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

vi The Aqueous Cleaning Handbook 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- more readily removed from a reaction mixture by distillation
based compounds such as CFCs, HCFCs, and PFCs. or evaporation. In cleaning substrates, the most common
• Aqueous cleaners—which use blends of detergent com- application for industrial solvents is to put dirty solid matter
pounds with surface active agents together with other (parts, products, etc.) into the solvent where foreign matter on
cleaning chemicals that use detergency to lift soil from a the surface is dissolved into the solvent. The substrate is then
surface by displacing it with surface active materials that removed from the solvent-dilute-foreign-matter mixture which
have a greater affinity for the surface than for the soil. evaporates and deposits a relatively much smaller amount of
foreign matter left over from the dilute mixture—leaving a
Soaps—A name stemming from the soapberry, the common proportionally clean substrate.
name for about 13 species of deciduous or evergreen trees in The principle of ‘like dissolves like’ was discovered early in
the soapberry family whose fruit contains a soapy substance human history by simple observation. In this trial-and-error
called saponin—a natural cleansing agent produced by the process some terpenes, natural organic compounds occurring
reaction of an alkali, typically sodium hydroxide (NaOH) and in the essential oils and oleoresins of plants (lemon, orange)
animal fat or vegetable oil. Its use dates at least from the third and conifers (balsam, pine), were found to have solvating pow-
millennium BC. (In fact, clay tablets in Mesopotamia con- ers. It is very important to match the solvent character of your
tained a recipe for soap that included potash—potassium car- soil or foreign matter to the type of solvent with which you are
bonate—and oil.) cleaning. A given solvent will be “like” some soils and “unlike”
The second-century writings of the Greek physician, other soils where it will not be able to dissolve and clean as
Galen, referenced soap as a cleansing, medicinal product that well as a solvent with like properties.
helped to cure skin ailments. Later, the ancient Romans
shared their knowledge of soap formulation (sapo, the Latin Synthetic Solvents—Nonaqueous solvent cleaners include
word for soap is still used to describe the saponifiers often chlorocarbons, chlorofluorocarbons (CFCs), and hydrochloro-
added to today’s synthetic detergents) and by the Middle Ages fluorocarbons (HCFCs). Chlorocarbons are carbon-chlorine
commercial soapmaking centers were established in such based solvents. Halocarbons are halogen-carbon compounds
European countries as France and Spain as well as in (chlorine, fluorine, bromine, and iodine).
England. Manufacturing methods were crude, however, until The most common examples used in cleaning are carbon
discoveries by Nicholas LeBlanc in the 1800s and a century tetrachloride, trichlorocarbon (TCA, “trike,” or methylchoro-
later by Michel Chevreul made it possible to make predictable form), and perchloroethylene (PCE, or “Perc”). Chlorofluoro-
soap formulations. carbons (CFCs) are carbon, fluorine, and chlorine based sol-
vents. The most common example used in cleaning is CFC-
Solvents—To understand solvents and their strengths and lia- 113. Hydrofluorochlorocarbons (HCFCs) are modified CFCs
bilities as cleaning materials, it’s important to understand “sol- with the addition of hydrogen. The HCFCs were developed as
vency”—the ability to dissolve. A solvent is usually a liquid less hazardous replacements for CFCs.
substance that is capable of forming a physical, homogeneous The chlorocarbons have good cleaning properties but
solution. Some materials are soluble in certain other materials unfortunately have toxic vapors, usually with a narcotic effect.
in all proportions, while others are soluble only up to a specif- The vapors also contribute to smog formation. Chlorocarbons
ic percentage and any excess precipitates out of the solution. are volatile organic compounds (VOCs).
Another important aspect of a solvent is its volatility, The chlorofluorocarbons (CFCs) are less toxic than chloro-
which is highly related to its boiling point. Solvents that have carbons, but unfortunately their vapors contribute to ozone
reasonably low boiling points are more volatile and can be depletion in the atmosphere which can also contribute to glob-

2 The Aqueous Cleaning Handbook What Is An Aqueous Cleaner? 3


al warming. The CFCs are ozone depleting substances (ODS), developing nations to restrict their use and manufacture. This
they have ozone depleting potential (ODP) and they have glob- agreement known as the Montreal Protocol on Substances that
al warming potential (GWP). Deplete the Ozone Layer was signed by 24 countries, including
The history of halocarbon chemistry played an important the U.S., on September 16, 1987. Today, more than 160 coun-
role in the development of solvents and synthetic industrial tries have signed the Protocol.
solvent cleaners—and was used to eventually foster develop- In addition to the above-mentioned compounds, brominat-
ment of aqueous cleaners as a replacement for environmental ed hydrocarbons, dibromomethane (for example, methylene
reasons. Carbon tetrachloride (“carbon tet”)—an important, bromine), are also used for cleaning, although on a much
nonflammable solvent for fats and oils, asphalt, rubber, bitu- smaller scale. In addition to immersion, vapor degreasers are
mens and gums, initially used as a degreasing and cleaning often employed with these types compounds in industrial
agent in the dry-cleaning and textile industries—was first pro- cleaning, but their mechanical action can be viewed as sec-
duced in Germany in 1839 and marketed as a grease remover. ondary because of their excellent solvating properties.
Its vapors, however, are highly toxic. Carbon tetra-chloride is In an effort to continue the use of CFC-related compounds,
also a volatile organic compound (VOC). Evaporating into the hydrochlorofluorocarbons (HCFCs) were developed. These are
atmosphere at ambient conditions, VOCs include almost all generally less toxic than chlorocarbons, and have less ozone
synthetic and plant-derived solvents as well as fuels. The cal- depleting potential than the CFCs. Nonetheless, the HCFCs
culation of the amount of VOC in a particular product or have sufficient ozone depleting potential and global warming
process is important since ozone, the primary component of potential to be of concern to end users.
smog, is affected by VOC emissions.
In the 1890s Swarts discovered that the carbon-fluorine SEMIAQUEOUS CLEANERS
bond could be formed with antimony fluoride and the addition The acute and chronic toxicological profiles of the aforemen-
of trace quantities of pentavalent antimony as a fluorine carri- tioned organic and first-alternative CFC cleaners, coupled with
er to form chlorofluorocarbons (CFCs) from chlorocarbons the negative environmental impact of second-generation
such as carbon tetrachloride. Through his work, carbon tetra- HCFC substitutes, stimulated the development of new, innova-
chloride also became known as tetrachloromethane, the chem- tive cleaning techniques and a rebirth of aqueous and semi-
ical precursor of CFCs—and led to the development of the first aqueous cleaning.
commercial refrigeration systems some thirty years later. Semiaqueous cleaning incorporates the principles of aque-
During the following 50 years, continuous reactor process- ous and organic cleaners. This is accomplished by combining a
es were developed to control the degree of fluorination of the surfactant with a low-volatility hydrocarbon such as a terpene,
carbon molecule for the manufacture of refrigerator coolants, in particular limonene and pinene (citrus or pine in origin), to
some of which exhibited excellent characteristics as a solvent form a cleaning blend. Terpenes are homocyclic hydrocarbons
and cleaning agent. and have a characteristic strong odor; turpentine is an illustra-
There are a number of carbon-derived cleaning com- tive solvent that is a mixture of terpenes. Semiaqueous cleaning
pounds, including hydrocarbons, halocarbons, chlorofluorcar- involves cleaning with a solvent or solvent/water mixture fol-
bons (CFCs), hydrochlorofluorocarbons (HCFCs), hydrofluo- lowed by rinsing with water as in traditional aqueous cleaning.
roether, and perfluorocarbons (PFCs). While each has its own Unlike traditional vapor degreasing, however, cleaning
cleaning advantages, they all have built-in environmental lia- with semiaqueous cleaners does not rely on boiling liquids,
bilities—CFCs, HCFCs and PFCs are believed to contribute to nor is it restricted to a constant boiling composition. In its
global warming. Manufacture of ozone-depleting compounds simplest form, semiaqueous cleaning involves using its organ-
was phased out after a world meeting among industrial and ic components to dissolve soils and its water component to

4 The Aqueous Cleaning Handbook 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 organic molecules) that are electrostatically attracted to par-
sodium or potassium. Examples include sodium alkylbenzene ticulates, creating a bridge between the water and the water
sulfonates, sodium stearate (a soap), and potassium alcohol insoluble solid particulate (in some cases even repelling the
sulfates. Anionic surfactants are ionic and are made up of two solid surface to help lift the particles into suspension).
ions—a positively charged usually metal ion and a negatively
charged organic ion. Emulsifiers—These cleaner ingredients help emulsify water-
insoluble oils into solution by helping to create a liquid-liquid
Nonionic surfactants—These are surfactants that have no mixture. Surfactants that use their hydrophobic (water-hating
ions. They derive their polarity from having an oxygen-rich or repelling) or oleophilic (oil-loving) end of their molecule to
portion of the molecule at one end and a large organic mole- mix with water-insoluble oils and their hydrophilic (water-lov-
cule at the other end. The oxygen component is usually ing) end to mix with water create a bridge to emulsify water-
derived from short polymers of ethylene oxide or propylene insoluble oils into solution. The specific structure of the bridge
oxide. Just as in water chemistry, the oxygen is a dense elec- is called a micelle that can be thought of as a hollow, oil-filled
tron-rich atom that gives the entire molecule a partial net-neg- round ball with a skin made of surfactants with their
ative charge which makes the whole molecule polar and able hydrophilic ends facing out in contact with the water solution
to participate in hydrogen bonding with water (as discussed in and the hydrophobic ends facing in to the oil-filled ball.
the first chapter). Examples of nonionic surfactants are alco-
hol ethoxylates, nonylphenoxy polyethylenoxy alcohols, and Wetting Agents—These are surfactants that lower the surface
ethylene oxide/propylene oxide block copolymers. tension of water and allow the cleaning solution to wet sur-
faces and penetrate into, under and around soils and surface
Cationic surfactants—These are positively charged molecules crevices. They create a bridge between the water and any
usually derived from nitrogen compounds. They are not much hydrophobic (water-hating or repelling) surface. You can think
used as cleaning agents in hard-surface cleaners because of of a wetting agent as having one end of the molecule attracted
the tendency of the cationic positively charged molecule to be to the surface while pulling the water solution towards the oth-
attracted to hard surfaces (that usually have a net-negative erwise water-repelling surface, allowing the water solution to
charge). Many cationic surfactants have bacteriacidal or other be in contact with more of the surface that needs to be cleaned.
sanitizing properties that are useful in creating disinfectants
that leave a cationic disinfectant film on the surface. Cationic Builders—These cleaner ingredients react with interfering
surfactants are usually incompatible with anionic surfactants, calcium, magnesium, or iron ions that may be present in the
because they will react with the negatively charged anionic water solution. They stop them from reacting with soils and
surfactant to form an insoluble or ineffective compound. other detergent ingredients to form water insoluble and diffi-
cult-to-clean calcium, magnesium, or iron salts. These metals
Amphoteric surfactants—Those surfactants that change their are present to varying degrees in all water, particularly tap
charge with pH. They can be anionic, nonionic, or cationic water. Builders are usually alkaline salts, chelating agents,
depending on pH. Usually, any one amphoteric can be any two and/or sequestering agents.
of the three charge states.
Alkaline salt builders—These are inorganic salts such as sodi-
Dispersant—This is a cleaner ingredient that helps disperse or um carbonate or sodium phosphates. They react with calcium,
suspend solid particles in solution. Dispersants include water- magnesium, or iron to form water soluble or water dispersible
soluble surfactants or water-soluble polymers (long-chain compounds that tie up the calcium, magnesium, and iron.

10 The Aqueous Cleaning Handbook The Chemistry of Aqueous Cleaning 11


Chelating agents—These are negatively charged or oxygen concentration, and the temperature of the cleaning formula-
containing molecules that react with positively charged metal tion. The surfactant lifts oils off the metal surfaces to form a
ions to form a stable complex. They have multiple locations in suspended oil-water-surfactant emulsion which is then
the molecule to react with multiple positive charges that may removed by rinsing.
be present on multivalent metal ions that have more than one Typically, immersion cleaning involves submerging parts in
positive charge on them. An example of a chelating agent is a bath and providing air agitation, turbulation, and mechani-
EDTA, ethylene diamine tetraacetic acid. EDTA has four acetic cal brushing or ultrasonics to realize desired levels of cleanli-
acid groups giving it a potential for four negatively charged ness while spray cleaning uses a pressurized wash stream to
acetates to bond with up to four positively charged sites in create even higher soil-removal rates.
metal ions with multiple positive charges, such as calcium Cleaning is then followed by water rinsing. In most aque-
which has two (2) positive charges associated with it. ous cleaning systems, more water is used in rinsing than in
cleaning. Also, rinse water must be purified by a recycling sys-
Sequestering agents—These are chelating agents (see above) tem to a higher level than the detergent solution. Rinse water
that bind particularly tightly with metal ions and sequester or also requires different separation equipment, since the rinse
separate them from reacting with other compounds. water is the last solution to touch the surface being cleaned.
The chemical and mechanical action involved in aqueous
Detergents use both chemical and physical action to clean, cleaning is actually a number of processes. These can be
which are affected in turn by temperature, time, type of mechan- described as:
ical action, cleaner concentration, and additives. Mechanical • Solubilization—a process whereby the solubility of a
action is provided by immersion, spray, or ultrasonics. substance is increased in a particular medium
The detergents’ chemical action saponifies certain oils, • Wetting—to lower surface and interfacial tensions so
producing water-soluble soap material. The surfactants used that the cleaner penetrates small spaces while getting
in a cleaning formulation then work to physically reduce the under the soil to lift it from the substrate
surface tension of the solution, in the process emulsifying and • Emulsification—creating an oil/water mixture by coat-
lifting soils away from the substrate being cleaned. These sur- ing of oil droplets with surfactant to keep them from
factant molecules can be both free and aggregate forms called recombining and migrating to the surface of a cleaning
micelles, and their ratio is based on the type of surfactant, its bath (see previous emulsifier discussion)
• Deflocculation—breaking down soil into fine particles
HOW ALKALINE CLEANERS WORK 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-

12 The Aqueous Cleaning Handbook The Chemistry of Aqueous Cleaning 13


ciencies), aqueous cleaners may include a number of the fol- • Saponifiers—Alkalies that react with fatty acids in oils
lowing ingredients, formulated to provide maximum cleaning to form soaps. Chemistry may be mineral (sodium or
effectiveness for specific for various types of substrates and potassium) or organic-based (such as solutions of
soils by reducing surface tension, forming emulsions, and sus- ethanol amines).
pending insoluble particles for removal in the cleaning bath: • Solvents—Aqueous or organic chemistries designed to
• Surfactants—alkaline surfactants that react with fatty enhance the removal of oily soils by dissolving them
acids to form soap. They improve cleaning action by (e.g., glycol ethers, ethylene [Butyl Cellosolve], and
reducing the water’s surface tension which also allows propylene compounds).
for greater penetration or wetting of the liquid onto the • Additives—act primarily as contaminant dispersants,
part surface. Used to either emulsify a soil from a sub- anti-redeposition agents, brighteners, viscosity modifiers,
strate or increase the surface’s wettability. Substances antifoaming agents, and corrosion inhibitors or they may
with both hydrophilic (water soluble) and lipophilic (oil have special detergency on a specific soil type. Examples
soluble) groups that may be cationic, anionic or nonionic include enzymes, amine compounds, and various poly-
depending on the charge of the hydrophilic end. Anionic mers.
surfactants are generally poor cleaners because of their • Sequestering agents—produced as powders or liquids
negative charge. Cationic or positively-charged surfac- to combine with calcium, magnesium, and other heavy
tants are water soluble and are commonly used in metals in hard water. They form molecules in which
immersion cleaning. Nonionic surfactants with no these ions are held securely, or sequestered, so that they
charge are used for surface cleaning when a lower-foam- can no longer react undesirably with other species in
ing detergent is required. A class of synthetic com- solution. Polyphosphates and polyacetates are commonly
pounds, nonionic surfactants are prepared by attaching used.
ethylene oxide molecules to water-insoluble polymers, • Chelating agents—employed to solubilize hard water
but are usually biodegradable in aqueous cleaners. In salts so that they remain in solution. Produced in both
addition to wetting, surfactants can also enhance the powdered and liquid forms, they do not degrade or lose
emulsifying and dispersing properties of a cleaner. their potency at elevated temperatures, which make them
• Builders—inorganic salts that provide alkalinity and ideal for aqueous cleaning. However, they can interfere
buffering capacity common to almost all aqueous clean- with the ability of other chemicals to remove emulsified
ers (pH may be alkaline >7, neutral ~7, or acidic <7). oils and dissolved metals from solution, which can lead
Alkalinity may be provided by hydroxides, carbonates, to waste disposal problems. In addition to EDTA, nitrilo
borates, silicates, phosphates, or zeolites (crystalline tri acetate (NTA) is also used.
hydrated aluminosilicates). Builders also soften water or • Corrosion Inhibiting agents—are often added to aque-
help with saponification or deflocculation. ous cleaners to minimize their effect on metal substrates.
• Emulsifiers—substances that can form liquid-liquid They are used for cleaning at high pH and as rust
mixtures (e.g., oil and grease) that do not dissolve in inhibitors to prevent the rusting or oxidation of cleaned
water. Emulsifiers are useful for low soil loading, but parts (or cleaning equipment that is not constructed of
their concentration in a detergent limits bath life. stainless steel).
Separation of soil and cleaner may be accomplished by • Stabilizers—added to extend the shelf life of detergent
making the emulsion unstable by lowering the pH and/or ingredients and to maintain the uniformity of detergent
temperature. They are chemically similar to the semi- blends. For example, dilute cleaner solutions may have a
aqueous cleaners described below. tendency to grow microbes. The presence of biocidal

14 The Aqueous Cleaning Handbook 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 Alkaline cleaners work best when the soil can be hydro-
It is important to keep in mind that a cleaner’s pH value can lyzed (typically natural oils and fats, fingerprints, natural
have a direct effect on cleaning effectiveness. Technically greases, some types of food products, and protein residues).
speaking, pH is the “negative log of the hydrogenion concen- The cleaning process should be enclosed to avoid exposure
tration.” This means that the higher the pH, the greater the in- hazards. (Workers should use personal protective equipment
crease in hydroxide concentration and the faster hydrolysis— with handheld sprays.)
the breaking down of a natural fat or oil into a soap—occurs. Time, temperature, and agitation also play important roles
Aqueous cleaners are classified according to pH value as in cleaning. But while maximum detergency is achieved at
being neutral, acidic, or alkaline on a scale of zero to 14, with high temperatures with high agitation over long periods of
a pH of 7 being neutral. Thus, a pH value of less than seven is time, the substrate must be robust since corrosion is also a
considered acidic, and higher than seven, alkaline. factor.
Each detergent formulation has maximum effectiveness at As a rule of thumb, it is best to use the mildest cleaner
a specific pH value. An acidic solution with a pH of 4.5, for possible.
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

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 erly if the temperature is hot enough. You need to know the
The cleaner or detergent used should be matched to the minimum temperature at which to use these cleaners.
desired cleaning method, and the surface and types of soils Finally, there are controlled foam cleaners that usually
being cleaned. For instance, a low-foaming detergent should have limited foam suppressing capabilities. The surfactants
be used for spray or machine cleaning, a good anti-redeposi- themselves do not foam excessively, but they will not be able
tion detergent for soak and ultrasonic cleaning, a high emulsi- to control much foam that results from soils.
fying and wetting detergent for manual cleaning. The deter- It is critical that the detergent be scientifically formulated
gent, temperature, and degree of agitation should be strong to clean effectively and to rinse away without leaving interfer-
enough to remove the soil to the desired level of cleanliness ing residues. A scientifically formulated detergent will typical-
without harming the substrate being cleaned. ly have appropriate surfactant ingredients and nondepositing
There are some particularly critical aspects to understand rinse-aids. The surfactant should have sufficient surface ten-
in selecting and using a low- or nonfoaming detergent for sion lowering properties to assist in proper rinsing. A surface
spray or machine washing. It is very important to not have tension below 35 dynes per centimeter for the cleaning solu-
foam when cleaning in or with a machine that relies on spray- tion as used is often sufficient for the surfactant to contribute
ing for mechanical agitation. to good rinsing. Nondepositing rinse-aids can help complete a
Foam may build up and spill over from the machine creat- formulation to meet the rinsing requirements of critical clean-
ing a mess. Foam will also build up on the substrate and inter- ing.
fere with the mechanical cleaning energy of the spray. And In addition, the detergents should be manufactured with
finally, foam may get sucked into recirculation pipes causing appropriate quality-control procedures. In many critical-clean-
problems with pumps in the machine. Foam is formed by the ing applications it is desirable to choose a detergent that has
presence of agitation at an air/solution interface when a foam- lot number tracking and can be supplied with certificates of
ing agent is present. analysis from the manufacturer. These certificates document
Surfactants are often foaming agents. Most aqueous clean- each lot of detergent to assure consistency and quality control
ers have surfactants in them. There are three basic types of from lot to lot in order to control for potential cleaning failure
aqueous cleaners that are suitable for machine washing: clean- due to inconsistencies in manufacturing or unannounced for-
ers with no surfactant, cleaners with a nonfoaming surfac- mulation changes. It is desirable to choose a detergent from a
tants, and cleaners with low- or controlled-foam surfactants. manufacturer that maintains quality control on their raw
There are important differences among these types of clean- materials and in turn keeps retained samples of each lot of
ers. Remember that foam forms in the presence of an agitated detergent that is used to be able to respond to concerns about
foaming agent where air is present. Many soils are foaming a particular batch.
agents. In particular, soap formed by saponifiers in electronic The detergent should be widely available and economical
solder flux cleaning is a foaming agent. A surfactant-free to use (for optimum economy, a concentrated detergent is typ-
cleaner will not protect against foam formed by soils. You ically used at 1:100 to 2:100 dilutions). The detergent concen-
should only clean nonfoaming soils with surfactant-free clean- trate should be diluted according to the manufacturer’s in-
ers. A nonfoaming cleaner usually has a nonionic polymer sur- structions; typically, warm (about 50°C) or hot (about 60°C)
factant. These surfactants have a unique property of coming water is used. Ambient temperature water may be acceptable,
out of solution at elevated temperatures and forming an oil especially for presoaking. For difficult soils, very hot water
slick on top of the solution. This oil slick is a barrier to air should be used (over 65°C), and the recommended detergent
contact which stops foam from forming or being stable. These concentration doubled.
cleaners will suppress foam from soils. They only work prop-

