, 141, 143,
145, 151, 162, 169
UV spectroscopy, 121
186
V
Vacuum drying, 25, 33, 39
Vapor degreasers, 5
Vesication, 86
Visual inspection, 54, 61, 141-
142, 144
VOC, v, 4, 8, 45, 162
VOCs, 3-4, 41
Volatile, v, ix, 2-4, 8, 41, 44-45,
48, 52, 59, 61, 91, 156, 158-159,
162, 164, 168
W
Wash cycle, 29, 72, 81, 111
Waste treatment, 52, 94,175
Waste-treatment filtration, 94
Wastewater treatment, iv, 129,
130, 131
Water break, 141-143, 146
Water drop surface energy test,
148
Water testing, 82
Wax melting points, 61
Wetting, 1, 9, 11, 13-14, 20, 43,
56, 90, 150, 153, 169
Wetting agent, 1, 9, 11, 169
WFI, 68, 74, 79, 111, 121
White residue, 86-87
Wiping and visual inspecting,
141, 142
Worker safety, 41, 52, 158, 160
Z
Zero-discharge, 156
The Aqueous Cleaning Handbook