20 The Aqueous Cleaning Handbook Aqueous Cleaning Processes 21


AGITATION Cleaning time can be accelerated by increased agitation,
Agitation can be a form of nonagitation (such as soaking), or more aggressive detergents, and by increasing temperature. If
performed through manual (cloth, sponge, brush), ultrasonic, agitation, detergent, or temperature cannot be increased—per-
flow-through clean-in-place (for pipes, tanks and tubes), spray haps because the substrate is too delicate or the proper equip-
cleaning (a dishwasher, for example), and high-pressure spray ment is unavailable—then one must be prepared to use longer
cleaning. In general, the more agitation, the more effective the cleaning times to achieve the desired cleanliness. While manu-
cleaning on bulk soils. al cleaning may take minutes, and spray cleaning might even
Cleaning often can be enhanced by presoaking, particular- take seconds, soaking for hours, or even overnight, may be
ly if soils are dried or baked onto the part to be cleaned. It is required to reach similar levels of cleanliness.
always desirable, whenever possible, to clean prior to soils There are some instances when long cleaning times may
becoming dried or baked onto surfaces. promote substrate corrosion, weakening, or swelling. The opti-
Different agitation methods are often chosen with (1) time mum cleaning time should be chosen relative to the specific
required and (2) number of parts being cleaned as the major substrate, temperature, cleaning method, and detergent.
considerations. If large numbers of parts must be cleaned
quickly, then a fast, high-agitation method such as spray wash- RINSE USED
ing often is used with an aggressive detergent. For smaller With aqueous cleaning, the last thing to come into contact
numbers of batch or batch-continuous quantities of parts, with the cleaned surface is the rinse water. A thorough rinse
ultrasonic soak cleaning with a milder detergent may be used. will remove soils which have been cleaned from the surface
and any residue from the detergent itself. Whatever contami-
TEMPERATURE nants are present in the rinse water to begin with can be pre-
In general, higher-temperature cleaning solutions result in bet- sent after rinsing. Therefore, the more stringent the cleaning
ter cleaning. In practice, there is typically an optimum temper- requirement, the greater the need for rinse water purity.
ature for a given combination of cleaning variables. Many The important consideration is to remove whatever conta-
soak, manual, and ultrasonic cleaning methods work best, for mination or residues are present to levels that will not inter-
example, at 50˚C to 55˚C. Many spray washing techniques fere with the further use of the parts or equipment.
work best at 60˚C to 70˚C. Waxy or oily soils are more easily • Standard critical cleaning. A thorough tap water rinse
cleaned at somewhat higher temperatures. Particulate soils followed by a deionized water or distilled water rinse is
tend to be more easily cleaned at slightly lower temperatures. usually sufficient. In general, a thorough rinse means
These are, of course, broad generalizations. It is not always rinsing with at least three times the amount of rinse
necessary or practical to clean at the optimum temperature. water as the cleaning solution used, (for example, a
You may have both waxy and particulate soils present, or the spray washing cycle of five minutes should be followed
part being cleaned may not be able to withstand the optimum by three rinse cycles of five minutes each in a spray
temperature. washing machine).
In soak or ultrasonically agitated rinsing, it is desir-
CLEANING TIME able to have two counterflow-cascade rinse tanks with
In general, the longer the cleaning time, the more thorough dripping “over the tank” for reduced dragout. Higher lev-
the cleaning. Many cleaning mechanisms such as emulsifying, els of cleaning may require the exclusive use of deion-
dissolving, suspending, and penetrating are time-dependent. ized or distilled water and in some cases more than three
Up to the point where cleaning has been completed, the longer times the volume of rinse water.
they’re employed, the more cleaning is accomplished.

22 The Aqueous Cleaning Handbook Aqueous Cleaning Processes 23


• Electronic component and circuit board cleaning. aqueous-cleaner solvent replacement system is evaluated on
Deionized water is preferred rather than tap water or the basis of the drying process. Equipment cost and process-
distilled water because deionized water has less potential ing speed are also factors when large volumes of ultrapure rin-
for metallic cation deposition which leave conductive sewater are required to remove small amounts of residue.
residues on sensitive electronic components. On metal There are two basic methods for drying substrates in aque-
parts, the use of deionized rinse water reduces the likeli- ous cleaning: physical drying and chemical drying. Physical
hood of depositing calcium, magnesium, and other drying consists of evaporation, forceful drying, and absorp-
water-spotting salts. tion, or a combination of these. Chemical drying includes sol-
With soak or ultrasonically agitated rinsing, it is ubilization (using a water-soluble solvent to dilute the water)
desirable to have two counter-flow cascade rinse tanks and displacement (using a surfactant-based solvent that is
with dripping “over the tank” to reduce dragout. In all insoluble in water). While these are usually faster than physi-
cases, running water or otherwise agitated rinse is better cal methods, they are not inherently environmentally safe. In
than a static soak-tank rinse. addition, proper operation must be followed to realize cost
Higher levels of cleaning may require the exclusive savings and ensure health and safety.
use of deionized or distilled water and in some cases Removing water by evaporation is the oldest and simplest
more than three times the volume of rinse water. physical drying process. Convection ovens do just that. Wet
parts are placed into an oven and heat is applied to remove the
For most cleanroom, electronic component, and cir-
water. Two problems are inherent with such drying solutions:
cuit board cleaning, deionized water is preferred over
either tap or distilled water because of its lesser potential • Convection or microwave ovens are not always applica-
for metallic cation deposition on sensitive electronic ble due to space and time constraints or lack of automa-
components, leaving conductive residues. On metal tion.
parts, the use of deionized rinse water reduces the likeli- • Some types of parts are heat sensitive and others may be
hood of depositing calcium, magnesium, or other water too big or too dense, requiring large amounts of energy,
spotting salts. to be efficiently dried by convection oven.

DRYING METHOD Mechanical systems for physical drying may be classified


Drying can affect residues and corrosion since impurities from by the following types:
rinse water can be deposited during evaporation. Water, par- • Vacuum drying—similar to convection drying—requires
ticularly high-purity rinse water, can be corrosive to metal a negative pressure to be applied. This causes a decrease
substrates during heated and air drying. The use of physical in the water’s boiling point in order to “suck” away the
removal or drying techniques or the addition of corrosion in- moisture. This method is ideal for removing trapped
hibitors (with the tolerance of corrosion inhibitor residues) to water from blind holes and crevices but may also deform
the rinse water can help minimize such corrosion. the part. Also, shorter drying times are balanced out by
With aqueous systems, adequately drying any remaining higher energy requirements. As with evaporation drying,
water from a part is critical to avoid corrosion of metals, par- an important consideration is that any contamination
ticulates sticking to surfaces, poor paint adhesion, short-cir- contained in the water will be left behind on a cleaned
cuiting of electronics, and problems related to cross-contami- surface. Multiple rinsing chambers with hot ultrapure
nation in food, beverage, and pharmaceutical processing. This water may not be sufficient to remove these residues and
last step in the manufacturing process is important both to the would add significantly to the time and cost involved.
end user and detergent supplier since the performance of an

24 The Aqueous Cleaning Handbook Aqueous Cleaning Processes 25


• Forced-air, or blow-drying—a relatively old concept for • Absorption—Moisture absorbing materials (corncobs,
removing water. A more advanced method is the use of drierite) are cheap, simple, environmentally safe, and
an “air knife” that forces clean, dry air through a long, reusable for many drying applications. They are usually
narrow chamber onto the substrate. Parts on a conveyor tumbled with the cleaned parts to increase contact with
system pass under this intense stream of air and the the water. Delicate parts may be damaged during tum-
water is simply blown off. Parts, however, must be bling and the drying agents themselves may further cont-
angled just right for water-soluble residues to be aminate the parts. Also, complex geometries with blind
removed and streaking to be avoided. Complex geome- holes cannot be dried adequately.
tries, nestled parts, and high production volumes are
also difficult problems, and noise may also be of con- The important thing to remember here is that not all dry-
cern. Large volumes of clean and dry air are required for ing processes are applicable in every situation. As with select-
drying to be successful. Automation may be easily ing an aqueous cleaner, the right drying process must be care-
accomplished, but batch processing is more difficult for fully assessed based on the parts being cleaned and manufac-
this type of drying system. turing volume.
• Centrifugal drying—uses gravitational forces to remove
water. Large volumes of parts and blind holes are han- POSTCLEANING HANDLING
dled easily; however, this approach is difficult to auto- The way in which parts and surfaces are handled after clean-
mate and delicate parts may be damaged. ing can impact their cleanliness. For this reason it is impor-
• Forced or filtered hot gas—combines convection heat- tant to consider how parts are handled and stored to ensure
ing with an air knife and offers the advantages of evapo- that the purpose of the cleaning process is maintained.
rative and blow-drying actions. In humid situations, Depending on the environment, it may be advisable to make
however, moisture can condense on the substrate, result- provisions for a clean storage place or conditions. It may be
ing in wet parts. Forced drying is environmentally safe appropriate to determine how long a surface or part will stay
and can handle large volumes of work. Air knives dry rel- clean while stored to determine if it needs to be re-cleaned
atively fast compared to most physical methods of dry- prior to use.
ing. They can also be economical and allow for automa-
tion. DETERMINING PART DRYNESS
Forced/filtered gases can be used to effectively dry Inspection is probably the most common method for deter-
parts, particularly in batch process systems where clean- mining dryness. For most precision cleaners, the observation
ing tanks are employed. After a tank is drained it con- of no visual wet spot constitutes a “dry” part. Tapping the
tains wet parts where dry gas (such as dry nitrogen, or parts on a brown paper towel will immediately indicate if
even heated dry nitrogen) is forced through the closed there is trapped water. If any solvent is present, the wet spot
chamber to dry the parts. This same principal can be will disappear very quickly. A more thorough test for measur-
used in a separate drying chamber in which a dry gas is ing remaining water involves using reagents found at any
also used to evaporate the water and sweep any water chemical supply house, solubilizing the water in methanol,
vapor away from the parts. Particular attention should and performing a relatively simple titration.
be paid to the quality of the gas being used. Typically, fil-
ters are employed on the incoming gas—with a filter size CLEANING METHODS
appropriate to the size of particulates which must bee There are ten types of mechanical cleaning methods used in
exclude from the surface. aqueous cleaning and each is employed—sometimes in combi-

26 The Aqueous Cleaning Handbook Aqueous Cleaning Processes 27


nation—for specific types of substrates, parts, and cleaning Of the two methods, spray clean in place uses far less solution
volume factors. They include: and can be more efficient.
• Manual—Manual cleaning is used to clean small batches Typically, the cleaning solution is circulated slowly for at
of parts and surfaces. To clean manually, the article to be least one-half hour—with several hours required for large sys-
cleaned should be wetted either by immersing it in the tems. Displace the cleaning solution by pumping in one full
detergent solution, or by using a soaking cloth or system capacity of water. Then complete rinsing by circulating
sponge. For nonabrasive scouring, undiluted detergent and draining at least two times the systems water capacity. For
should be poured onto a wet cloth or sponge for scrub- spray clean-in-place, a low foaming detergent is used, followed
bing. A cloth, sponge, brush, or pad can be used for by rinsing and flushing thoroughly.
cleaning. A thorough rinse follows. Protective gloves and • Ultrasonic—Ultrasonic cleaning is used for larger num-
eye protection should be worn if recommended or bers and repetitive batches of parts. To clean in an ultra-
required. sonic tank, a solution is made up in a separate container,
• Immersion/Soak—Soaking is used to clean small items the ultrasonic tank filled, and the machine run for sever-
and the insides of larger vessels. It should be used as a al minutes to degas the solution and allow the heater to
pretreatment to prevent soils from drying onto a part. reach the correct temperature. Small articles should be
Soiled parts can be placed in a soak tank until such time placed in racks or baskets; irregularly shaped articles
that they can be washed. Soaking is also effective to aligned so that the long axis faces the ultrasonic trans-
clean or pretreat very difficult, dried-on residues. To ducer (usually the bottom); the machine should run 2–10
clean by soaking, a detergent recommended for soaking minutes until parts are clean. A thorough rinse follows.
should be used, and a detergent soak solution made up • Machine—Machine washing is used for cleaning large
according to the directions. The article should be com- quantities of components. The machine’s directions
pletely submerged to prevent any deposits or etching at should be consulted for details on proper use. In general,
the air/solution interface. Soils should be soaked until the parts are loaded on racks with open ends facing the
they are removed; this may take several hours. Some spray nozzles. Narrow-necked parts should be placed in
soils may require additional agitation or wiping in order the center of the racks, preferably on specifically
to remove them. A thorough rinse follows. designed spindles with spray nozzles directed into the
• Clean-in-Place (CIP)—Clean-in-Place is used to clean necks. Small articles should be grouped in baskets to
pipes, tanks, and filtration systems. Its chief advantage is prevent dislodging by spray. Avoid loading parts touch-
that, as its name implies, it assures clean systems with- ing each other where possible. Only low foam detergents
out disassembly. It requires, however, good circulation designed for these machines should be used. Typically,
for effective cleaning. 10 g or 10 mL of detergent per liter of hot, wash-cycle
There are two main clean-in-place methods: water (approximately 60˚C) is used.
• Circulate clean-in-place—which involves filling a • Power Spray Wand—Commonly called a power washer,
tank and system with solution and circulating it it consists of a pressurized tank with hot water and/or
through the system. steam that is connected to a hand-held wand. The wand
will have a trigger to release the hot water or steam and
• Spray clean-in-place—which involves partially fill-
usually has a detergent metering device or injection
ing the system and circulating the cleaning solution
device to meter in detergent during spraying.
through spray nozzles.

28 The Aqueous Cleaning Handbook Aqueous Cleaning Processes 29


• Washer/sanitizer—A high temperature washing pense detergent and rinse water. There is a class of PC
machine usually larger than a home dishwasher; it has board washer that is called a conveyorized or continuous
racks where devices to be cleaned are placed with very washer that has a conveyor belt that carries the boards
hot water used during cleaning to give some thermal past a series of washing spray stations and rinsing sta-
sanitation. Versions of these machines that are used in tions.
cleaning medical instruments may even have pressure
seals and use high pressure steam to achieve higher tem- IMPROVING PERFORMANCE BY
peratures for higher degrees of disinfection. CONTROLLING EFFICIENCY VARIABLES
• Glassware Washers—Glassware washers are used for By choosing an appropriate cleaning method, using the right
washing laboratory glassware. They are usually available rinsing and drying process, then varying the cleaner, concen-
in small under counter sizes that are approximately the tration, temperature, and time, an optimized aqueous-cleaning
size and dimension of a home dishwasher, or a variety of system can be achieved.
larger floor standing models for cleaning higher volumes Getting the greatest performance in aqueous critical clean-
of glassware. As glassware washers, these will often be ing requires controlling the eight important variables that
connected to a deionized water source in order to be affect cleaning performance.
able to rinse with the deionized water. In laboratory
cleaning it is often critical to have a deionized water 1. Precleaning handling
rinse to prevent any residue left from the rinse water. As a general rule, parts and surfaces must be cleaned promptly
• Parts washers—Parts washers are a class of washing after becoming soiled to avoid drying and setting up the dirt
machinery used in industrial cleaning that covers a wide on them. Clean storage conditions for parts, or proper packing
variety of types of cleaners. These vary from ultrasonic of parts by the parts supplier, can make it easier to successful-
washers which were discussed previously, to immersion ly clean parts or surfaces.
soak tanks, to elaborate agitation machines having
immersion tanks with bubbles running through them or 2. Agitation/cleaning method
with some kind of inert media that is vibrated inside Usually the cleaning method is selected first—depending, of
them with a solution, to variations on the washer sanitiz- course, upon the practical considerations of your cleaning
ers or glassware washers as discussed above. If you are problem. The cleaning method, in turn, dictates the type of
dealing with a machine called the parts washer it can be agitation available. While very large items or large quantities
important to determine which kind of parts washer it is. of items with less critical throughput requirements may be
If it is a parts washer which relies on spray agitation or handled in large dip tanks, critical items—and their volume—
pressurized spray as in a glassware washer or washer will determine the type of cleaning procedure.
sanitizer, then you need a low-foaming detergent. If it is Examples:
a ultrasonic cleaner or an agitation under immersion • Small items—Cleaning by hand with cloth, sponge, or
cleaner you may be better off with those detergents suit- brush agitation may be acceptable for items that are
able for those kinds of cleaners. small in volume and size.
• PC Board Washer—Like glassware washers these typi- • Important items—You may want to clean in ultrasonic
cally come in under counter sizes, and floor standing immersion tanks for items requiring more controlled,
models for larger numbers of boards or larger sizes of reliable, and reproducible cleaning that is less subject to
boards. These are usually spray wash machines that have human error.
racks mounted inside them with spray nozzles to dis-

30 The Aqueous Cleaning Handbook Aqueous Cleaning Processes 31


• Large quantities—May also dictate the use of ultrasonic 4. Drying method
immersion cleaning, batch-parts washers, or mechanical You can dry by physically removing rinse water or by evapo-
washers. rating rinse water. Physically removing by wiping, blowing,
• Very large quantities—Parts with rapid throughput centrifuging, drying fluids, or other physical removal tech-
requirements may require conveyor-type spray washers. niques will remove the rinse water before it has a chance to
evaporate. Such methods avoid precipitating out any impuri-
3. Rinse procedure ties or salts that may be present in the rinse water.
Rinsing methods are usually dictated by practical considera- Evaporation drying methods such as air drying, heat dry-
tions that are compatible with the cleaning method you have ing, and vacuum drying can potentially deposit any non-
chosen. volatile impurities present in the rinse water. Note that vacu-
It is also important to use sufficient rinse water to assure um drying can evaporate a wide range of impurities that are
complete soil and detergent removal. For basic crude cleaning, nonvolatile at room temperatures.
two volumes of rinse water for every volume of wash water
may be sufficient; for higher level cleaning three or more vol- 5. Cleaner type and concentration
umes of rinse water are usually required. Detergents should be compatible with the cleaning method
Agitated or running water is always preferable to stagnant and effective on the soils you are removing—one that will not
soak rinsing. It is important to choose rinse water that is free damage the substrate you are cleaning.
of problem residues. Choose a cleaner with the appropriate combination of
Be aware that the rinse water is the last thing to touch the cleaning functions for your soil that will perform well with
item you are cleaning. Whatever is in the rinse water can end your cleaning method.
up on your surface. The substrate and application for your
parts also help determine the type of rinse water. 6. Temperature
Examples: Changing this variable gives the most dramatic results.
• Electronic components—Use ion-free deionized water Generally, the higher the temperature, the faster and more effi-
for components that are conductive ion sensitive. cient the cleaning. For cleaning mechanisms that have first-
• Pharmaceutical, medical device, optical, and coating order reaction kinetics (such as emulsifying, saponifying, and
applications—Use organic-free distilled or reverse- dispersing), an increase of 10˚C (18˚F) will double the rate of
osmosis water for organic, film-sensitive compounds or cleaning.
parts. High temperatures are particularly important in
machine/spray washing where a droplet of solution only has a
• Manufacturing—Use low calcium/magnesium soft
split second to react with the soil before the next droplet of
water, deionized water, or distilled water to avoid calci-
cleaning solution displaces it from the surface. High tempera-
um/magnesium water spot deposits.
tures also help remove soils such as wax or silicon oil that typ-
ically can only be softened at temperatures above 170˚F in
If the purified water is expensive to use, you can often get
conjunction with a high-emulsifying cleaner. It’s important to
by with an initial regular tapwater rinse followed by a final,
note, however, that high temperatures are not always desir-
purified-water rinse. Another way to minimize rinse water
able. They must be balanced against a commensurate increase
deposits is to dry by a water-removing method rather a water-
in corrosion.
evaporating one.

32 The Aqueous Cleaning Handbook Aqueous Cleaning Processes 33


Also, many materials require using only the highest tem- Keep in mind, however, switching from an immersion- or
perature that will cause no harm to a substrate. Examples manual-cleaning method to a spray-cleaning method, may
include plastics, which often cannot be cleaned above 70˚C require reconsidering the choice of detergent. This can be
(160˚F), aluminum not above 60˚C (140˚F), and proteins not important in a validated cleaning environment—where a
above 55˚C (130˚F). future change in cleaning methods will also add additional
concerns for validation. Therefore, at a smaller volume, it is
7. Cleaning time and concentration often wise to use a cleaning method that can be scaled up to
Above a certain minimum concentration of detergent, dou- high-volume manufacturing, if this level of output is anticipat-
bling the detergent concentration may only give a 10% ed.
increase in ability to remove soil and a 25% increase in bath The following are the predominant cleaning methods:
life. Beyond a certain minimum cleaning time, doubling the • Manual cleaning—typically chosen for small-volume
cleaning time may only give a 10% increase in ability to batch cleaning. The levels of cleanliness that can be
remove soil. The minimum concentration and the minimum achieved by manual cleaning are actually very high,
length of cleaning time may be around 25% of a typical con- although the operator determines the consistency of
servative recommendation from a detergent manufacturer. cleanliness. For consistent manual cleaning, rigorous
To optimize your system, bracket the cleaner manufactur- operator training and retraining needs to be considered.
er’s recommendation and then increase or decrease the time, Well-written cleaning procedures and training proce-
temperature, concentration, and agitation according to your dures should be provided for—even going go so far as to
needs, recognizing that decreasing any one of these variables certify operators in different cleaning methods with peri-
may require increasing the others. In many cases dropping the odic recertification.
temperature significantly can result in cleaning performance • Soak cleaning—usually chosen for small quantities of
decreases that cannot be made up for by increasing time, agi- parts when there is sufficient time in which to clean
tation, or cleaner concentration. them. Soaking is not labor intensive, although it is typi-
cally a slow process. Care should be taken in choosing a
8. Postcleaning Handling soak method of delicate parts are being cleaned. Due to
Providing for clean storage or clean packaging in which to put the longer times involved in soaking, there is also more
your clean parts or surfaces can help maintain them in a clean time for corrosion due to interaction between the sur-
state. face being cleaned and the solution used to clean it. As a
result, soaking is best suited to small volumes of robust
SELECTING A CLEANING METHOD parts where time is not terribly important.
The choice of cleaning method is determined by the quantity • Ultrasonic cleaning—particularly effective on small
of parts to be cleaned, their configuration, the cleanliness level parts with blind holes and crevices that are inaccessible
that needs to be achieved, and the budget available for equip- by spray cleaning. This process is essentially soak clean-
ment. ing enhanced by ultrasonic sound energy. This greatly
Often a cleaning method choice is based on volume, for accelerates the speed of cleaning and can greatly
example, manual cleaning for small volumes. As the volumes improve cleaning in small spaces or crevices. Ultrasound
or quantity of the parts or surfaces being cleaned increases, helps with dispersing and mass transfer of the cleaner
immersion cleaning system, possibly even including ultrasonic and the replenishing of fresh cleaning solution to the
agitation, may be indicated. As the parts and volumes increase surface of the parts being cleaned. Ultrasonic cleaning
further still, some form of high-volume spray cleaning applica- involves more expensive equipment and is typically suit-
tion will be required.

34 The Aqueous Cleaning Handbook Aqueous Cleaning Processes 35


able for somewhat larger volume batches where a higher BATH-LIFE EXTENSION AND CONTROL
level of cleaning is required. For the highest levels of critical cleaning only freshly made up
• Clean-in-place by circulation system—typically used solutions should be used for cleaning to avoid any potential for
for piping or small tank systems where a spray clean in cross contamination. For industrial critical cleaning applica-
place system can not used or in filtration systems where tions high levels of cleaning can still be achieved with extended
the filters being cleaned can not be accessed by spray bath life. In general, a pH change of 1 pH unit towards neutral
nozzles. indicates an exhausted cleaning solution. Bath life can also be
• Spray clean-in-place—typically used in larger tank sys- extended by physical filtration of particulates and cooling and
tems where the efficiency achieved by less solution usage settling of sludge and skimming of oils. Bath life can also be
warrants the cost of installing the spray system. The extended by adding one half as much detergent of the initial
spray cleaning of tanks can also give more reliable, com- load after partially depleting the cleaning life of a bath. Under
plete coverage of the tank. (Also, an immersion cleaning frequent daily use, detergent solutions can rarely be used more
system may have difficulty cleaning the top of a tank, than a week even with these bath life extension techniques.
requiring additional manual cleaning.) Conductivity, pH and, % solids by refractometer can be used to
control bath detergent concentration.
One must keep in mind when choosing which method to Free alkalinity titration can also be used to control bath
use for cleaning tanks that a detergent that performs well for life of alkaline cleaners where the soil being cleaned depletes
soak cleaning may not perform as well in spray cleaning. free alkalinity—as is often the case with oily soils. The process:
Therefore, if it is anticipated that a process will ultimately be • Titrate a fresh solution to determine new-solution free-
scaled up to a spray clean-in-place system, it may be wise to alkalinity.
consider using a spray-cleaning detergent that will also perform • Titrate the used solution to determine the percent drop in
adequately in soaking operations. free alkalinity.
The choice of a cleaning machine depends on the batch and • Add more detergent to the bath to bring the free alkalini-
size of the pieces being cleaned. As batch volumes move up ty back to the new solution free alkalinity. (For example
from those that may be best addressed by ultrasonics, it often if the initial solution is made up with 100 ml of cleaner
makes sense to employ some form of cabinet, under-counter, or concentrate and a 25% drop in free alkalinity is
floor standing washer. observed, try adding 25 ml of cleaner concentrate to
For very high-volume parts washing, a conveyorized system, recharge your solution.)
whereby parts are placed on a conveyor and are cleaned with
spray nozzles as they pass through the conveyor cleaning sys- Perform a new free-alkalinity titration to confirm the
tem, may be appropriate. recharge the first few times this recharging method is used to
Spray cleaning systems are very good for parts and surfaces be sure that the detergent being used is linear with respect to
that are readily accessible to the spray. They are not as good at free alkalinity depletion. This form of bath life extension can-
dealing with blind holes and small crevices. For instances where not run indefinitely, sludge will eventually form. Fresh solu-
you have higher volumes of parts where it makes sense to use tions must be made up periodically.
spray cleaning, you should investigate spray under immersion. Bath lives can be controlled to extend them by using con-
For cleaning very, very large parts (where an operator can ductivity. Most cleaners have conductive salts in their ingredi-
physically move around the part, for example, vehicles or very ents, which are detectable by conductivity. By knowing the
large assemblies) it makes sense to use a power spray want or conductivity response of the detergent, the depletion of those
handheld pressure spray device to clean part exteriors. conductive salts can be measured.

36 The Aqueous Cleaning Handbook Aqueous Cleaning Processes 37


Many cleaner manufacturers can supply the curves of order of importance) use less heat, lower pH detergents, and
detergent concentration versus conductivity. By adapting these shorten cleaning time and agitation.
curves to your conditions and measuring the conductivity, de- In general, use the mildest pH detergent to limit metal cor-
tergent depletion and dilution by make-up water can be deter- rosion. Higher pH detergents may have metasilicate corrosion
mined. This determination can be used to figure out how inhibitors that often allow it to be used successfully to clean
much detergent to add to the cleaning solution to restore soft metals such as aluminum. In general, to reduce plastic
cleaning performance. Typically this kind of measure and corrosion, use less aggres-sive cleaners that have less solvent
recharge can be carried out through several iterations. or surfactant character or use lower concentrations of those
Keep in mind, however, the bath will ultimately reach a cleaners, use lower cleaning temperatures, use less contact
point where it forms sludge (or where some other failure time, and finally, use less agitation.
mechanism occurs), at which time the bath must be dumped With aqueous cleaning, metal corrosion can occur during
and a complete batch of new cleaner employed. The time to rinsing and drying. Corrosion inhibitors can be added to rinse
dump the bath and start over is often defined as being after a water provided that any associated inhibitor residue does not
certain number of parts or length of time as determined using interfere with the surface being cleaned. Keeping the surfaces
some sort of cleanliness measurement. The conductivity will cleaned hot by using hot rinse water and by using rapid heat
typically not detect the point of cleaning failure, but will only or vacuum drying can accelerate drying and minimize metal
detect concentration of cleaner present, whether depleted or corrosion. Forced air drying and air knives that physically
not. The following table gives specific examples of concentra- remove rinse water can also minimize corrosion, as well as
tion vs. conductivity for some specific Alconox-brand cleaners. drying with hot oxygen-free gas such as nitrogen.
Using the data below one can derive the concentration of With mild steel one can have “flash rusting” when rinsing
detergent from measured conductivity. Note that conductivity with hot water and drying with hot air. In some instances, low-
is very temperature dependant and detergent solutions do not ering the water temperature or drying temperature can help
have the same slope as many default settings on temperature- avoid corrosion on mild steel. For instance, in a case where
correcting conductivity meters. For best results, allow hot flash rusting on mild steel had been occurring due to using
detergent solutions to cool to a consistent temperature for 150°F rinse water and ambient air drying, it was found that
comparison. 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, Finally, particulate soils are best removed by disper-
plastic, rubber. For example, substrates such as magne- sant cleaners that can lift them into solution and form a
sium, aluminum, and similar metals may be attacked by suspension. Very small particulates, for example submi-
some types of chemicals. Stainless steel alloys, on the cron particulates, need to be cleaned by a very high wet-
other hand, often have a high resistance to both acids ting, low surface tension cleaner that has the ability to
and alkalies. lower the boundary layer between the surface and the
• Type of soil—What type of soil is it? Heavy or light, solution down to submicron distances to allow the agita-
organic or inorganic, oil or particulate matter. This is tion in the cleaning solution to access the submicron
perhaps the single most important question to ask when particulate.
you are selecting an aqueous detergent. Heavy soils • Part complexity—Are there severe undercuts, blind
require heavy-duty detergents or cleaners to re-move holes, or numerous part cavities? Higher-powered wet-
them. The detergent should have a high concentration of ting detergents with low surface tension may be
cleaning ingredients to give it a high capacity for remov- required.
ing soil; typically heavy soils require very aggressive • Level of cleanliness required—If the part being cleaned
cleaners. A heavy soil may often be best handled by a or the manufacturing process does not require excep-
high dispersing cleaner that is able to move bulk quanti- tionally high technical specifications for cleanliness,
ties of soil without having to react chemically with each harsh, toxic cleaning agents can often be avoided.
individual molecule of soil. • Manufacturing process—For example, if a part arrives
Light soils require a detergent that matches the exact wet at the cleaning station, an aqueous chemistry may
type of soil in order to be able to most completely be best.
remove them. If you have a light soil it is more impor- • Cleaning efficiency—As a rule, cleaning efficiency
tant to know more about what kind of soil it is so that increases with time, temperature, and agitation, though
you can go from a surface that is almost clean to a sur- each may affect other important considerations such as
face that’s extremely clean or meets your level of cleanli- foaming, costs, health, or safety.
ness. For example, many organic soils have limited water
• Environmental considerations—The environmental
solubility. These oily soils are often best cleaned by a
impact of cleaning operations can often be minimized or
high emulsifying cleaner. An inorganic soil again may or
reduced by selecting the most appropriate aqueous
may not be water soluble, but if it is not water soluble it
cleaning agent, and appropriate cleaning and/or recy-
is often able to be removed by chelation using a deter-
cling system.
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 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- The cleaner may not be appropriate for the higher agitation
ting, penetrating, and dispersing. Spray cleaners need to be system, or the particle sizes of the soil may not be as easily
more aggressive and faster acting since they have but a fraction cleaned in higher-turbulence, higher-boundary layer conditions.
of a second to do their cleaning before the next droplet of spray Again, when performing bench-scale testing for spray clean-
sweeps them from the surface. Immersion cleaning can have ing systems it is important to mimic the characteristics of the
minutes or hours of contact time. actual cleaning system. For instance, mimic the drenching of a
It is possible to test a cleaner that will perform only margin- surface by pouring or gently pumping cleaning solution over a
ally in immersion cleaning but performs excellently in a spray- surface in order to mimic high volume/low pressure cleaning, or
washing environment. It is also very possible (and even likely) mimic the blasting of a surface using a pump and nozzle or
that a cleaner that performs excellently in immersion cleaning Water Pik®.
will be very ineffective in a spray washing environment. It is important to stress that although ultrasonic cleaning
In particular, high-foaming cleaners that can work very well can result in very high localized agitation from the cavitation
in immersion do not perform well in enclosed spray cabinet caused by the sound waves, the agitation occurs under immer-
washers where the foam can create a barrier to the mechanical sion where immersion cleaning mechanisms are still effective.
energy of the spray, and where the foam may burst the seals of Even spray under immersion can allow for some of the kineti-
the cabinet (and, possibly, cause cavitation in the circulating cally slower immersion cleaning mechanisms to work, although
pumps). there is much more movement in the cleaning solution that
There is another more subtle difference in spray cleaning occurs during spray under immersion and, thus, kinetically less
systems where, in simplified terms, one is dealing with two time available for slower immersion cleaning mechanisms.
major kinds of agitation. There is the high volume/low pressure The following table outlines bench scale cleaning methods
method of spray washing and the low volume/high pressure and how they mimic larger-scale cleaning:
method of spray washing. The first involves gently spraying a
high volume of cleaning solution over the surface of a substrate, TABLE 5D TYPICAL BENCH-SCALE CLEANING SYSTEMS
which results in a cascade of solution running down the surface AND THE SCALE-UP SYSTEMS THEY MIMIC
to be cleaned. This results in a more nearly laminar flow at the CLEANING METHODS
surface with a smaller boundary layer that allows for a wider
Bench-Scale Full-Scale
range of cleaning mechanisms and, in particular, the occur-
rence of greater small-particulate dispersion. Manual cleaning with tool Manual cleaning with tool
It is not unusual for what is called a low-foaming or con- Immersion in a small tank Immersion in a big tank
trolled foaming cleaner to perform well in such high Small tank with stirrer A clean-in-place,
volume/low pressure washers. In low volume/high pressure agitated big tank
spray washing, there is much greater turbulence and more Small ultrasonic tank (be sure to use Bigger ultrasonic tank
mechanical energy with cleaning solution bouncing off the sur- same frequencies and power densities)
faces with less cascading and sheeting action down the surface. Gently hosing or pouring High volume/low pressure
In these very high agitation cleaning systems you may need a washer onto a surface
nonfoaming cleaner.
Power spray onto surface Low volume/high pressure
A problem that sometimes occurs is when a perfectly suc-
washer
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 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- processes, but may become very difficult to remove if it dries
ganic soils from metals it is often important to use the exact on the surface for several hours. (If possible, it may be wise to
metal that will be cleaned when a process is scaled-up. The try to avoid allowing soils to dry onto a surface in the actual
same is true for porous surfaces—such as gold and some ce- cleaning conditions.)
ramics—which may require use of the same substrate for If using the exact soils that will be present during actual
bench-scale testing in order to develop a reliable cleaning sys- cleaning is not possible, try to match the characteristics of the
tem. soil. Match the particulate sizes, oil viscosities, wax melting
Similarly, it can also be very important to use the same points, chemical character (for example, do not use a natural
surface for testing in order to be sure that the cleaning system oil to mimic a synthetic or petrochemical oil and vice versa).
will not corrode or damage the surface. This is especially true Try to apply the soil to the surfaces in the same manner and
for aluminum. quantity that will be present under actual cleaning conditions.
It can be very useful to work with standard clean coupons. (Soiling the substrate on the heavy side can be helpful in de-
There are several suppliers of standard coupons that are more signing a robust cleaning system.)
commonly used with corrosion testing, but that can be adapt- In addition, it may be critical to develop a way of uniform-
ed for use in cleaning testing. Some suppliers include: ly soiling a surface in order to get significant reproducible
results that are suitable for comparing cleaning systems. One
Metal Samples Corrosion Monitoring Systems approach is to create a uniform slurry, paste, or solution of the
A Division of Alabama Specialty Products, Inc. soil, possibly employing a volatile solvent carrier to apply the
P.O. Box 8, 152 Metal Samples Rd. liquid mixture to surface, then using a glass rod with spacers
Munford, AL 36268 to spread a uniform film of soil onto a coupon to achieve uni-
(256) 358-4202 form reproducible soil levels.
http://www.alspi.com/msc.htm If the objective is to find a way to absolutely clean a soil—
rather than compare cleaning systems—simply smearing or
Metaspec CO applying some soil to the surface for visual inspection that
790 West Mayfield Boulevard some soil is present can suffice.
San Antonio, TX 78211
(210) 923-5999 SELECTING AN AQUEOUS CLEANER
After establishing combinations of cleaning, rinsing, and dry-
Q-PANEL LAB PRODUCTS ing, try a cleaner at different time, temperature, and detergent
800 Canterbury Road concentrations to determine if the system will work. Review
Cleveland, OH 44145 the information in Chapter Four on Detergent Selection to
PH: (440) 835-8700 make sure you are testing a cleaner that has a reasonable
http://www.q-panel.com chance of success. Match the cleaner to the desired cleaning
method, soil, and surface being cleaned.
SELECT A TEST SOIL
It is often more important to pay attention to the soil than the PERFORM TEST CLEANINGS
surface during cleaning system development—using the same It is advisable to perform at least three cleanings using each
soil in bench-top testing as in scale-up. Pay careful attention to set of conditions to help minimize anomalous results. For crit-
how dried-on the soil will be in the actual process. A freshly ical-cleaning system development, it is desirable to perform at
applied soil may be very easy to remove in bench-scale least six repetitions of each set of conditions.

60 The Aqueous Cleaning Handbook 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 from the US FDA, the EU (European Union), and the Interna-
made of light-duty plastics or aluminum. Therefore, the clean- tional Conference on Harmonization (ICH), to name a few.
ing agents chosen must not damage the light-duty plastic or For a discussion of the cleaning validations required under
aluminum instrument-handling trays. these regulations see the chapter 8 on cleaning validation. For
examples of the types of standard operating procedures
TABLE 6A DETERGENT SELECTION GUIDE FOR HEALTHCARE CLEANING (SOPs) used in pharmaceutical process equipment cleaning
Application Recommended
see the Chapter 7 on cleaning procedures.
Key Concerns Articles Cleaned/Soil Removed Cleaning Method Detergent The types of residues that need to be cleaned range from
Healthcare Surgical, anaesthetic, and examin- Manual, Ultrasonic, Soak Mild alkaline easy to clean water-soluble excipients to difficult
Effective prepara- ing instruments and equipment. Machine washer, Inhibited low-
tion for steriliza- Catheters and tubes. sani-sterilizer foam alkaline petrolatum/metal oxide mixtures. To simplify regulatory com-
tion, longer instru-
ment life. Minimize Difficult proteinaceous soils, blood Manual, Ultrasonic, Soak Enzyme pliance, it is desirable to use as few cleaners as you can to
cross-contamina- and other body fluids, tissue on Machine washer, Inhibited low-
tion. Reduce waste. instruments. sani-sterilizer 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
Healthcare instruments that are cleaned are usually exam- manual, soak and ultrasonic cleaning to clean-in-place spray
ining instruments of one kind or another. Most healthcare systems.
instruments that come into contact with blood or body fluids The materials of construction that typically need to be
are disposed of so as to completely eliminate, or substantially cleaned are glass, 316L stainless steel, Teflon, polypropylene,
reduce, the risk of cross-contamination from blood-born and silicon elastomers used in seals. In some cases, pharma-
pathogens. Some reusable examining and probing instruments ceutical manufacturers will use disposable seals, pipes and fil-
(such as endoscopes) actually come in contact with blood or ters to avoid having to validate their cleaning. It can be safer
body fluids and must be cleaned very carefully. and more cost effective to use some equipment once rather
Cleaning healthcare instruments varies from cleaning than clean it.
small groups of instruments—such as what may be found in There is no more demanding application for precision
an individual doctor’s office or clinic—that are handled in cleaning than pharmaceutical manufacturing—where cross-
small soak trays and sometimes cleaned ultrasonically, to contamination can be costly in lost product and the creation
large-scale central cleaning found in hospitals and large med- of risk to human and animal health.
ical centers. In control cleaning, the instruments in the entire Today many leading drug companies, as well as firms that
facility are grouped in trays and sent to a central cleaning or manufacture medical devices, are finding that aqueous clean-
central sterilization facility. These facilities will typically use ers provide the same kind of scrupulous cleaning required for
large batch washer/sterilizers to perform their cleaning. processing healthcare products. Examples:
• Capsules and tablets—Some pharmaceutical ingredi-
PHARMACEUTICAL ents resist going into solution, making tablet presses and
Pharmaceutical process equipment cleaning includes every- dies difficult to clean. Even stubborn, sustained-release
thing from bench scale lab production for trial use to full scale product residues come clean quickly with appropriate
manufacturing of bulk pharmaceuticals. All share the need to aqueous cleaners.
clean and document to government regulated standards. These • Suspensions—Aqueous cleaners also eliminate intensive
standards are commonly called GMP (good manufacturing scrubbing and human contact in cleaning large stainless
practice) or the update as cGMP (current good manufacturing steel tanks (even 2,000 gal) used in manufacturing liquid
practice). There are regulations that need to be complied with suspensions.

66 The Aqueous Cleaning Handbook Industrial Cleaning Applications 67


• Intermediates—Aqueous cleaners are ideal for cleaning Pyrogens on packaging materials can be controlled by
heating alone or in combination with alkali or strong oxi-
glass-lined chemical reactors used in processing pharma- dizing solutions or by washing with detergent
ceutical intermediates such as powders, fillers, binding (1)...Pharmaceutical makers can render plastic containers
agents, and other chemicals. 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
TABLE 6B DETERGENT SELECTION GUIDE FOR PHARMACEUTICAL CLEANING of choice, any cleaning agent residue must be adequately
removed...The favored method of removing pyrogens form
Application Recommended stoppers is washing... many stopper makers now offer pre-
Key Concerns Articles Cleaned/Soil Removed Cleaning Method Detergent washed stopers, which are treated to reduce endotoxin lev-
Pharmaceutical Product-contact surfaces. Manual, Ultrasonic, Soak, Mild alkaline els by 3 logs. 1
Passing cleaning C-I-P*
validation for FDA Machine washer, Low-foam alkaline
good manufactur- power wash Liqui-nox is certainly a detergent that is used in pyrogen
ing practices.
Inorganic residues, salts, metallics, Manual, Ultrasonic, Soak, Mild acid
pigments. C-I-P* control. Most laboratories that do LAL testing for pyrogens
Protein/ferment residues. R/O, U/F Manual, Ultrasonic, Soak, Enzyme use Liqui-nox to clean their glassware and testing equipment.
membranes. C-I-P*
Stainless Steel Cleaning—Since stainless steel and glass
*Clean-in-Place by circulating, for spray clean-in-place see machine washer detergents.
are common substrates cleaned, it is worth taking a closer
In research and development, aqueous cleaners have long look at some of their surface properties and how that effects
been used in cleaning metal, glass, plastic, and polymer com- cleaning and how to optimize thermodynamics of cleaning by
ponents for benchtop labware as well as for difficult-to-clean controlling the pH of the cleaning solution.
pilot processing equipment such as bioreactors and fermenta- In aqueous critical cleaning there are numerous well-
tion systems. understood factors in detergency affected by pH. Far less well
Controlling Pyrogens—One of the considerations in phar- known, however, is the role pH can play in harnessing electro-
maceutical process equipment for parenteral product cleaning static affects to improve cleaning efficiency. Since like charges
is controlling pyrogens. Pyrogens are endotoxins or cellular repel, choosing a cleaner of appropriate pH relative to the iso-
debris that can cause fevers if people are internally exposed. electric point of the surface and the pKa (inverse log of the
Pyrogens are often controlled using heat. The cleaner acid dissociation constant, see table 1) of the residue makes
Liqui-nox (Alconox, Inc. catalog number 1201) and Alconox cleaning far more efficient—especially when cleaning residues
(Alconox, Inc. catalog number 1104) are used to depyrogenate such as acids, bases, and amphoteric proteins, all of which can
heat sensitive surfaces (as well as those treated by standard have their electrical charges manipulated by pH.
heat treatment). As standard cleaning with 1% 120 deg F (50 The isoelectric point of a surface is the pH at which the
deg C) Liqui-nox by manual, soak, or ultrasonic agitation fol- surface’s electric charge is neutral with regard to its acid/base
lowed by a thorough rinse with WFI (pyrogen free water— and electron donor-acceptor reactions. Moving to a higher or
water for injection) and post cleaning handling in a pyrogen lower in pH will shift the effective surface charge or electron
controlled environment or packaging can give adequate pyro- density in a negative or positive direction. Examples:
gen control. Stoppers for injectables are cleaned using Alconox • Steel—typically has an isoelectric point of 8.5 associated
powdered detergent solutions. with the reactivity of the oxygen in the oxides Fe2O3,
A recent article (Hallie Forcinio, Pyrogen Control, March Fe3O4, and Cr2O3 on the surface of the metal and the
2001 Pharmaceutical Technology p38) made reference to con- hydrates and hydroxides formed in aqueous solutions.
trolling pyrogens with the following:

1
W.A. Jenkins and K R Osborn, Packaging Drugs and Pharmaceuticals, Technomic Publishing
Co, Lancaster PA, 1993, p 28.

68 The Aqueous Cleaning Handbook Industrial Cleaning Applications 69


• Glass—has an isoelectric point of 2.5 associated with the reversed to be below the pH at the pKa and the isoelectric point of
SiO2. the surface being cleaned in order to achieve a positive-positive
repulsion, or at least a neutral residue and a positive-character sur-
Raising the cleaner solution pH (past the isoelectric point), face without attraction.
causes the surface takes on a more negatively charged charac-
ter. If the residue to be remove also has a negative charge at TABLE 2 OPTIMIZING THERMODYNAMIC CLEANING CONDITIONS
that pH, then the negative surface will repel the negatively FOR SURFACE/RESIDUE ELECTROSTATIC REPULSION
charged residue. Acidic residues pH > pKa and isoelectric point of surface
In addition to material surfaces, many residues can also Akaline or basic residues pH < pKa and isoelectric point of surface
undergo a change in electrical charge due to a simple change
in their pH. For most acids, the pKa indicates the pH at which For any cleaning, however, it is important to also consider the
the hydronium ions and conjugate base are present in equal corrosive effect of pH on the surface being cleaned. Typically, it is
concentrations. Moving higher in pH shifts the equilibrium desirable to choose a cleaner with a pH that will not etch or cor-
toward the right, thereby increasing the concentration of the rode the surface—for stainless steel, within the limits of passiva-
negative conjugate base. Thus, when cleaning acids it is desir- tion, and for glass, within the limits of etching. (It is important to
able to use a cleaning solution with a pH above the isoelectric note that the addition of corrosion inhibitors can also extend the
point and the pKa of the acid. This results in an increase in acceptable pH range.)
the concentration of the negative conjugate base, with a pH Clean-in-place (CIP) Cleaning—As pharmaceutical processes
above the isoelectric point of the surface where the surface go from R&D to pilot scale to manufacturing, the cleaning tech-
will take on a repelling negative character. niques and equipment can change to fit the needs of the scale of
manufacturing. A bench scale system can often be adequately
TABLE 1 RELATIONSHIP OF pKA, CONJUGATE BASE cleaned by manual and soak cleaning procedures. As systems
AND HYDRONIUM ION CONCENTRATION become larger it can be worthwhile to install clean-in-place (CIP)
HA + H2O ➔ H3O+ + A- systems. Parts of the following discussion on CIP cleaning is para-
[HA] = acid concentration H2O = water H3O+] = hydronium [A-] = conjugate base phrased from the website operated by Dale Seiberling—the self
concentration concentration proclaimed CIP Evangelist (www.seiberling4cip.com).
pKa = –log [H O+ ][A-]/[HA]
3
CIP cleaning can be accomplished by the action of a cleaning
solutions with spray or recirculation under pressure of the initial
For example, with stearic acid (C17H35COOH), the conjugate flush, wash, and rinse solutions by controlling time, temperature
base is the negatively charged stearate ion (C17H35COO-). The pKa and cleaner concentration.
is about 5. This means that at a pH of 5 and above, we begin to • Piping Systems can be effectively cleaned via recirculation
drive the reaction toward the right, thereby converting stearic acid of flush, wash, and rinse solutions at flow rates which will
to negatively charged stearate ion. produce a velocity of 5 feet per second or more in the largest
If the stearate ion is a residue on steel and the pH is as high as diameter piping in the CIP circuit.
8.5 and above, then not only do we have negatively charged • Mixers, tanks and blenders can be effectively cleaned by
stearate ions due to being above the pH of 5, but also steel surfaces distributing flush, wash and rinse solutions on the uppers
that are negative in character by virtue of their being at a pH above surfaces at pumping rates equivalent to 2.0-2.5 Gpm per foot
the isoelectric point. The steel and the stearate ions repel each of circumference for vertical vessels, or at 0.2-0.3 Gpm per
other, facilitating cleaning. square foot of internal surface for horizontal and rectangular
As in table 2, for basic residues, these condition would be tanks.

70 The Aqueous Cleaning Handbook Industrial Cleaning Applications 71


• Integrated CIP Design may be applied to combine the clean- ance. The overall scope of the design criteria is to follow FDA’s
ing of vessels and piping in one pass in which flush, wash rationale that cleaning equipment should “prevent contamina-
and rinse solutions to the sprays, and providing for solution tion or adulteration of drug products.”
return to the CIP system. This concept can accomplish CIP at Structural Flexibility—The design of the GMP washer
the minimal capital cost and is highly effective in reducing has evolved over the past 10 years from a modified laboratory
the post CIP recontamination that often follows conventional washer manufactured in a common production line, to a spe-
cleaning of lines and vessels in separate circuits. cific product division within the most up to date manufactur-
ers. Complete separation of tooling and superior welder quali-
A CIP monitoring and control system can be installed to ensure fications are requirements for this range of products as quality
that the CIP system works reliably, rendering the process vessels control and documentation of the entire construction process
and piping molecularly spotless after every product run—or alarm is closely recorded and provided as a deliverable in the final
loudly if it fails. The CIP monitoring and control system can docu- documents. The washer/dryer must be able to perform a multi-
ment the system’s operation and history, and archive this informa- use task while taking into consideration effective utility and
tion for regulatory compliance. One way to set up a monitoring floor plan consumption. Effective use of the chassis must
system is to first circulate and flush water through the CIP system allow for service and technician access as well.
with the control system monitoring the valves and pressure to For the outer shell of the washer, materials of construction
assure and record proper operation; proceed to the wash cycle, should be 316L so as to allow for integration into the clean
possibly using conductivity control to measure and record proper suite arena and be able to withstand the cleaning chemicals
addition of cleaner solution; flush out the cleaner solutions and used in this arena. Service panels should be able to be
proceed to neutralization and rinsing steps. Final rinses can be cir- designed to allow for access to the critical components
culated to equilibration for rinse water sampling if desired. through mechanical chases or locations that the design of the
GMP Washing Machines—Equipment that is disassem- facility allows. Many times, the washer must adapt to the par-
bled for cleaning, manufacturing tools, and bench scale pro- ticular features of the room that requires the positioning of
duction equipment that can be loaded into racks can often be the internal components to be accessed by the facilities or vali-
best cleaned in a washer that can do validated cleaning. dation teams during and after the installation and calibration
GMP Washer/dryer design—within the pharmaceutical process. Temperature and monitoring instrumentation should
industry there has been, and continues to be, a struggle for a be able to be removed from their ports via tri-clamped connec-
clear definition of mechanical washer/dryer to properly tion and have enough coil length to be able to be placed on a
address the requirements of GMP applications. Within the metrology cart outside of the structure of the washer. This will
GMP regs there exists several specifications (Part 133.4, 1963, allow for easy calibration and verification during validation.
and part 211.67, 1978) that attempt to bring some clarity to Freestanding or recessed models must be available to give
the design concept. Unfortunately, these regulations leave the facility the product flow characteristics required for their
many areas open for interpretation with respect to specific process.
construction criteria for a GMP Washer. With no clear defini- Chamber Flexibility—for faster cycle times, effective use
tion, many variations of “lab style” washers have been adapted of the chamber will allow for a minimization of cycles and a
for this arena with their limitations not evident until long after higher throughput of the washer/dryer during the production
the purchase and installation. day.
There are inherent design criteria required for washer/dry- Chamber design should allow for minimal water retention.
ers that will clean parts, glassware, plasticware and tooling Chamber corners should carry a minimum of 1” radius and all
used in pharmaceutical production adhering to GMP compli- surfaces should be sloped to the drain. Internal structures of

72 The Aqueous Cleaning Handbook Industrial Cleaning Applications 73


the chamber should feature rounded edges with no threads or ulate migration into or out of the chamber. The door in
entrapment areas. 316L stainless steel finished to a uniform 25 the down position provides an effective loading table for
Ra should be a baseline for these washers. the operators to easily access three sides of the rack to
Care should be taken with respect to the mating of the place components to be cleaned. Heavy parts can be
inventory systems to the hydraulic circuit. There should be no placed on the door without having to reach into the
mechanical attachment required for the accessory racks. chamber of the washer. Teflon wheels on the racks can
Spray headers should be positioned at the top and the bottom provide for a smooth transition into the chamber.
of the basin to aid in the cleaning of the parts positioned In
keeping with design criteria of utility savings and GMP con- Component Selection—Internal components must be
struction, the chamber volume should be sized to match the compliant to GMP requirements. Sanitary diaphragm valves
load configuration required for a specific facility. should be available for all areas that come into contact with
Care should also be taken to match the items to be cleaned process fluid. Plumbing should utilize orbital welds wherever
so that an effective load and unload pattern can be established possible and be finished to a minimum of 25 Ra. Dead legs
that minimizes operator errors. Multiple level loading configu- should be kept to a minimum of 6 pipe diameters. 316L stain-
rations will allow for maximum utilization of the chamber vol- less steel should be the material of choice for all metallic
ume while minimizing the consumption of WFI. areas. Cold rolled steel, copper, and other forms of stainless
Effective use of Teflon and stainless will allow racks and (except 304L for the frame) should be avoided at all times.
baskets to mate to the chamber of the washer. (Threaded con- Special attention should be placed with the chemical deliv-
nections are to be avoided as they are entrapment areas for ery system. This has been an overlooked area of GMP washer
water and particulate that could lead to cross contamination design due to the difficulty and expense of providing for an
of the products being cleaned.) effective solution. Delivery systems must allow for the addition
Since loads for GMP cleaning can range from glass to plas- of precise amounts of additives (caustic detergents and acid
tic to stainless parts, the design of a loading surface should based products) and must withstand to the harsh nature of the
allow for the weight associated with these components. Two ingredients that is being delivered. Many times, a commercial
types of doors are typically available for this application: laundry chemical system is used only to be the source of fail-
• Vertical doors—These allow for easy access to the items ure months after qualification, resulting in costly down time
to be cleaned but make it difficult to provide for a seal to of the production facility.
the chamber and require the use of loading trolleys, thus Drying systems should provide complete coverage to all
adding to the number of accessories in the clean suite. aspects of the load. Additionally, the washer itself should be
Vertical doors typically have a window built in that has dried entirely and prepared for the next validated cycle. Non-
become popular with lab-style washers but have no func- shedding materials should be used throughout the drying cir-
tionality in GMP. (Internal lights required for their use cuit. High temperature rated HEPA filters should be the final
need gaskets that have maintenance issues and the doors point for the air entering the basin or accessories so as to pro-
are prone to leakage and service maintenance that may vide for a clean, particulate free drying process. DOP challenge
not be possible during a production run. ) ports should be provided so that the integrity of the HEPA’s
• Horizontal drop-down doors—These provide for an can be challenged on a regular interval. Separate circuits for
effective loading table that also serve as an effective con- the basin and the hydraulic circuit (including the internal
tainment structure for the chamber. Gaskets can be parts for the loading accessories) will provide for the fastest
matched to GMP requirements that will allow for com- and most effective cycles. This design is inherently more
plete sealing of the chamber thus allowing for no partic- expensive but can be justified quickly.

74 The Aqueous Cleaning Handbook Industrial Cleaning Applications 75


Inventory Systems—As important as the construction of glassware or parts for the lab or research function. Additional
the chamber, chassis, and internal components are to the over- challenges such as materials of construction, soiling of active
all performance of the washer, the inventory is often the most pharmaceuticals, load configurations, and regulatory con-
overlooked aspect part of the project. Most often, manufactur- straints add to the difficulty of this operation. However, when
ers are criticized for the mating of the inventory system to the properly managed, this task can be easily transitioned and
chamber and to the parts to be cleaned. This aspect of the pro- implemented. A typical procedure for the understanding and
ject involves a complete inventory of the components to be evaluation of a wash protocol would include the following:
cleaned, their dimensional information, weight and specific A. A clear understanding of the items to be cleaned. This
cleaning requirements. Once this information is assembled the definition is paramount to the success of a validated
parts need to be grouped together in the loads that are system in that the operator must load and unload in
required by the facility to be cleaned and an idea can then be specific steps so as to maintain the validation of the
formulated as to the chamber volume required to complete the cycle. Ergonomics of the load and rack must be
task. Ergonomics should be reviewed so as to not overload the addressed at this point so as to make the additional
operator and to maximize the parts/run in order to minimize design and steelwork feasible.
the utility consumption of the facility. B. An understanding of the soiling that will be on the parts
Documentation Requirements—The final part of the to be cleaned. Any active pharmaceuticals must be
package for a GMP washer is the associated documentation addressed and evaluated as to their abilities to be
that will give the validation teams the information whereby a cleaned within the limits of time/temperature/chemi-
complete qualification of all aspects of the system can be cal/agitation.
implemented.
C. Load patterns must then be addressed. In many applica-
The documentation package should contain (as a mini-
tions specific components must be kept together during
mum) the following components:
the cleaning phase so as to maintain their validated sta-
• User’s manual tus in the scope of the process. This challenge requires
• Maintenance manual that the design function of the inventory systems for the
• Instrument list GMP washer have a full understanding of the materials
• Electrical diagram that will be cleaned as well as their dimensional aspects.
• Piping and instrumentation diagram Parts can then be arranged on a CAD drawing to illus-
trate the functionality of the rack and determine if there
• Spare parts list
are going to be any load/unload problems to overcome.
• Exploded view It is this point that a clear definition of the cleaning
• Welding report and welder certificate cycle parameters can begin to come into focus.
• Source codes are provided in the form of a written copy, D. Programming aspects of the PLC or microprocessor can
a floppy disc, and a spare E-prom then take into account the requirements of the washer
• Passivation report to perform the task to clean the items in the chamber.
• As built drawings System monitoring and data transfer to other monitor-
• IQ/OQ documentation ing locations will occur at this point and will play a part
in the design.
Cleaning of components utilized in a GMP environment
presents obstacles that are not found in generic washing of With these considerations, it is possible to successfully use
a GMP washer to clean pharmaceutical equipment.

76 The Aqueous Cleaning Handbook Industrial Cleaning Applications 77


BIOTECHNOLOGY processes—or small particulates that are present in the rela-
When biotechnology goes into production for biopharmaceuti- tively clean manufacturing environment—requires selecting
cals and gene-therapy products, the cleaning requirements can extremely free-rinsing detergents suitable for immersion
be very similar to pharmaceutical needs. The residues that cleaning.
need to be cleaned are often complex mixtures resulting from For parenteral medical devices designed to be implanted
fermentation and cell culture. The cleaners used must not inside the body, a key consideration is that there be no endo-
leave interfering residues that inhibit culture growth or unac- toxins or pyrogens present on the surface. Endotoxins or pyro-
ceptable levels of batch-to-batch contamination. As in pharma- gens are fever-causing cell debris or cell-waste products widely
ceutical process equipment cleaning, disposable single use present in the environment. Cleaning these pyrogens or endo-
items may be used for piping, seals, and filters. When pharma- toxins requires the use of a high-emulsifying cleaner combined
ceuticals are manufactured, even at R&D pilot scale for trials, with heat, followed by rinsing with pyrogen-free or endotoxin-
GMP procedures must be followed. The GMP washers free water. This type of water is often called water for injection
described in the preceding section are often used for biophar- (WFI). WFI is very high purity water derived from high-purity
maceutical cleaning. See chapter 8 on cleaning validation and water filtration systems.
Chapter 7 on standard operating procedures, particularly the
example given on cleaning fermentation equipment. LABORATORY CLEANING
Despite the increasing use of disposable plastics in the laboratory,
MEDICAL DEVICE MANUFACTURING reusable glass labware is still widely employed. This is due to envi-
The cleaning done during medical device manufacturing is ronmental concerns (recycling issues and disposal problems asso-
performed in preparation for sterilizing and sterile packaging ciated with plastics), and because the vast majority of procedures
of medical devices. When selecting a detergent, careful consid- require glass. In addition, there are instruments and equipment,
eration must be given to the materials from which these which for scientific or economic reasons, must be reused.
devices are composed. Usually medical devices are made of The principal concern for any scientist or technician working
fairly robust materials that can withstand corrosive blood and with laboratory glassware, instruments, and equipment is that they
body fluids. In some instances, one portion of the device is be free of interfering residues. These often unseen residues can
intended to come into contact with skin, blood, or body fluids. cause invalid analytical results. For example, they can erroneously
Other parts of the device are exterior to the human body and accelerate or decelerate rate dependent experiments by causing
may be made of less sturdy plastics or aluminum. If these less localized high concentrations of reactants inside micelles. They can
sturdy materials are present, a milder detergent should be inhibit culture growth, cross-contaminate batches, and cause non-
selected. reproducible results.
Medical devices are usually assembled under fairly clean To solve these problems, equipment must be cleaned thorough-
conditions. As a result, a light-duty cleaner is usually selected ly and any interfering residues removed. This requires that an
to remove light quantities and types of soils. appropriate laboratory detergent be selected and an effective clean-
Good medical device design entails creating devices that ing method used (Table 6C).
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 Industrial Cleaning Applications 79


3. Ultrasonic cleaning is used for larger numbers and repeti-
TABLE 6C DETERGENT SELECTION GUIDE FOR LABORATORY CLEANING
tive batches of labware cleaning. To clean in an ultrasonic
Application Recommended
Key Concerns Articles Cleaned/Soil Removed Cleaning Method Detergent tank, a solution is made up in a separate container, the ultra-
Laboratory Glass, metal, plastic labware, ceramics, tis-Manual, Ultrasonic, Soak, C-I-P* Mild alkaline sonic tank filled, and the machine run for several minutes to
Reproducible sue culture, porcelain, clean rooms, animal
results, no interfer- cages, bioreactors, tubing, benches, safety
Machine, powerspray, labware
washer, washer-sterilizer, cage-
Low-foaming alkaline degas the solution and allow the heater to reach the correct
ing residues, equipment.
extending equip- washers temperature. Small articles should be placed in racks or bas-
ment life. Keep lab- Tubes, reusable pipets. Siphon-type washer-rinsers Tablet
oratory accredita- kets; irregularly shaped articles aligned so that the long axis
Water and environmental sampling. Manual, Ultrasonic, Soak, C-I-P* Mild alkaline
tion. Laboratory Phosphate-sensitive labware. EPA procedures. Machine washer, labware washer faces the ultrasonic transducer (usually the bottom); and the
safety. Phosphate-free, low foam
Radioactive equipment/contaminants. Manual, Ultrasonic, Soak, C-I-P* High emulsifying, mild alkaline ma-chine should run 2–10 minutes until parts are clean. A
Stopcock grease. Machine washer, warewasher Low-foaming alkaline,
high emulsifying, alkaline
thorough rinse follows.
Trace metals, metal oxides, scale. Manual, Ultrasonic, Soak, C-I-P* Mild acid 4. Automatic syphon washing is an effective way to clean
Proteinaceous soils, bio-wastes, tissue, blood Manual, Ultrasonic, Soak, C-I-P* Enzyme Cleaner
and other body fluids, fermentation residues Glassware washer reusable pipets. The pipets should be placed completely cov-
Low-foaming alkaline
*Clean-in-Place by circulating, for spray clean-in-place see machine washer detergents.
ered in a detergent soak solution as soon as is practical after
use. This prevents soils from drying onto the pipes. When
The following are common laboratory-cleaning procedures, ready to clean, the pipets are placed in a holder; an efferves-
along with guidelines for eliminating interfering residues. cent tablet cleaner is dropped into the washer; the pipets are
placed in a holder over the tablet; and the cold or warm
1. Soaking is used to clean small items and the insides of
water is turned on at a rate that will fill the washer to cover
larger vessels. It should be used as a pretreatment to prevent
all of the pipets and allow them to drain thoroughly. This
soils from drying onto labware. A soak tank should be kept
may take as long as an hour. For analytical use, a final rinse
at the laboratory bench for immersing used labware until
in deionized or distilled water may be required.
such time that it can be washed. Soaking is also effective to
clean or pretreat very difficult, dried-on residues. To clean 5. Machine washing is used in laboratories for cleaning
by soaking, a detergent recommended for soaking should be large quantities of reusable labware. The machine’s direc-
used, and a detergent soak solution made up according to tions should be consulted for details on its proper use. In
the directions. The article should be completely submerged general, the labware is loaded on racks with open ends fac-
to prevent any deposits or etching at the air/solution inter- ing the spray nozzles. Narrownecked flasks should be placed
face. Soils should be soaked until they are removed; this in the center of the racks, preferably on specially designed
may take several hours. Some soils may require additional spindles with spray nozzles directed into the necks.
agitation or wiping in order to remove them. A thorough Handling of the labware in the racks should be kept to a
rinse follows. minimum. Small articles should be grouped in baskets to
prevent dislodging by spray. Only low-foaming detergents
2. Manual cleaning is used to clean small batches of labware
designed for these machines should be used. Typically, 10
equipment and benches. It is the most commonly used labo-
mL of detergent per liter of hot, wash-cycle water (approxi-
ratory cleaning method. To clean manually, the article to be
mately 60˚C) is used.
cleaned should be wet either by immersing it in the deter-
gent solution, or by using a soaked cloth or sponge. For 6. Rinsing is an often overlooked and very important part of
nonabrasive scouring, un-diluted detergent should be laboratory cleaning. A thorough running water rinse that
poured onto a wet cloth or sponge for scrubbing. A cloth, contacts all surfaces of an article for at least ten seconds per
sponge, brush, or pad can be used for cleaning. A thorough surface may be required. Filling and emptying small vessels
rinse follows. Protective gloves and eye protection should be with rinse water at least three times is a good rinse proce-
worn if recommended or required. dure. For machine cleaning, there should be at least three

80 The Aqueous Cleaning Handbook 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 criteria.
Ceramic insulators and Manual, Ultrasonic, Soak Mild alkaline
of food or beverage products. Examples include juice and decaffeinat- components. Parts washers Low-foam alkaline
ed coffee processing as well as cheese manufacturing. Such processes
often result in highly fouled, difficult-to-clean filter membranes Additional types of soils encountered in electronics cleaning are
which are often very expensive filters with high value. Effective clean- solder flux residues, mold release agents, as well as metal oxides
ing maximizes their useful life and returns their performance to high formed on vacuum components. For example, metal oxides may be
rates of throughput. found on frame holders.
Since the foods being filtered are by definition foods or nutrients, While organic residues usually require some type of emulsifier
these membranes are also frequently fouled by biocontamination that for their removal, metal oxides are frequently better removed by an
grows on the nutrient value of the food, causing a condition known acid cleaner with high chelating or sequestering capacities.
as bio-fouling or bio-film. This type of fouling is often effectively
removed by an enzyme-based cleaner. Enzyme-based cleaners are PC BOARDS
also desirable because they often can be made with a neutral or near- A wide variety of contaminants can remain on the completed assem-
neutral pH that won’t damage the membranes. bly surface if they are not properly cleaned. These contaminants can
It is important to note that since some membranes are delicate be:
and cannot face harsh alkaline or acid cleaners, it is crucial to select
• Ionic—those with an ionic charge, typically salts such as sodi-
a detergent which will not cause membrane damage.
um, potassium, and chlorides. These are of particular concern
because they are potentially conductive, mobile residues.
GENERAL ELECTRONICS CLEANING
• Polar—having a dipole moment (a molecule with partially
Electronic components are usually made of metal due to their con-
charged, positive or negative ends or poles), in the sense that
ductive nature and their ability to be bonded by soldering. Soldering
“like dissolves like,” which tend to solvate ionic residues lead-
involves the use of flux, an undesirable contaminant since it is not
ing to the concerns previously discussed.
only unsightly but acidic, thus causing corrosion of electronic com-
ponents. • Nonpolar—having no dipole moment, typically an organic
Other types of electronic components are glass or ceramic insula- film with insulating and adhesion interfering properties for
tors. It is important to clean the surface completely in order to pre- bonding or marking.
serve their insulating properties. Oils or other conductive residues or • Nonionic—organic compounds that have no ionic charge and
particulates must often be removed. are not salts. They may be either polar or nonpolar (as dis-
A special consideration in electronics cleaning involves compo- cussed previously).
nents that rely on a vacuum to create an insulator. These include light
bulbs and vacuum tubes where residue can “outgas” into the vacuum, 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, residue is not always white. It can be gray, tan, beige, or amber in
organic acids such as the rosin acids and organic acids used as acti- color. There are several possible causes. In some instances the assem-
vators are ionic. An organic molecule by definition is one based on bly butter coat is removed, thus revealing the glass weave intersec-
the element carbon. tions. This is known as measling. This can result if too harsh a sol-
The most detrimental type of contaminant is the ionic type. If not vent is used for cleaning. Another instance of white residue is when
cleaned away, ionic species of contaminants can cause serious prob- activator materials are left behind on the assembly surface. This can
lems including leakage currents between traces on a board as well as come about if the solvent used for defluxing has become depleted of
severe corrosion. The presence of moisture greatly accelerates the alcohol (this is especially true of solvents based on trichlorotribluo-
activity of ionic species since water solvates the ions and enables roethane or CFC-113).
them to become mobile. In the presence of an applied voltage across Another cause of white residue is solder paste. Solder paste con-
circuit traces and moisture, dendritic growth can occur. This occurs tains materials known as thickening agents (thixotropic agents or
when atoms of the circuit trace migrate outward across the bare lam- rheological modifiers). These materials are difficult to remove during
inate until they bridge the circuit width, causing an electrical short. the defluxing operation, especially without the expenditure of
Mobile ionic species speed up this form of growth. Mobile ionic mechanical energy, e.g., sprays. These thickening agent residues are
species are also responsible for corrosion products being formed on prone to form a white residue, especially if exposed to alcohol.
the assembly surface. Military contractors are required to apply a Exposure to alcohol can come about either from alcohol in the
conformal coating to protect the assembly surface from moisture. A defluxing solvent or alcohol in an ionic contamination tester.
conformal coating is, of course, a polymeric material such as an However, the principal cause of white residue is due to thermal
epoxy, polyurethane, or acrylic designed to protect the assembly sur- degradation of rosin. Rosin readily undergoes degradation and poly-
face from moisture. In addition, conformal coatings also isolate cont- merization (the molecules bond together to form a much larger mole-
aminants and prevent them from migrating or being dislodged during cule). This is especially true when it is heated around 260˚C (500° F)
temperature-moisture cycling, high vibration, shock environments, or higher. The rosin also interacts with tin and lead salts formed dur-
etc. ing the fluxing operation by the activator action on the solder oxides.
Nonionic contaminants remaining on the assembly surface can The rosin interaction products are termed tin and lead abietates. The
also lead to performance problems. These contaminants can interfere polymerized rosin and/or tin and lead abietates are much more diffi-
with electrical bed-of-nails testing by creating electrical “opens.” They cult to remove by a defluxing solvent because of their more insoluble
can also lead to adhesion problems if a conformal coating is being nature. Typically, the white residue appears after the defluxing opera-
applied. tion after the defluxing solvent has flashed off. Both rosin fluxes and
Ionic materials and some hygroscopic nonionic materials under rosin pastes are prone to form this type of white residue.
conformal coatings can also lead to blistering during If this type of white residue appears, what can be done? First, it
temperature/humidity cycling. This phenomenon is also called meal- is necessary to ascertain that the flux (or paste) is truly the source of
ing or vesication, and it takes place because no conformal coating is the white residue and to verify that the white residue does not have
100% effective against moisture penetration. In fact, the presence of another cause.
ionic material or hygroscopic material on the surface under the con-
formal coating actually acts to promote water penetration since such PRECISION ELECTRONICS
contamination attracts water. Once the contaminant becomes hydrat- Aqueous cleaning technology is used to meet the high level cleaning
ed, it builds up osmotic pressure which causes a lifting of the confor- requirements in precision electronics manufacturing of disk drives,
mal coating thus leading to the blister or vesicle. This type of phe- semiconductors, and electrooptics. These industries use high purity
nomenon must be considered detrimental to the finished assembly. aqueous cleaners in controlled environment manufacturing settings.
Finally, there is the phenomenon of white residue (WR). White These cleaners are made from high purity ingredients with filtration

86 The Aqueous Cleaning Handbook 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 c. Do not remove parts from shipping containers prior to
defined, the type of report or logbook entry should be defined, being ready to clean them promptly—if you know that
the trigger points and alert levels should be defined, actions unpacking the parts increases the risk of new contami-
taken in response to these levels and finally the conditions nants, or
under which the bath is dumped should be defined. d. Handle all parts with finger cots to avoid adding finger-
prints to surfaces – if you do not want to add any new
ITEMS FOR A MANUAL PARTS OR fingerprints to a surface where you are using a cleaning
MANUAL SURFACE CLEANING SOP process that is only designed to remove particulates
1. List of parts or surfaces being cleaned. Define the scope e. Presoak the parts in a defined detergent solution at a
of the SOP, the maximum number of parts or surface area defined temperature and time prior to cleaning – for
this process is designed to clean. Define any level of training example presoak parts completely immersed in 1% Terg-
or certification required to perform this cleaning operation a-zyme detergent (1.25 ounces Terg-a-zyme in 1 gallon
2. List of Materials of water) at 120 deg F for 20 minutes prior to cleaning—
a. Detergent—define full name, manufacturer, manufactur- if you know your parts have dried on protein soils that
er part number, distributor/supplier, and internal part are difficult to clean without presoaking
number as appropriate 4. Directions for making up the detergent solution: Make
b. Water of suitable purity—define tap water, deionized up detergent solution diluted in water of suitable purity
water, distilled water or water-for-injection as is appro- according to directions in a container of suitable size at a
priate given temperature.
c. Brush, absorbent cloth or sponge—whatever is used a. For example: Mix 1.25 ounces of Alconox powdered
d. Container of suitable size for the detergent solution— detergent in 1 gallon of 120 deg F hot tap water in a 2.5
define container gallon bucket. Use cleaning solution within 15 minutes
before the temperature drops below 120 deg F.
e. Any baskets for handling small parts, if used
5. Manual cleaning description:
f. Any rinsing containers, if used
a. Wet part or surface with solution by
g. Any drying equipment, if used
i. Dunking the part in the solution, or
h. Any required protective equipment, gloves, eye protec-
tion, clothing etc. ii. Wiping the part with a solution soaked brush,
absorbent cloth or sponge
3. List any requirements for handling prior to cleaning.
The type of things you could optionally list as they apply b. Clean by scrubbing with the brush, absorbent cloth or
would be: sponge –
a. Parts to be cleaned within 4 hours of being processed to i. define any particular cleaning or scrubbing actions
remove grime—if you knew that the grime had a tenden- required such as: brush all surfaces vigorously, but
cy to dry onto the parts and become more difficult to particularly be sure to use brush vigorously on the
clean, or inside of the port for at least 30 seconds
b. Tank to be cleaned within 3 days of last use—if you had 6. Rinse Procedure:
validated that the tank could be successfully allowed to a. For example: place parts in basket and run them under
sit dirty for 3 days and still be cleaned by this manual running tap water for 20 seconds while moving basket to
procedure, or assure all parts are exposed to running water, or

98 The Aqueous Cleaning Handbook Standard Operating Procedures 99


b. Hose down all surfaces with running water assuring that g. sponge
all parts of surface are rinsed for at least 10 seconds, or h. non-abrassive pad
c. Dip part in bucket of rinse water for initial rinse, dip in 3. Precleaning requirements and procedures:
second bucket of rinse water for second rinse, and then a. When the fermentation run is complete, it is necessary
place under running water at the sink for 10 seconds as to carefully shut the process down. First all operating
a final rinse. parameters (agitation, temperature, dissolved oxygen
7. Drying procedure (D.O.) level, pH, and gas feed) must be set from their
a. Such as, place parts on rack and allow to air dry, or current control modes (such as “PID”, “D.O.”, “Base”) to
b. Place parts on tray and place in 210 deg F drying oven the “Off” mode. Note that the manual air valve on the
for 40 minutes, or side of the unit should also be closed as well.
c. Open all ports in tank and allow tank to air dry Additionally, if a supplemental oxygen feed was used, it
8. Any post cleaning handling procedures, such as: will be necessary to close the gas tank valve and the
lines leading from it to the unit. If a recirculating chiller
a. Define any inspection actions such as: take 10 parts
is in use, it should be shut off when the temperature
from the batch and inspect for particulates and visible
control is shut off. Feed lines from any addition bottles
smudges with a 10X magnifying glass. Record results in
which have been used should be clamped off prior to
batch record. Reject entire lot if there are any failures.
detaching them from the vessel, and should then be
Or,
removed.
b. Mark tank with “clean tags” recording time, date, and
i. The next step is to disconnect the vessel from the
operator who performed cleaning. The next day after the
unit. The temperature probe needs to be removed
tank has dried, close the ports to keep out dust. Or,
from the thermowell. Remove the motor and place
c. Dispose of used detergent solution down the drain.
the protective cap over the agitation shaft. Always
disconnect the water lines by disconnecting the
An example of a manual cleaning SOP written for manual incoming lines prior to the outgoing lines. The air
cleaning of a bench top fermentation reactor adapted from line must be disconnected from the sparger.
“Fundamentals of Fermentation: Techniques For Benchtop Disconnect the pH and D.O. probes from the unit
Fermentors Part I - E. coli” which was prepared by the R & D and replace their protective caps. The D.O. probe
Lab, New Brunswick Scientific Co., Inc. is: presents an easy removal as you simply unscrew
1. Scope the thread and gently pull it out. It should be
a. For cleaning bench top fermentation reactors immediately rinsed off and then wiped dry gently,
b. Operator training a qualification required always remembering to avoid touching the mem-
2. Materials brane at the tip. Some runs will result in an accu-
a. Liqui-nox Detergent (Alconox, Inc. Catalog Number mulation of biomaterial on the probe and it may be
1201) necessary to wipe the probe down more vigorously
but in no case should the tip be touched. After
b. Water
cleaning the D.O. probe the tip can be visually
c. Kimwipes®
inspected for damage. The probe should then be
d. pH 7 buffer stored in a clean area in such a way as to protect
e. chemical resistant gloves the sensitive tip. Removing the pH probe is usually
f. glycerine not as difficult a process as inserting it because the

100 The Aqueous Cleaning Handbook Standard Operating Procedures 101


shaft will be wet and thus should be relatively easy the liquid level, as is the case with a side harvest line).
to remove. However the danger of probe breakage The headplate should be detached by loosening and
is still very real and extreme care must be taken then removing the clamps that hold it to the rest of the
when removing it. It is still necessary to use two vessel. Those clamps may require rinsing. The remain-
hands with one hand at the top of the port acting as ing culture broth should be sterilized or emptied into a
a guide to ensure proper removal. A gentle pace for bucket and disinfected by using bleach or other accept-
this is required. If at any point in this process the ed disinfectant prior to disposal. Note that some media
probe jams, it is essential to avoid trying to force it. may be incompatible with this procedure, in which case
It may be necessary to reinsert it part way and the media can be placed into another container for ster-
apply a lubricant such as glycerin to the shaft and ilization prior to disposal. The headplate should be
port in order to effect the probes' removal. In washed thoroughly with warm water and then de-ion-
extreme cases it may be necessary to remove the ized (DI) water. It may be necessary to scrub accumula-
headplate with the probe still inside so that you can tions of biomaterial off. A pad that won't scratch the
approach the problem from both ends. In this case, steel is required for this. The agitation shaft, the ther-
it is critical to remove the headplate very carefully. mowell, harvest and sparger tubes and the short beveled
(We recommend that you have a spare probe avail- tips of the interior portion of the base-type addition
able at all times, in case of breakage.) Once the pH ports will often require special attention. All tubes and
probe has been removed, it should be immediately shafts must be cleaned. Note that there may be some
washed off with warm water. If biomaterial has residual base or acid left in those lines, so extreme cau-
accumulated on the probe, using a sponge (or an tion and the use of chemically-resistant gloves is recom-
equivalent that will not scratch glass) and gentle mended for this procedure. It is often necessary to hand
pressure to clean the surface. The very tip of the wipe surfaces with a paper towel in order to fully
probe should be handled with extreme care and a remove residual traces of small particulate debris.
Kimwipe® should be used to gently dry it off after b. The washing of the bottom portion of the vessel
washing. The probe should be stored with the tip requires the same procedures as the headplate. Note
immersed in either electrolyte or pH 7 buffer. This that the sides of the vessel, particularly where the baffle
electrolyte/buffer can be reused, but it should was adjacent to it, and side ports (plugged or
always be inspected prior to each use for precipita- unplugged) may require special attention.
tion or contamination. c. The vessel can now be cleaned by washing with deter-
4. Manual cleaning, rinsing and drying description gent, or by using a cleaning solution. If the vessel is to
a. Now that the vessel is detached from the unit, it can be be sterilized, all standard precautions must be taken.
cleaned. To do this it will be necessary to remove any Note that for this purpose, the vessel does not need to be
remaining cotton and foil covering the ports. The rub- sealed except for those previously cited valves and tub-
ber bulb on the sampler should be removed and rinsed ing which run under the liquid level. It will be necessary
separately. The glass wool can be removed at this point to use water in the vessel. We recommend the use of DI
as well. The sampling tube is detached and washed sep- water, and the fill should be at least as high as your stan-
arately. The valve on the sampling port and all clamps dard level for a run. Unless you have already specifically
on all tubing connected to ports will need to be open for wiped the residual grease off the top of the glass cylin-
proper washing. (Note that the media will need to be der, there should be enough so that the headplate can be
removed prior to unclamping any tubing that is below clamped to the lower portion of the vessel. Note that it is

102 The Aqueous Cleaning Handbook Standard Operating Procedures 103


neither necessary nor desirable to fasten these clamps d. Baskets for handling small parts, if used
with the same force used for attaching the headplate e. Any rinsing containers or equipment
prior to a run, as this could lead to vessel damage. f. Any drying equipment, if used
Instead, the lightest possible pressure should be used. g. Any required protective equipment, gloves, eye protec-
The advantage to sterilization is that not only are resid- tion, clothing etc.
ual viable organisms killed, but residual debris will
3. List any requirements for handling prior to cleaning.
loosen and become removable by washing after the ves-
The type of things you could optionally list as they apply
sel has cooled. If a cleaning solution is required, use a
would be:
1% dilution of Liqui-nox cleaning solution (Alconox, Inc.
a. Degas solution for 10 minutes to remove dissolved
catalog number 1201). Alternatively, if you are using the
gasses that will dissipate cavitation energy and decrease
vessel for consecutive runs with the same media, a rins-
cleaning performance
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 b. Turn on heaters and preheat the tank to 120 deg F (50
has grease on it, the grease should be removed by wiping deg C)
it off with a wet paper towel. c. Parts to be cleaned within 4 hours of being processed to
d. In cases where the vessel must be decontaminated prior remove grime – if you knew that the grime had a tenden-
to cleaning, add water so that the liquid level reaches cy to dry onto the parts and become more difficult to
the maximum working volume of the vessel. This will clean, or
help prevent biological materials from adhering. d. Do not remove parts from shipping containers prior to
e. Allow vessel to air dry after thorough rinsing being ready to clean them promptly – if you know that
unpacking the parts increases the risk of new contami-
5. Post cleaning procedure
nants, or
a. Store vessel in a clean area.
e. Handle all parts with finger cots to avoid adding finger-
b. Inspect visually prior rinsing and sterilization for next
prints to surfaces – if you do not want to add any new
use.
fingerprints to a surface where you are using a cleaning
process that is only designed to remove particulates
ITEMS FOR A ULTRASONIC CLEANING SOP f. Presoak the parts in a defined detergent solution at a
1. List of parts the process is intended to clean. Define the defined temperature and time prior to cleaning – for
maximum number of parts to put into a batch to be example presoak parts completely immersed in 1% Terg-
cleaned. Define any level of training or certification a-zyme detergent (1.25 ounces Terg-a-zyme in 1 gallon of
required to perform this cleaning operation. water) at 120 deg F for 20 minutes prior to cleaning – if
2. List of Materials you know your parts have dried on protein soils that are
a. Detergent—define full name, manufacturer, manufactur- difficult to clean without presoaking
er part number, distributor/supplier, and internal part 4. Directions for making up the detergent solution: Make up
number as appropriate detergent solution diluted in water of suitable purity according
b. Water of suitable purity—define tap water, deionized to directions in a container of suitable size at a given tempera-
water, distilled water or water-for-injection as is appro- ture.
priate a. For example: Mix 1.25 ounces of Alconox powdered deter-
c. Ultrasonic cleaning tank—define size, frequency, config- gent in 1 gallon of 120 deg F (50 deg C) hot tap water which
uration, manufacturer, and identifying specifications will fill to tank to within 1 inch of the top of the tank

104 The Aqueous Cleaning Handbook Standard Operating Procedures 105


b. For another example: Fill the tank within 1 inch of top deionized water – change rinse water when it reaches 50
and turn on heaters. Make up 1% Alconox solution in a Kohms resistance.
beaker (20 g Alconox in 200 ml water in a 250 ml 7. Drying procedure
beaker). Place beaker of Alconox solution in a beaker a. Place parts on rack and allow to air dry, or
tray with the beaker immersed in the heated water. Fill 3 b. Place parts on tray and place in 210 deg F drying oven
other beakers with deionized water for rinsing and place for 40 minutes, or
them in the beaker tray.
8. Any post cleaning handling procedures, such as:
c. Degas solution for 10 minutes to remove dissolved
a. Define any inspection actions such as: take 10 parts
gasses that will dissipate cavitation energy and decrease
from the batch and inspect for particulates and visible
cleaning performance. This is particularly important for
smudges with a 10X magnifying glass. Record results in
freshly made up solutions.
batch record. Reject entire lot for recleaning if there are
d. Turn on heaters and preheat the tank to 120 deg F (50 any failures. Or,
deg C)
b. Dispose of used detergent solution down the drain.
5. Ultrasonic cleaning steps:
a. Never place parts or receptacles directly on the bottom
An example of an ultrasonic cleaning procedure adapted
of the unit. It can cause the unit to fail because the parts
from a manufacturer of small stainless steel and aluminum
will reflect the ultrasonic energy back into the transduc-
parts is:
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 1. Scope
when a beaker or tray is in place. a. For the cleaning of small stainless steel and aluminum
b. If using a tray or basket to lower the parts into the solu- parts
tion, it is better to use a holder that is of open construc- b. To be carried out by trained and qualified operators
tion, either an open mesh basket or an insert tray, that is 2. List of Materials
adequately perforated for drainage. This also permits a. Alcojet powdered detergent (Alconox, Inc. catalog num-
free access of the sound waves to the parts. ber 1450)
c. Clean the parts to be cleaned in the solution by b. Drain rack with mounting pins to mount connectors on
i. Placing them in basket and immersing them in the for cleaning operation
ultrasonic tank for 10 minutes c. Ultrasonic cleaning tanks
ii. After 10 minutes lift basket and allow it to drip off d. Ultrasonic rinsing tanks
for 1 minute to reduce dragout e. Air knife, filtered hot air dryers
iii. Cover ultrasonic tank after removing and draining f. Deionized water
basket g. Drying ovens
6. Rinse Procedure: h. 10X magnifying glass
a. For example: take basket and run them under running i. alkaline resistant rubber gloves
tap water for 20 seconds while moving basket to assure 3. Flow chart showing handling, cleaning, rinsing, drying,
all parts are exposed to running water, do a final rinse control and post cleaning handling
by immersing in a second ultrasonic tank filled with
a. (see chart on pages 107-108)

106 The Aqueous Cleaning Handbook 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 effect), over the entire surface. If areas greater than _ inch
ULTRASONIC CLEANER TEST PROCEDURE square show no pebbling, there may be a problem with the
In working with ultrasonics, it is sometimes useful to be able unit. Retest with new foil to substantiate the failure. The
to test the performance of your ultrasonic washer. The follow- unit, along with its latest foil record, should be returned to
ing aluminum foil test adapted from a Brooks Airforce Base your service center for service, if both samples fail. Foil
procedure (http://www.brooks.af.mil/dis/ic guidelines/ samples may be retained for future comparison. If future
attach2.htm) can be useful. tests show marked changes over time you may need to ser-
vice your unit. Foil samples may be sent with units returned
1. Prepare an aluminum foil sample. Obtain a roll of standard
to the manufacturer for service.
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- CLEAN-OUT-OF-PLACE IN RACK LOADED
sion) of the tank. For example: A tank with dimensions of 9 SPRAY-IN-AIR WASHER
inches long by 5 inches wide by 4 inches deep would require
a foil sample measuring 9 inches by 5 inches. Use scissors to Standard Operating Procedures for the wash cycle in a
cut the foil. Do not tear. machine washer, which does not include the scope and list of
2. Prepare a fresh solution of ultrasonic cleaning solution materials is:
according to the manufacturer’s instructions and fill the 1. Precleaning is only required to remove bulk ingredients
ultrasonic tank to one inch of the brim. from the items to be washed and should be accomplished by
3. If heaters are supplied with the cleaner, turn them off for a thorough rinsing. Handling of the items to be washed
the remainder of the test. Also, if the unit is supplied with a must be done according to manufacturers recommenda-
HI/LO switch, or intensity, it should be set in the highest tions. All safety regulations of your company should be fol-
position. lowed in handling and transporting the items to be washed.
4. Before placing the foil in the tank, turn the ultrasonic clean- 2. Cleaning chemistry and concentrations of the cleaning
er on for five (5) minutes using the timer located on the chemicals is specific to the soiling on the items to be
cleaner. Be sure to turn the timer to 20 minutes, then back washed. The GMP Washer should utilize precise dosing
to the 5 minutes setting for maximum time accuracy if it is pumps to deliver chemicals to the wash chamber. The dos-
an analog timer. Digital timers can be set directly. ing time will determine the amount of chemical delivered to
the fixed volume of water in the wash chamber.
5. Place foil sample which was prepared in Step 1 into the
tank in a vertical position. The foil long dimension should 3. Temperatures in the GMP washer should be user program-
be positioned with the long tank dimension. The foil should mable up to 95 degrees Centigrade.
extend downward, but should not touch the tank bottom. 4. Exposure time of the cleaning chemistry at setpoint temper-
6. Hold the foil, approximately centered front to back, as ature will account for proper cleaning. GMP Washers vali-
steady as possible. Turn the ultrasonic cleaner on for exactly date exposure time through continual monitoring of all
20 seconds. parameters.
7. Turn the cleaner off and remove the foil sample. Shake the 5. Purified Water rinsing (i.e. WFI, USP) is performed to
foil sample dry of any water droplets. Allow foil to air dry, ensure removal of all cleaning chemicals at the end of the
being careful not to wrinkle the foil. wash cycle. Conductivity measurement of final rinse water
can be taken to validate rinsing efficiency.
8. Properly functioning units will result in foil surfaces that
are uniformly “peppered” (covered with a tiny pebbling

110 The Aqueous Cleaning Handbook 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 at 4.5 gallons/min at 345-1035 Kpa pressure for a 4 inch
BRINE WATER FILTER SYSTEM CLEANING system. Use the chiller to maintain the temperature
1. Scope below 35 deg C.
a. To clean a large ultrafiltration brine water filter system f. The cleaning progress can be monitored by observing the
color of the effluent. Circulate continuously or by alter-
b. Operators must be trained and qualified
nately circulate/soak for 15 minute intervals. Circulate
2. Materials
for at least 2 hours for a 4 inch system. Continue until
a. Good quality chlorine-free tap water (total dissolved
the return effluent is no longer badly discolored.
solids less than 5,000 mg/l)
g. When cleaning is completed, stop recirculation, drain
b. 316 stainless steel mix tank sized appropriately to the
mix tank to waste. Flush residual cleaner with feed
system (minimum of 3 minute retention time during cir-
water at 4.5 gallons per minute (for 4 inch systems) at
culation) with an exhaust fan, mixer, cooling coil, and
345-518 Kpa pressure (for 4 inch systems) sending both
temperature indicator
brine and product side to drain. Collect sample of efflu-
c. 316 stainless steel centrifuge pump sized for appropriate ent in a small jar, cover, shake and observe foam indicat-
flow rates ing the presence of detergent. Rinse jar between uses.
d. 10 micron cartridge prefilter Continue flushing until no foam is observed in the shak-
e. Flow meters en sample jar.
f. Suitable flexible piping, sampling ports and port connec- 5. Post
tors a. Perform post treatment procedures and return block to
g. Terg-a-zyme (Alconox cat no 1350) enzyme cleaner normal operations. Observe pressure and performance
3. Pre cleaning conditions to determine if further treatment with a citric cleaner
such as Citranox (Alconox, White Plains NY USA cat no
a. Filter system suffering from biofouling and/or inorganic
1815) may need to be performed to reduce particulate
particulate build-up
and inorganic scale buildup.
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
CLEAN-IN-PLACE LARGE TANK FILL,
normally. SOAK AND AGITATE CLEANING
1. Scope
b. Flush filter element block with water once through (10
gallons for a typical 4 inch diameter filter element unit – a. To clean a large stainless steel tank to remove a blended
different sized units would take proportionally more or material that contains a thick high melting wax.
less water) b. Operators must be trained and qualified
c. In the mix tank, dissolve enough Terg-a-zyme to make a 2. Materials
0.5% solution taking into account the volume of the a. Detergent
tanks and filter element blocks (2.5 gallons for a 4 inch b. Brush
system). c. Bucket
d. Turn on mixer to dissolve detergent d. Recirculation pump
e. Circulate the cleaning solution through the filter block. e. Hot water hose
Send the first 20% of the solution to drain via the brine 3. Precleaning conditions
return valve. Circulate the rest of the cleaning solution a. Tank with waxy residue shall be cleaned within 24 hours.

114 The Aqueous Cleaning Handbook Standard Operating Procedures 115


b. Tank ports should be kept closed while in holding Note, adjustment of the recommended 4 hour clean-
4. Cleaning, rinsing and drying description: ing time may need to be done as experience is gained
a. Fill tank full with hot plant water with specific soils and tanks. This cleaning regimen is
b. Add detergent recommended for the type of residue in designed for a wax, which melts around 200 deg F in
the tank (see note) mind. Many soils may not require heating to an excess of
200 deg F. Many waxes are melted by 170 deg F and this
c. Turn on mixer wipers to agitate
procedure could be adapted to use a lower temperature
d. Turn on tank heaters to raise temperature above 200 deg for lower melting waxes of for residues that did not
F (see note) require such high temperatures.
e. Turn on pumps and connect pipes to recirculate through
any lines that need to be cleaned. Note pumps should be The previous sections in this chapter give examples of
operated with sufficient head or at a slow enough speed standard operating procedures. The types of considerations
to avoid cavitation due to foam formation. and procedures could be adapted to many other kinds of
f. Run for 4 hours. Depending on how well sealed the tank cleaning. There are many types of cleaning machines, each
is, you may need to top up the solution to compensate would have its own machine specific standard operating pro-
for evaporation cedure. You could have procedures for a range of machines
g. Open top and manually scrub with a brush dipped in the such as vibratory washers, oscillating washers, reel-to-reel
hot solution the unexposed top sections of the tank that washers, spray cabinet washers, and a range of other industri-
were not immersed by the cleaner al washers. As long as the general topics outlined here are cov-
h. Drain the tank ered a successful SOP can be written. The machine manufac-
turer should be able to help you understand the proper use of
i. Fill the tank with hot plant water that had been heated to
the machine. You can add your own understanding of your sit-
200 deg F with the agitation and any recirculation pump
uation to adapt this to a successful SOP.
turned on for 10 minutes.
j. Use a hose with hot water to rinse the top part of the
REFERENCES
tank above the immersion line
DuPont Company Bulletin 507 “Cleaning Procedures” p 1-4 (1982)
k. Drain the tank Durkee, JB, The Parts Cleaning Handbook, Gardner Publications,
l. Visually inspect the interior of the tank and clean any Cincinnati, 1994
known problem areas with a hot bucket of detergent Dollard, R M Keeping Validation Current: Elements of an Effective
solution and a brush. Change Control Program, Philadelphia. presented at Cleaning
Validation and Cleaning Processes Jan 14-15 Philadelphia, PA (2002)
m. Rinse the tank thoroughly with hose of hot plant water James Fry, Private communication regarding Lancer Washers May 2002
or a spray ball apparatus with hot plant water.
n. Drain the tank.
RESOURCES
o. Allow tank to air dry with ports open
www.alconox.com
5. Postcleaning conditions www.lancer.com
a. Tag the tank as clean with a date to allow control for http://www.brooks.af.mil/dis/icguidelines/attach2.htm
clean hold times
b. Record cleaning in equipment log, recording date, time,
and operator

116 The Aqueous Cleaning Handbook 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 • Sampling method selection,
cross contamination. The people or departments involved in • Setting residue acceptance criteria,
carrying out the validation with defined responsibilities would • Methods validation and recovery studies, and finally
include:
• Writing a procedure and training operators.
• Validation Specialist—writes, coordinates validation
• Manufacturing—write SOPs, do training This procedure is used to document acceptable residues
• Quality Assure/Control—approve and do analytical three or more times and then a rational monitoring program
methods to maintain a validated state is put in place. If changing any
• Engineering—inform of changes, provide equipment part of the procedure or cleaner, first clean the new way, col-
data lect data and then clean the old way before using any equip-
• R&D—recovery, validate methods, transfer methods, ment while in the process of validating the new procedure.
new cleaners Residue identification—in a pharmaceutical manufactur-
ing environment this involves: the cleaner, primary ingredi-
In the course of the validation one can simplify things by ents, excipients, decomposition products, and preservatives.
assembling an equipment matrix that defines all shared and This document is intended to help with the cleaner residue
dedicated equipment. Work can be done to justify which identification.
equipment represents worst case hardest to clean equipment Residue detection method selection—for cleaners can
that in turn must have a full validation done to represent the involve specific methods for specific cleaner ingredients such
documented easier to clean equipment. as: high-performance liquid chromatography (HPLC), ion
By the same token, a matrix of residues can be assembled selective electrodes, flame photometry, derivative UV spec-
to classify into residue groups of types that are cleaned by a troscopy, enzymatic detection and titration. It can also involve
given set of conditions and then determine which is hardest to non-specific methods that detect the presence of a blend of
clean. In this way, a worst-case residue or worst-case for a ingredients such as: total organic carbon, pH, and conductivi-
residue class can be confirmed. A matrix of cleaning proce- ty. The FDA prefers specific methods, but will accept non-spe-
dures can then be assembled in order to standardize on as few cific methods with adequate rationales for their use. For inves-
procedures as is practical to improve execution and training tigations of failures or action levels, a specific method is usual-
for these procedures. ly preferable. (A later section of this chapter lists references to
It is important to validate a worst case scenario and to jus- several methods for each cleaner brand.)
tify the choice of “worst-case.” The worst case is typically cho- Sampling method selection—for cleaners involves choos-
sen based on product solubility in cleaner or detergent, the ing between rinse water sampling, swabbing surfaces, coupon
toxicity of the products or degredants being cleaned, dose sampling, or placebo sampling.
sizes and size normal therapeutic dose (smaller may be more Rinse water sampling involves taking a sample of an equi-
critical to validate), hardest to clean equipment/residue, and librated post-final rinse that has been recirculated over all sur-
worst interactions with the next batch to be cleaned. faces. Rinse samples should be correlated to a direct measur-
The cleaning validation for a specific cleaner involves test- ing technique such as swabbing.
ing for acceptable residues on pharmaceutical manufacturing Swabbing involves using wipe or swab that is moistened
or medical device surfaces. The validation involves: with high purity water (WFI) that is typically wiped over a
defined area in a systematic multi-pass way always going from
• Residue identification,
clean to dirty areas to avoid recontamination – i.e. 10 side by
• Residue detection method selection, side strokes vertically, 10 horizontally and 10 each with the

120 The Aqueous Cleaning Handbook Cleaning Validation 121


flip side of the swab in each diagonal direction. For TOC Limit (mg/cm2 or L) = ADI carryover – see below (mg) X Smallest Next Batch (kg)
analysis very clean low background swabs or wipes and sam- Size of Shared Equipment (cm2 or L) X Biggest Daily Dose or of Next Batch (kg)
ple vials such should be used. The Texwipe large Alpha Swab ADI carryover (mg) = LD50 by administration route (mg/kg)
714A or 761 have been used, these are available in kits with X body weight (kg) X (1/ 10,000 or 1/1000*)
clean sample containers.
Quartz glass fiber filter papers have been used successfully. Comparison calculation of limit based on no more than 10
Coupon sampling involves the use of a coupons or an actual ppm carryover:
removable piece of pipe that is dipped into high purity water Limit (mg/cm2) = 10 mg residue on just cleaned surface X Next Batch Size (kg or L)
to extract residues for analysis. 1 kg of L of next product X Size (cm2 or L) shared equipment
Placebo testing involves using placebo product and analyz-
ing for residues from the previous batch. Note that for many residues one can validate a visual
Setting residue acceptance criteria—in pharmaceutical detection limit on the order of 1-4 ug/cm2. It is possible that
and medical device manufacturing requires setting residue the visually clean criteria will be the most stringent criteria.
acceptance levels for potential residues such as the active Example with a cleaner that has an rat oral LD50 of over 5
drug, excipients, degradation products, cleaning agents, g/kg, the ADI calculation using a 70 kg person and a safety fac-
bioburden and endotoxins. These levels are determined based tor of 1000 gives a result of 350mg (5 g/kg X 70 kg / 1000 ).
on potential pharmacological, safety, toxicity, stability, and The calculated residual acceptance limit for a 2000 kg mixer
contamination effects on the next product using that surface and line where there might be a next smallest batch of 1000
or equipment. Limits are typically set for visual, chemical, and kg, and the area of the mixer and filling equipment which is
microbiological residues. all used in the next batch is 100,000 m2 and the daily dose of
The cleaning agent limits are generally covered under the next product is 0.005 kg results in a calculated residual
chemical criteria. Chemical limits can be expressed as a maxi- acceptance criteria of 700 mg/cm2 (350 mg X1000 kg/(100,000
mum concentration in the next product (ug/ml), amount per cm2 X 0.005 kg). By comparison, the 10 ppm in next batch
surface area (ug/cm2), amount in a swab sample (ug or ug/ml), limit gives an acceptance criteria of 100 ug /cm2 (10 mg X
maximum carryover in a train (mg or g), or concentration in 1000 kg/(1 kg X 100,000 cm2) X 1000ug/mg. In this case, it is
equilabrated rinse water (ug/ml). You should have a calculated likely that you will be able to show that you can visually detect
safety based acceptance limit, and you can have a lower inter- down to 4 ug/cm2 and since you need to have a visually clean
nal action level, and a lower process control level based on surface, your most stringent acceptance criteria will be the
actual manufacturing and measuring experience. visual limit.
Cleaning agent safety based limits are typically calculated Note that in this example you are trying to avoid getting
from a safety factor of an acceptable daily intake (ADI), a more than 350 mg of residue in a daily dose of the next prod-
(1/1000 or more) reduction of an LD50 preferably by the same uct. In the case of small final filling equipment such as filling
route of administration, or reproductive hazard levels. If the needles for vials or tablet punches and dies, you might need to
calculated limit is found to be higher than a less than 10 ppm do separate residue studies on the filling needles or punches to
carryover to the next batch, then the limit can be set to the be sure that there was not enough residue just on that equip-
more stringent 10 ppm carryover level for the safety based ment to contaminate the first few bottles or tablets of the next
limit. batch with a residue of 350 mg/daily dose.
Calculated safety based limit in mg/cm2 or mg/ml of clean- If the safety based limit in this example is set at 100
er residue on a just cleaned equipment: ug/cm2. Then this limit can be expressed as a rinse water con-

122 The Aqueous Cleaning Handbook 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 an activated carbon filter, capable of absorbing material
in a cleaning bath not only improves cleaner perfor- many times its own weight within its extensive pore net-
mance, but extends bath life. Further, upon filtering out work.
any particulates or fines, oils collected may be evaluated However, activated carbon is used for organic materi-
for reuse, rather than destined for disposal. als only. Metal contaminants and other inorganic materi-
Traditional mechanical separation of oil from waste- als will remain dissolved or suspended in the wastewater.
water involves the use of skimmers, tank overflow, and An activated carbon filter can be used as one of the last
decanting methods. Such out-of-process, post-produc- stages before discharge or recycling, in order to assure
tion, end-of-pipe wastewater treatment approaches tend cleanliness. Filters can be arranged in series or parallel.
to perform less efficiently in a continuous manufactur- A parallel arrangement allows for change-out of one fil-
ing operation and contribute to disposal problems. ter while the others remain operational.
• UV Systems—Ultraviolet (UV) light is an effective means
EQUIPMENT OPTIONS to destroy biological organisms. A UV-oxidation system
• Evaporators—Evaporation is commonly used to reduce can be employed, as necessary, to reduce the BOD of the
the volume of water for further treatment. The contami- wastewater.
nants then become concentrated within the bottom
sludge and the water is transferred to a holding tank, SELECTION CONSIDERATIONS
where it is allowed to cool to room temperature. The The following are basic guidelines for selection of a waste-
water is either discharged to drain (with the necessary water treatment system:
permits and approvals in place), or undergoes further • Treatment options should be studied by an engineer to
treatment. assess process alternatives. The system should be opti-
• Separators—Gravity separation of nonemulsified oil in mized for proper flow rates, filter capacities, through-
wastewater can occur in the clarification tank. The influ- puts, etc.
ent and effluent flow rates are optimized to allow effi- • Design, maintenance, and operations should have con-
cient separation of the lighter oil layer from the water. tingencies for downtime.
An inclined plate can be used to direct the flow of the oil • Capital and operating costs may justify the recycling of
layer away from the wastewater. wastewater in a closed-loop system.
A current method of oil-water separation applies
Bernoulli’s principle, whereby the wastewater is split CLEANER RECYCLING
into two laminar flows. Oil is continuously collected and As numerous ozone-depleting compounds became legislated
concentrated in a second chamber, which is separated by out of use, a large number of companies chose aqueous clean-
a baffle from the primary chamber and a reduced-pres- ing solutions as replacement alternatives to solvent degreasing.
sure area below. The reduced pressure directs the flow of In the early transitional days, many process and manufac-
water down, away from the second chamber. turing engineers were concerned that aqueous processes
The oil is recovered from the top of the concentrated would reduce part quality and throughput while creating addi-
layer, when the layer reaches a designed thickness. Higher- tional waste and wastewater treatment problems and costs.
quality oil is recovered this way, and is able to be reused. Some alternatives to aqueous cleaning systems include
• Activated carbon—Suspended organic materials can be “drop-in” semi-aqueous or solvent-based cleaning systems.
removed from the waste stream with the application of However, these are not without their own problems, namely

130 The Aqueous Cleaning Handbook Wastewater Treatment and Cleaner Recycling 131
employee health concerns, flash points (flammability), and very fine suspensions of particulates).
possible worker discomfort due to odors. • Physical separation—such as cooling and skimming,
One public lab where solvent replacement work has been settling, and emulsion breakup. Cooling solutions allow
done is The University of Massachusetts at Lowell’s Toxics Use emulsions and suspensions to break. Settling allows
Reduction Institute. The Institute has shown the viability of water-insoluble materials to separate by density; heavy
aqueous cleaning in industrial settings. Aqueous cleaning has sludge will generally settle to the bottom when a suspen-
provided a sound alternative to vapor degreasing in as many sion breaks. In emulsion breakup, light oils will general-
as four out of five applications that the Institute reviews on a ly rise to the surface and the overflow can be physically
laboratory scale for industry clients. skimmed off with oleophilic wicks or cycling bands of
Modern closed-loop aqueous cleaning systems remove oleophilic material, leaving reusable cleaning solution.
contaminants from both the cleaning bath and rinse water, • Solution recharge—is when a detergent solution life can
and compared to solvent cleaning systems, may be relatively be extended by using the detergent to exhaustion, and
inexpensive to install. then adding some amount of additional detergent (for
Recycling can help reduce or eliminate liquid waste by example, 50 percent of the original dose). The concentra-
trading dilute liquid waste for more easily disposed solid tion of useable detergent will then be sufficiently raised
waste in the form of spent filters or concentrated sludge. to a level where effective cleaning will occur.
Recycling can also help reduce detergent consumption in
• Ultrafiltration—is when multiplex membrane filters are
order to get more parts clean per pound or gallon. It may also
packaged into a variety of cartridge configurations and
save time and increase throughput while reducing system set-
integrated into the cleaning process. A feed solution is
up requirements.
pumped through the filters’ cartridge and split into a
The first place to install recycling equipment is in the rinse
permeate or filtrate (material retained by the membrane)
water portion of the cleaning system. In sequential tank clean-
and retentate (fluid retained by the membrane). The soil-
ing this is accomplished by using a series of countercurrent
free permeate stream is then recycled back to the parts
cascading rinse tanks with each tank’s water being progres-
washer.
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 FILTER SELECTION
expensive to install.) Today, many kinds of filters are available for ultrafiltration
In addition, it is easier to recycle the detergent solution due to advances in membrane types and the continued evolu-
separately from the rinse water because the equipment used is tion of systems with better temperature and chemical stability.
merely separating soils, not trying to create high-purity water, For example, extremely hydrophilic (water-absorbing and oil-
for which you need activated carbon, deionizing resins or repellent) polymeric membranes have been developed to resist
reverse-osmosis. Treating cleaning solutions can be accom- fouling by free oils, emulsions, and other hydrophobic solutes
plished through one or more of the following procedures: in order to achieve efficient filtration rates over extended peri-
ods.
• Physical filtration—uses gravity or low-pressure pump
Filters can be either symmetric, with fairly uniform pore
cartridges at one to 100 micron levels of filtration to
diameters throughout the membrane, or asymmetric, consist-
remove suspended particulates.
ing of a thin “selective” layer over a thick, porous substructure.
• Microfiltration—uses low-pressure pumps, dead-end, or Membrane selection is critical to the effectiveness of any
cross-flow filter membranes to realize 0.1 to 1.0 micron recycling system. Before deciding on a system, users should
levels of particulate filtration (used to break and remove ask the following questions:

132 The Aqueous Cleaning Handbook Wastewater Treatment and Cleaner Recycling 133
• Surface chemistry—Has the membrane been engi- content of both the recycled bath and the rinse water used.
neered for easy cleaning or to resist fouling by free-float- In a separate system, rinse water must be purified. The
ing and emulsified oils? rinsing recycle systems can be designed to deliver water to a
• Stability—Is it physically and chemically stable toward a level that leaves parts able to meet required cleanliness stan-
broad range of pH and aggressive chemicals? dards.
• Pore size—Has it been designed to ensure complete pas- In addition to particle, micro- and ultrafiltration, these
sage of all cleaner components while sufficiently retain- recycling systems may also use reverse osmosis (RO) in con-
ing the oils? junction with microfiltration in order to protect the filter
membrane. Activated carbon may be used for the removal of
• Temperature tolerance—What is the membrane’s tem-
the majority of organic contaminants. Ion exchange is another
perature tolerance?
type of system that uses specially designed resins to capture
cations and anions such as chlorine, heavy metals, calcium,
While not all aqueous cleaning applications require the use
and magnesium. Since these types of cations and anions may
of membrane-based filtration, their use can be especially help-
be considered hazardous waste, they must be shipped back to
ful in achieving steady conditions, desirable for maintaining
suppliers for regeneration.
quality control in high-production applications. Detergents
must be selected for their compatibility with the specific mem-
brane employed, and vice versa. 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
CLOSING THE LOOP ON AQUEOUS CLEANING AND RINSING be recharged with detergent and when it is spent, mandating a
There are a number of methods for removing contaminants
fresh batch. There are numerous sophisticated analytical
from aqueous-cleaner solutions. These are selected for particu-
chemistry techniques, such as FTIR (Fourier Transform
lar applications based on the size of the contaminants.
Infrared Spectroscopy), HPLC (high pressure liquid chro-
Particulates may be removed using settling tanks, chip bas-
matography), COD (chemical oxygen demand) and TOC (total
kets, media filtration, or canister filters. Oils are collected
organic carbon), for analyzing recycled cleaner. Free
using skimmers and coalescers. Most of the remaining conta-
Alkalinity, a process which measures unreacted builder in the
minants can be removed using micro- and ultrafiltration.
cleaner, can also be used, as well as Total Alkalinity, which
Usually you have separate rinse water recycling and cleaner
measures total alkalinity as well as the alkalinity consumed in
solution recycling. Cleaners are recycled using physical filters,
the cleaning process due to sludge formation or hydrolysis of
oil separators, ultrafiltration, and microfiltration.
animal or vegetable-based oils. Neither Free Alkalinity nor
Microfiltration uses a membrane with pore sizes from 0.1
Total Alkalinity, however, measure the level of surfactants, ren-
to 1.0 microns, while ultrafiltration pore sizes range from
dering them inappropriate in procedures which depend on the
0.0005 to 0.1 microns.
removal of soil.
Ultrafiltration membrane pore sizes are also specified by
Some very simple, yet effective, techniques can be used to
molecular weight cutoffs (MWCOs). Contaminants with a
monitor bath life, including:
diameter greater than the membrane’s MWCO are thus filtered
out. • Conductivity—The measurement of ionic content of the
It is important to keep in mind that both micro- and ultra- cleaning solution using electrodes connected to a con-
filtration are pressure-driven processes. Neither will reject ductivity meter. This is a useful technique for figuring
salts, which can adversely affect its performance and make dis- out when to add more detergent to a cleaning solution
posal necessary. It is therefore important to monitor the salt with high ionic content, such as those based on salts

134 The Aqueous Cleaning Handbook Wastewater Treatment and Cleaner Recycling 135
(potassium hydroxide or sodium metasilicate, for exam- fying or dispersing detergent to remove oils or particulate types
ple). Conductivity will drop as soils react with the salts. of soils, refractometry can be an effective means of measure-
This is not a useful technique for monitoring high emul- ment and control. Foam height is most applicable to cleaners
sifying cleaners that rely on surfactants for a significant based on foaming surfactants that rely on emulsification of
part of the cleaning mechanism. oily soils for their removal. When cleaning with an alkaline
• Refractometry—The indirect measure of the concentra- detergent and the soil is either acidic or neutralizing in charac-
tion of dissolved components which influence the refrac- ter (as most soils are), pH can be used as a control measure.
tive index of a sample of solution using a simple hand-
held refractometer. It can be used to monitor the build TABLE 7A BASIC MONITORING AND CONTROL TECHNIQUE
up of soils and concentration of a solution due to water SELECTION BASED ON TYPE OF DETERGENT USED
evaporation. Empirical observations of cleaning solu- Conductivity Ionic cleaner removing nonionic soil such as a high
tions in use compared with recorded measurements can alkaline cleaner used for degreasing
be used to derive appropriate times to recharge or dis- Refractometry High emulsifying and dispersing cleaner used on
card solutions. mixed particulate and oily soil
• Foam Height—Observation of the foam height of a vol- Foam height High-foaming cleaner used to clean oily soils
ume sample of cleaning solution in a vigorously-agitated, pH decrease Alkaline cleaner used to clean acidic or hydrolyzable
stoppered test tube will show a decrease in foam height soils that react with the cleaner (most soils are acidic
and foam stability with the build up of oils. As foam or hydrolyzable)
height decreases, cleaning solution should be recharged
pH increase Acidic cleaner used to clean an alkaline or neutral soil
or discarded. Observations must be made at the same
temperatures.
ECONOMIC FACTORS
• pH—Measurement of the acidity or alkalinity of a solu-
One must keep in mind that where detergent recycling is con-
tion on a scale of 0–14, expressed as the negative log of
cerned, it is possible to be penny-wise and pound-foolish. It
the hydrogen ion concentration, which is measured
may not be worth risking inadequate, or even uncontrolled,
using electrodes dipped in the solution connected to a
cleaning simply to get every last penny of performance from a
pH meter. Note that pH paper should not be used with
detergent solution.
surfactant-containing cleaners, because they commonly
The cost of installing recycling and reuse equipment and
interfere with accurate readings. A given brand of deter-
procedures must be weighed against the cost of disposal and
gent will have a typical pH. If the soils are acidic, inor-
solution use. The value of the parts being cleaned, the
ganic, or saponifiable natural oils, the pH will drop as
increased risk of cleaning failure with each new part cleaned
the cleaning solution is used up. Typically, as pH drops
and the chance of cleaner exhaustion or soil redeposition must
0.5 pH units, the detergent should be recharged. Then
all be considered.
the solution can be used to exhaustion as it drops one
One question that needs to be asked and answered is:
full pH unit.
Is it cheaper and better to send partially used cleaner to
Each of the above methods has its application, based on drain and make up a fresh batch of cleaner?
the type of detergent used and the soils that need to be
removed. When using an ionic cleaner to remove nonionic With nonhazardous detergents and wastes, probably
soils, for example, conductivity can be used to monitor dilu- cheaper and better to send to drain and make fresh solution.
tion, dragout, and loss of detergent. When using a high-emulsi- With easily treated hazardous wastes, perhaps not. Where reg-

136 The Aqueous Cleaning Handbook Wastewater Treatment and Cleaner Recycling 137
ulatory compliance costs are prohibitive or no drain is avail- It is important to note, however, that manufacturers
able, the answer is, in all probability, better to recycle. already using aqueous-cleaning solutions don’t need a closed-
Another factor to consider is the volume of your cleaning loop system to begin recycling today. In fact, recycling can be
system. In high-volume, high-performance cleaning applica- as simple as making up a large soak tank for continuous use
tions with quality control inspection or low fault-tolerance throughout the manufacturing process, saving time and
parts such as electronic components and optical parts, recy- money merely by recycling wash-tank water through a skim-
cling may well be worth it. But in low-volume, extreme-clean- mer, then recharging with detergent at midweek intervals. This
ing performance applications such as pharmaceutical process will allow you to avoid downtime during draining, refilling,
equipment, medical devices and high-priced, soil-sensitive recharging with detergent, and reheating the tank.
equipment, recycling the detergent may not be.
Also, before considering recycling as an option, an evalua- REFERENCES
tion and determination must be undertaken as to whether the Alkaline Cleaner Recycle Handbook, Membrex, Inc., Fairfield, NJ 1994, p.
EPA needs to be involved, including the completion of a SARA 5.
report of discharge quantities of any listed chemical that is Precision Cleaning, June 1997, article “Closed-Loop Cleaner Recycling by
either in the soil or detergent discharge. Malcolm McLaughlin, p. 17–24.
The following additional parameters must also be fully Personal interview, University of Massachusetts at Lowell, Toxics Use
Reduction Institute.
reviewed: Alkaline Cleaner Recycle Handbook, Membrex, Inc., Fairfield, NJ 1994, p.
• Toxicity—by TCLP (Toxicity Characteristic Leaching 5.
Procedure) Ibid., pp. 4–5.
• Corrosivity—pH below 2 or higher than 12.5 Ibid., pp. 3–5.
Closed-Loop Aqueous Cleaning, University of Massachusetts, Toxics Use
• Ignitability—flash point below 60˚C (140˚F) ignitable Reduction Institute, Lowell, MA, 1995, p. 6.
Ibid, p. 10.
In addition, compressed gases and oxidizers as well as Precision Cleaning, December 1997 issue, article “Wastewater
reactivity of the waste stream should be reviewed to determine Treatment,” p. 50.
if RCRA regulations apply as covered in 40 CFR 261.21-.24, as Precision Cleaning, December 1997 issue, article “Filtration Systems,” p.
38.
well as any applicable state and local discharge regulations.
Precision Cleaning, November 1996, article “Aqueous Cleaning System
Design: Recycling, p. 36–42.
PROVEN TECHNOLOGIES Precision Cleaning, December 1997, article “Sifting Through Filtration
There are numerous suppliers of closed-loop aqueous-cleaning Options,” p. 16–23.
systems designed to increase process efficiency by decreasing Precision Cleaning, October 1996, article “Aqueous Cleaning Technology:
How long is a Cleaning Bath Really Effective?”, p. 21–27.
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- RESOURCES
latory considerations. The benefits of sophisticated closed- www.alconox.com
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 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- prints. It will not readily detect non-hydrophobic
els below 1 microgram per sq. cm. can be detected—are suit- residues. This test is often used for parts washing; it may
able for use in semiconductor, disk drive, and medical device not always be suitable for precision cleaning applica-
applications. The kinds of techniques that are used for this tions.
level of precise cleanliness measurement are: • Atomizer test—A variation of the water-break test, this
• Carbon coulometry requires observing whether a gently sprayed water mist
• Electron spectroscopy for chemical analysis (ESCA) deposits uniformly or whether water repulsion occurs
• Fourier transform infrared (FTIR) (usually due to a hydrophobic soil). The atomizer test is
slightly more sensitive to hydrophobic soils than the
• Gas chromatography/mass spectrophotometry (GC/MS)
water break test. In the water break test the kinetic ener-
• Ion chromatography (IC) gy of the flowing water may overcome a hydrophobic
• Optically stimulated electronic emissions (OSEE) residue where in the atomizer test you may be able to
• Particle counting, scanning electron microscopy (SEM) see the results of a little droplet of water being repelled
• Secondary ion mass spectroscopy (SIMS) by a hydrophobic contaminant.
• Nonvolatile Residue Inspection (NVR)—The NVR test
The following are summaries of these various cleanliness involves extraction of soil from a dirty surface into a sol-
measuring techniques as appropriate to each of the three lev- vent, just as is done with the extraction method above.
els of cleanliness required. The solvent is then evaporated onto a coupon of known
weight and after the solvent is evaporated off any residue
CLEANLINESS DETECTION AT 0.01 GRAMS PER SQ. CM is deposited on the coupon. When the coupon is re-
• Visual inspection—is best used to detect residues of weighed, any increase in weight is recorded as the non-
contrasting color or texture. Good lighting can enhance volatile residue. Many solvents can be used for this pur-
visual inspection, fiber optic lights providing light across pose. It is important to use a solvent that can dissolve
a surface improve detection, and magnification of course the soil being detected. (Isopropyl alcohol, methalyne
improves detection. chloride, acetone and other solvents have been used for
this purpose.)
• Low-power microscope inspection—This is an excel-
lent way to quickly and efficiently verify cleanliness of • Surface Ultraviolet Florescence (UV)—Many organic
residual oils and greases, flux residues, particles and sur- and some inorganic contaminants will fluoresce under
faces. UV light. Shining a UV light on the surface will cause the
residues to easily be seen, particularly in a slightly dark-
• Wiping and visual inspecting—Wiping a surface with a
ened or dark room. The higher the intensity of the light
white wipe will provide a contrasting surface with which
used, the lower the level of contaminants which can be
to detect dark residues (the white glove test).
easily detected. Note, however, that the typical black
• Water-break test—Use running water and let it sheet light found in novelty or specialty gift stores may not be
across the surface. Observe if any breaks in the water strong enough to cause much residue to fluoresce. More
occur due to hydrophobic (water-fearing) residues. (See powerful UV lights available from scientific supply hous-
“The Hydrophobic Surface Film by the Water Break es or industrial suppliers will give far higher levels of
Test,” ASTM Method F 22-65—found at www.astm.org.) detection. The test is performed by shining the light on
The water break test is a fairly crude test which is suit- the surface and observing a fluorescent, typically a yel-
able for detecting films of process oils and heavy finger- low, orange or green, sometimes red, color which glows

142 The Aqueous Cleaning Handbook Measuring Cleanliness 143


under the light and is easily seen. analysis for detergent residues it is advisable to use
• Tape Test—The Tape Test is a simple method for aiding water as the solvent. (The sensitivity of an extraction test
visual inspection and is well suited to determining the depends on the method of trace analysis.)
cleanliness of smooth metal and plastic parts. It involves The types of trace analyses most often used are UV
attaching transparent adhesive tape to the surface being visible spectrophotometry, total organic carbon (TOC)
measured, firmly pressing it down, carefully removing it analysis, high performance liquid chromatography
and then placing it on a sheet of clean white paper. (HPLC), atomic absorption (AA) or inorganic residues,
Comparing the sample with an adjacent piece of white and liquid chromatography (LC). (These techniques are
paper provides a fast, easy way to visually monitor par- discussed separately in this chapter under “Detection
ticulates and sometimes even film residues. below 1 microgram per sq. cm.”)
• Oil Evaporation—For filmy residues, a few drops of
CLEANLINESS DETECTION AT organic solvent can be deposited on the surface and then
0.01 TO .001 GRAMS PER SQ. CM removed via pipette and placed on a watch glass. If any
• Millipore Filter Measurement—The Millipore Test— filmy residues are present, one should observe a charac-
also known as the “patch” test—involves spraying sam- teristic ring of organic-material deposits.
ples of parts with filtered hexane, isopropyl alcohol, or • Oil Soluble Fluorescence—Involves immersing a part
trichlorethylene at pressures of 60 to 80 psi through a in a fluorescent oil soluble penetrant dye and then
1.2-micron filter membrane inside a jet nozzle. The observing under fluorescent light to see if any dye pene-
spray is collected, vacuum-filtered onto a clean filter trates or adheres indicating the presence of oil. This
membrane followed by microscope inspection for any method is outlined in ASTM F601-98 “Standard Practice
particle-per-micron contaminants. (The membrane can for Fluorescent Penetrant Inspection of Metallic Surgical
also be weighed to determine total contaminants in mil- Implants.” Of course cleaning procedures need to be
ligrams.) established to remove the dye after testing.
• Optical Microscopy—High-power compound micro- • Gravimetric Analysis—With small parts of known
scopes can also be used (typically on circuit boards), weight, the amount of excess weight indicated the
however, these are more delicate and more expensive amount of soil present.
than simple, low-power microscopes and generally After cleaning if the part returns to it’s clean weight
require greater operator skill and training. one can conclude that the part is clean. Gravimetric
• Extraction—a particularly useful method for detecting analysis is also very useful as a screening tool in lab
detergent residues, this measurement technique employs cleaning situations where a coupon is weighed before
a solvent-soaked glass filter paper, or high purity swabs soiling, after soiling with an artificial soil, and then
to wipe surfaces. The filter paper or swab is then extract- weighed again after cleaning to derive percent of soil
ed or digested and trace analysis performed on the removed.
extract. This procedure can be quantitative if one wipes • Surface energy—Any hard, flat material has a character-
a known area. istic surface energy. As a result, a deposit of a known vol-
Extraction methods can be highly sensitive to a wide ume of pure liquid (typically deionized water) will form
range of possible soils and residues. The limitations on a droplet of predictable size based on the amount of that
this method, however, is that an appropriate solvent energy. Measuring droplet size will determine surface
must be used to extract any soils. When performing trace cleanliness. Generally, hydrophobic soils create smaller

144 The Aqueous Cleaning Handbook Measuring Cleanliness 145


droplets; hydrophilic soils, larger ones. The surface-ener- now employ ultrasonic cleaning baths as well.
gy test is far more sensitive than the atomizer or water- In-situ particle monitoring (ISPM) provides a tool to
break test and has the advantage of being able to detect observe particle removal behavior in the ultrasonic cleaning
both hydrophilic and hydrophobic soils. The problem bath process at work and in real time, thus providing the abili-
with the surface energy test is it only tests the surface ty to quickly select, adjust, and optimize the cleaning process.
directly underneath the droplet where you are measur- Once the process is optimized, ISPM can be used to monitor
ing. If you have a broad, large surface where measuring bath performance, and monitor filtration recycle performance.
one little area of it would be representative of the level of ISPM measures particle counts directly during the cleaning
the cleaning that went on the entire surface, this can be process in both ultrasonic rinse and wash baths.
an excellent and highly sensitive method. If you have a
part that has lots of cracks and crevices and holes, the AN EXAMPLE OF HOW IN SITU PARTICLE MONITORING WORKS
surfaces that are accessible for you to place a droplet of In work done by John Hunt (Pacific Scientific Instruments,
liquid to measure surface energy may not be representa- Grants Pass, OR) to optimize a choice or concentration of
tive of the types of soils that may be hidden in any cleaning agent, a known amount/type of particle contamina-
cracks, crevices, or blind holes. (For a fuller description tion was deposited on glass slide test coupons. Several clean-
of this measurement technique see “More on water-drop ing agents were tested for their effectiveness in removing the
surface energy test,” which follows this section.) contamination by monitoring the rate of particle removal in
• Contact angle measurement—A variation of surface the bath by recycling the bath through a filtration loop and
energy testing is contact-angle, defined simply as the detecting particles just before filtration.. For each concentra-
relationship of certain forces when a liquid stabilizes on tion and each detergent, various particle sizes were observed
a part’s surface. This method can be used to determine in the bath at the addition of increased concentration of deter-
cleanliness since the properties of various contaminated gent, and then again when the soiled glass plate is added to
surfaces are reflected by different contact angles. the bath. When the soiled plate is added, a number of parti-
Contact-angle measurement is especially suited to manu- cles per ml per minute is determined by integrating the area
facturing operations such as wire bonding on PCBs or under the particle size counting curves for a given length of
the application of thin films on quartz glass which time for each particle size monitored at each concentration of
require a cleanliness test that is nondestructive. Vapors each detergent. If you are trying to optimize detergent con-
from the process itself, such as vacuum or diffusion centrations, be sure to allow any bubble interference to reach
pump oils, various process chemicals, or even human baseline after addition of increased concentration of detergent
perspiration, are all contaminants whose presence can prior to placing the soiled plate in the bath. By observing the
be detected by changes in the contact angle. (For a fuller shape of the particle counting curve, you will typically see an
description of this measurement technique see “More on initial spike of particles coming off the plate when you add the
Contact Angle Measurement Methods,” which follows soiled plate and then see particles continue to come off over
this section.) time. Typically after 10 or 15 minutes no more particles are
• In-situ Particle Counting (ISPM)—Part cleanliness observed. This information can be used to optimize cleaning
becomes critically important as mechanical, optical, and times in addition to cleaner concentrations. By the same
electronic parts shrink in size and formerly inconsequen- token, during cleaning, real-time particle counting could be
tial particles grow in comparison. High-technology used to determine when to take the parts out of the bath by
cleaning techniques, such as ultrasonic bath cleaning are observing when the particle counts had dropped back to base-
widely used. Today’s precision industrial applications line.

146 The Aqueous Cleaning Handbook Measuring Cleanliness 147


MORE ON WATER DROP SURFACE ENERGY TEST droplet and its measurement.
Surface energy can be indirectly detected by measuring the • Use medical-grade, ultra-purified deionized water from a
size of a droplet of known volume sitting on a surface. Using a laboratory supply house in order to have a consistent
volumetric pipette a drop of typically 0.2 ml of water is placed measuring liquid. This will limit the number of measure-
carefully onto a surface being investigated. The droplet size is ment variables.
measured with a micrometer. If the droplet is circular the area • Use test liquids of larger surface tension than the solid’s
is determined by the pi r squared method. Note that any surface energy in order to obtain easy-to-read results.
machining or scoring will distort droplets, it may be easier to • Neutralize the effects of static charges on substrates.
use a length times width method of estimating droplets – do Substrates that are electrostatically charged can skew
not vary area calculations within a set of measurements. contact angle readings up to 5 degrees.
Typically a surface with a hydrophobic oily residue film will
• Accurately control liquid droplets so that they are repeat-
repel the water and cause the droplets to be smaller than are
edly deposited onto the sample. Gently move the sample
observed on the clean surface.
to the liquid droplet formed at the end of the syringe/dis-
This method works well on glass and metal surfaces. It is
penser in order to minimize gravitational effects.
better at detecting films on smooth surfaces rather than par-
ticulates. If the surface is scratched during cleaning, the • In the case of very high contact angles, you may find it
droplet size will become smaller causing false readings if the difficult to adhere the droplet from the needle to the
test is used as a before and after test. If a volumentric pipette solid sample. Use a Teflon-coated needle of a higher
is not available, then using an eyedropper to deposit drops and gauge (smaller inner diameter).
using a scale sensitive to 0.001 grams, the ratio of droplet • In case of very low contact angles, use the highest possi-
weight to area can be used to detect changes in surface energy. ble needle gauge (smallest inner diameter needle) for
Again, a rise in this ratio indicated going from a dirty to a controlling very small droplet volumes onto the sample.
clean surface. It is useful to work with some known cleaned
surface to observe droplet size behavior and known soiled sur- MORE ON CONTACT-ANGLE MEASURING METHODS
faces to confirm that the residue will give the observed Accepted methods of measuring contact angles to determine
changes. surface characteristics include the inverted bubble, Wilhelmy
As with other cleanliness verification techniques, special Plate, and sessile drop techniques. The latter is the most wide-
tips for contact angle measurement, if practiced, will increase ly practiced quality control technique, as it is relatively quick
the repeatability and validity of the measurement results. The and requires minimal investment in time and financial
following tips from Precision Cleaning magazine, (Oct. 97 p. resources.
23) were helpfully compiled: In the sessile drop technique, the specimen to be measured
• Use gloves when handling the samples to be measured. is loaded onto a specimen holder. A liquid droplet 3 to 4 mm
Organics, such as finger oils, cosmetics, and other conta- in diameter is carefully deposited onto the substrate surface. A
minants, will skew the contact angle results. tangent line is drawn at the three-phase interface point in
• Note the nature of the droplet after applying it to the sur- order to determine the contact angle. Alternately, a line is
face. Wait until the droplet has ceased its advancement drawn from the three-phase interface point through the apex.
and no more change in lateral movement has occurred. This angle turns out to be equal to 1/2 of the tangent angle and
Measure this time interval, making sure that you wait is reproducible by different operators.
this period of time after every measurement. Retain con- Several “real world” examples will help illustrate what can
sistent time intervals between the placement of the be learned from the use of the contact angle measuring tech-

148 The Aqueous Cleaning Handbook Measuring Cleanliness 149


nique to determine the existence of impurities on a surface. • Fourier Transform Infrared Spectroscopy (FTIR)—
LCD (Liquid Crystal Display) panel surfaces contaminated FTIR spectroscopy is used for structural characterization
with organic matter will be less accepting of a variety of films, of organic and inorganic molecules in solids, liquids,
such as metals and protective layers, resulting in poor manu- gases, and on surfaces. Spectrometers record the interac-
facturing yields. Sources of such contaminants include the tion of light energy in the form of infrared radiation with
vapor of process materials, chemicals, and human perspira- an experimental sample, measuring the frequencies at
tion. Very thin organic contaminants several monolayers in which the sample absorbs the radiation and the intensi-
thickness (greater than 10 angstroms) can be evaluated using ties of the absorption. After using an extraction method
the contact angle technique. or by using a surface scanning machine, by comparing
In fact, it is generally agreed that the wetting behavior the unknown spectra to the standard frequency at which
involves only the last layer or two atoms on either side of a specific molecules are known to absorb light, the sam-
solid’s interface. The water contact angle correlates the “clean- ple’s chemical makeup as well as it’s concentration can
liness” of the surface to the adhesion of the copper deposited be determined.
onto the surface of the LCD. • Gas Chromatography/Mass Spectrophotometry
Water contact angles can be used in various processes to (GC/MS)—GC/MS is used to identify surface contamina-
determine contamination levels, predict cleanliness and adhe- tion by extracting contaminants into a solvent and ana-
sive bond strengths, and monitor cleaning operations. lyzing them. Organic compounds are then separated via
Whether you are checking the moisture effects on silicon GC and are then identified, based on molecular weight,
wafers or LCD quartz panel glass metal adhesion, all that is by MS.
needed is an understanding of the basic theory involved and • Ion Chromatography (IC)—Ion Chromotography is a
proper measurement techniques. form of liquid chromatography of aqueous samples used
to determine ionic contamination on critical compo-
DETECTION BELOW 1 MICROGRAM PER SQ. CM nents. Columns containing ion- exchange resins are
• Carbon Coulometry—The technique employs in-situ used to separate the atomic or molecular sample ions
direct oxidation of surface carbon to carbon dioxide based on their partition ratios as they pass through the
(CO2), followed by automatic CO2 coulometric detec- columns. It is the only technique that can provide quan-
tion. (For a fuller description of additional in-situ moni- titative analysis of anions at the ppb level of an extract
toring techniques, see the “In-Situ Particulate that has been swabbed or wiped from a surface and
Monitoring” section of this chapter.) extracted into solution for analysis.
• Electron Spectroscopy for Chemical Analysis • Optically Stimulated Electronic Emissions—When
(ESCA)—ESCA is an extremely surface-sensitive tech- high-energy UV light hits a surface, electrons are emit-
nique, which employs the photoelectric effect, for the ted, and the reflected current can be measured. A clean
detection of elements and determination of elemental surface will give the highest return current, so any drop
composition. Electrons are ejected from a solid surface in current represents contamination. This method is
by irradiating the surface with an x-ray monobeam. The good for determining low levels of contamination (both
emitted photoelectrons have a kinetic energy equal to ionic and nonionic). However, while optically stimulated
the x-ray less the binding energy of the electron. The electronic emissions can detect contamination, it cannot
measured kinetic energy of the electrons can therefore identify it.
be converted to binding energies, enabling element iden-
tification.

150 The Aqueous Cleaning Handbook Measuring Cleanliness 151


• Scanning Electron Microscopy (SEM)—By scanning REFERENCES
high energy electrons across a specimen, SEM allows the Alconox Cleaning Solutions newsletter, Vol. 1, Number 1 article “How
study of both morphology and composition of biological Clean is Clean?”
and physical materials. When high energy primary elec- ASTM. F-2265, The American Society of Testing Materials.
trons impact the specimen they are deflected or scat- Carol LeBlanc; Turi, Massachusetts, Toxics Use Reduction Program for
tered. Those that are deflected at an angle greater than The 22nd Mr. Clean Conference, Oct. 96.
Carrasco, Armando, “Moisture Induced Stress Sensitivity Reduction of
90o can reenter the vacuum above the specimen and
FSRAM 52 Lead PLCC’s,” 1996 Surface Mount International
make up the backscatter signal. The proportion of pri- Conference, p. 607–611.
mary electrons collected as backscatter electrons (bse) Cleaning Printed Wiring Assemblies in Today’s Environment, p. 94
increases as a function of the atomic number of the sam- “Testing for cleanliness,” and p. 197 “Cleanliness Verification”
ple specimen, thereby portraying its chemistry. Forward Cleantech “Cleanliness Verification,” CleanTech Vol 3, No. 3, S1-S12
(March 2001)
scattering primary electrons, those that are deflected at
Djennas, Frank, Prack, Edward, and Matsuda, Yushi, , “Investigation of
an angle of 90o or less, travel through the specimen Plasma Effects on Plastic Packages Delamination and Cracking.”
while loosing energy. The atomic electrons gain this lost IEEE Trans. CHMT, 16. 1993, p. 91–924, edited by Les Hymes.
energy, allowing them to escape from their atoms. Those G. Gould and E.A. Irene, “An Inside Study of Aqueous HF Treatment of
that are very close to the surface (within the escape Silicon by Contact Angle Measurement and Ellipsometry,” Journal of
The Electrochemical Society, 135 (1988), p. 1535–39.
depth) may have sufficient energy to escape from the
Geosling, C and Koran, J “Contamination Control and Analytical
sample surface back into the vacuum as secondary elec- Techniques,” in Ch 3.2 Handbook for Critical Cleaning, Kanegsberg, B.
trons (SE). Because an incline surface exposes a larger Ed., CRC Press Publishers, Boca Raton, 2001, 431-448
area to the electron beam, thereby impacting more elec- Good, R.J. and Stromberg. R.R., Ed., “Colloid and Surface Science,”
trons within the escape depth, production of secondary Plenum, Volume 11, New York, 1979.
Hawkins, George, Ganesan. Gans, Lewis, Gary and Berg, Howard. “The
electrons is attributable to the specimen being at high
PBGA: A Systematic Study of Moisture Resistance,” The ISHM
incident angles with the electron probe. The resultant se Journal of Microcircuits & Electronic Packaging, 18, No. 2, 122–132,
image thus reflects the surface topography of the speci- 1995.
men. Herard, Laurent, “Surface Treatment for Plastic Ball Grid Array
Assembly and Its Effect on Package Reliability,” ISHM Workshop on
• Secondary Ion Mass Spectroscopy (SIMS)—SIMS is Flip Chip and Ball Grid Arrays, Berlin, Germany, November 13–15,
an extremely sensitive surface analytical technique used 1995, p. 1.
for chemical determination of surface constituents, both Japan, Kuman- Gypta, “Comparative Studies of the Contact Angle as a
elemental and molecular, as well as ppb concentrations Measure of Adherence for Photoresist,” Thin Solid Films, 75 (1981), p.
319–329.
of impurities in semiconductors and metals. The materi-
Mittal, K.L., Ed., “Contact Angle, Wettability and Adhesion,” VSP,
al under investigation is bombarded with primary ions Volume 1, the Netherlands. 1993.
which, upon impact, cause secondary ions to be ejected Precision Cleaning, October 1997 article “Contact Angles Measure
from the sample’s surface. These secondary ions can be Component Cleanliness,” p. 21–24.
identified by their mass, which is determined by measur- Toshiaki Matsunaga, J., “Relationship Between Surface Energy and
Surface Contamination,” Physical Chemistry, 71 (1967), p. 4176.
ing their travel time from surface to analyzer.
Trent Thompson, “Moisture Absorption and Autoclave Performance
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152 The Aqueous Cleaning Handbook 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- these cycles are relevant to aqueous-cleaning ingredients.
ardous, polluting process. But by the same token, industrial However, all of these cycles involve far more chemical trans-
cleaning can also involve the use of an aqueous cleaner that formations and slower processes with longer residence times
has no hazardous ingredients used to clean the same haz- in various long-term forms. For example, one step in the car-
ardous soils whereby the cleaning solutions are treated prior bon cycle involves extensive time spent as geological carbon-
to discharge—resulting in a clean and relatively safer process. ates—in the same way nitrogen stays for extensive periods as
Improvement in safety can be achieved by eliminating the nitrogen in the air. Oxygen is also tied as geological carbon-
source of the hazardous soil in the process. Taking this a step ates. These elements simply do not cycle as rapidly, in a puri-
further one can effect a reduced waste process by incorporat- fying sense, as does water.
ing some degree of soil recycling, cleaning solution recycling,
and rinse water recycling. It is possible to design a so-called ENVIRONMENTAL ISSUES IN AQUEOUS CLEANING
“zero-discharge” system with no fluid effluent, limited volatile The environmental issues involved in aqueous cleaning are
effluent and reduced solid waste by recycling cleaning and mostly associated with the ingredients and their ultimate dis-
rinsing solutions with filters. In order to move toward a clean, charge into the environment. Taking a larger view of the envi-
safe and sustainable process, however, one would need to ronmental issues concerning aqueous-cleaning processes it is
eliminate the use of whatever caused the hazardous soil and reasonable to consider the energy and resources used in mak-
replace it with a nonhazardous biodegradable soil. Then, after ing the cleaner, and the energy and resources consumed in
the water used in the cleaning and rinsing process has been using the cleaner.
recycled sufficiently to create sustainable energy consumption There are several important factors concerning discharge
rates, the now nonhazardous soil in the effluent would not cre- of spent cleaning solutions into the environment: biodegrad-
ate a hazard in the environment. Any water released could ability, aquatic toxicity, and eutrophication potential.
safely be incorporated into the natural water cycle (surface Historically, early detergent formulations contained poorly
water to evaporated water to clouds to rain, and finally, once biodegradable surfactants that were capable of causing foam-
again returning to surface water). ing in surface lakes and rivers when the spent solutions were
Most nonaqueous chemical cleaning methods generally discharged to drain. Today, all modern detergent formulations
have much greater difficulty in achieving clean, safe, sustain- use biodegradable surfactants that do no buildup and persist
able processes. Many nonaqueous cleaners are themselves in the environment and cause surface water-foaming prob-
health hazards, water pollutants, or air pollutants. Certainly lems.
not all nonaqueous cleaners are hazardous and/or pollutants, Aquatic toxicity can come from very high or very low pH
but most do not have a basic natural process such as the or the toxicity of the ingredients. Where extreme pH cleaning
water-cycle to purify and recycle key ingredients. (Of course, is required, it is advisable to neutralize or discharge spent
this is an oversimplification; viewed from the standpoint of a solutions in small enough quantities to avoid problems. The
long enough time scale, almost anything can be considered to sur-factants in aqueous cleaners can have aquatic toxicity
have a sustainable natural cycle of synthesis and decay. We are associated with them. The use of biodegradable surfactants
considering here natural processes that can contribute to sus- and the discharge of limited quantities of cleaning solutions
tainable processes achievable in the course of human life- generally results in no toxic concentration of surfactants in
times.) surface water. Older more highly toxic surfactants are no
One might argue that the carbon cycle, the nitrogen cycle, longer widely used in aqueous-cleaner formulations.
the oxygen cycle and many other elemental cycles also become Eutrophication involves cleaners that contain phosphates.
involved in nonaqueous cleaning processes. In fact, many of Phosphorus is an essential nutrient for algae. When significant

156 The Aqueous Cleaning Handbook Environmental Health and Safety Considerations 157
amounts of phosphorus are discharged into surface water, it cleaners may contain volatile solvents that require special ven-
can result in vigorously growing algae blooms. The algae die tilation and possibly even flammability controls.
and settle to the bottom of the water causing more rapid than While it is relatively unusual for an aqueous cleaner to
normal filling in of lakes and ponds with silt and organic mat- contain any carcinogenic ingredients, a review of the cleaner’s
ter. Although eutrophication is a normal, natural process, the material safety data sheet should disclose any long-term
acceleration of this process by phosphates is undesirable. The chronic exposure concerns relating to carcinogenicity.
main source of phosphorous to surface waters is agricultural Physical safety issues with aqueous cleaners are generally
run-off from farming. There are no national regulations concern storage and handling to avoid any hazardous reac-
restricting the use of phosphates in cleaners, however many tions with other industrial chemicals. Good industrial practice
states and municipalities have enacted legislation that restricts usually involves storing acid and alkaline chemicals separately
the use of phosphates in household cleaners. There are cur- to avoid any reactions between them and aqueous cleaners in
rently no restrictions on the use of phosphate containing the event of accidental spills. Some aqueous cleaners contain
cleaners in industrial cleaning applications. bleaches or other oxidizing agents that should be stored away
from reactive chemicals that might undergo hazardous oxida-
SAFETY ISSUES IN AQUEOUS CLEANING tion reactions. As previously mentioned, most completely
Worker safety issues with aqueous cleaners can involve skin aqueous cleaners are usually not flammable. However, some
exposure, eye exposure, ingestion, inhalation, and chronic sys- aqueous cleaners can contain ingredients that can create haz-
temic exposure. Consult the label and material safety data ardous chemicals when burned. (It is considered good practice
sheet on the cleaner for warnings and safety precautions. to wear respiratory protection when fighting any fire involving
When cleaning by hand, it is always good practice to wear industrial chemicals.)
protective gloves. Even the mildest cleaners can sometimes
cause “dishpan-hand” skin irritation. Gloves also afford a PRACTICAL REGULATORY REVIEW
degree of comfort when working manually with hot solutions. In today’s manufacturing environments, it is realistic to try to
In fact, many highly acidic or alkaline cleaners require the use achieve safe, clean, and reduced waste cleaning processes—
of chemical-resistant gloves for worker safety. and to continually strive toward achieving ultimately sustain-
Eye exposure is also a concern with many aqueous clean- able processes. At the very least, processes that comply with
ers. Eye tissue is particularly prone to attack by chemically current environmental and health safety regulations should be
active aqueous solutions. Accordingly, it is also considered used.
good industrial practice to wear safety glasses or other eye The first step in evaluating the environmental health and
protection when working with aqueous-cleaning solutions. safety of an aqueous cleaner is to secure the material safety
Particularly hazardous aqueous cleaners should have warn- data sheet and technical bulletins for the cleaners you plan to
ings and recommended eye protection on the label. test or use, and to assemble as much information as you can
In addition, inhalation hazards can exist with some aque- about the soils you will be removing. A review of this informa-
ous cleaners. Because aqueous cleaners generally do not have tion should disclose important environmental and health haz-
volatile solvent ingredients, it is somewhat unusual to find the ards and regulatory issues.
need for respiratory protection with such cleaners. However, it When performing an initial review of regulatory issues for
is considered good industrial practice to have some respirato- an aqueous cleaner, it is important to consider OSHA
ry protection when working with sprays and mists in open- (Occupational Safety and Health Administration) regulations,
spray cleaning. Any special ventilation required should be NPDES (National Pollutant Discharge Elimination System)
noted on the material safety data sheet. Some semiaqueous discharge permits, DEP (Department of Environmental

158 The Aqueous Cleaning Handbook 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

Glossary of
Key Concerns Articles Cleaned/Soil Removed Cleaning Method Detergent
Healthcare Surgical, anaesthetic, and examining instruments Manual, Ultrasonic, Soak ALCONOX, LIQUI-NOX
Effective preparation for and equipment. Catheters and tubes. Machine washer, sani-sterilizer ALCOJET, LUMINOX, CITRAJET
sterilization, longer instru-
ment life. Minimize cross- Difficult proteinaceous soils, blood and other Manual, Ultrasonic, Soak TERG-A-ZYME
contamination. Reduce 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. Manual, Ultrasonic, Soak, C-I-P* TERG-A-ZYME 483—the warning letter threaten close from FDA.
Laboratory
Reproducible results, no
Glass, metal, plastic labware, ceramics, tissue
culture, porcelain, clean rooms, animal cages,
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
interfering residues,
extending equipment life.
bioreactors, tubing, benches, safety equipment. washer-sterilizer, cage-washers DET-O-JET, CITRAJET 7, typically below a pH of 5.5. Acid cleaners contain acids and often
Keep laboratory accredita-
tion. Laboratory safety.
Tubes, reusable pipets.
Water and environmental sampling. Phosphate-
Siphon-type washer-rinsers
Manual, Ultrasonic, Soak, C-I-P*
ALCOTABS
LIQUI-NOX, CITRANOX
other cleaning ingredients such as surfactants. Acid cleaners are
sensitive labware. EPA procedures. Machine washer, labware washer DETERGENT 8,, CITRAJET able to clean using the cleaning mechanism of acid solubalization
Radioactive equipment/contaminants. Manual, Ultrasonic, Soak, C-I-P* ALCONOX (see other definitions) where an acid reacts with a soil molecule to
Stopcock grease.
Trace metals, metal oxides, scale.
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
Proteinaceous soils, bio-wastes, tissue, blood
and other body fluids, fermentation residues.
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

Parts washers
gent contains anionic surfactants. Anionic surfactants can be and
ALCOJET, DET-O-JET, CITRAJET
usually are emulsifiers (see other definitions) and dispersants(see
Food and Dairy Stainless steel, food-contact equipment. Manual, Ultrasonic, Soak, C-I-P* ALCONOX, LIQUI-NOX
Avoid interfering residues Machine wash, pressure washers ALCOJET, DET-O-JET, CITRAJET
other definitions). Typical anionic surfactants include organic sul-
on food-contact equip-
ment. Oxides, scale, trace metals, salts, milkstone. Manual, Ultrasonic, Soak, C-I-P* CITRANOX fates, sulfonates and carboxylates. The most common anionic sur-
Machine wash, pressure washers
Manual, Ultrasonic, Soak, C-I-P*
CITRAJET
factant is sodium dodecylbenzene sulfonate.
Filter membranes. Proteinaceous soils. 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 HPLC—high performance liquid chromatography.
alkalinity; buffers a cleaner to maintain alkalinity; emulsifies oils; Hydrolyze—to break a molecule apart using acid (H+) and hydroxyl
disperses particulates; inhibits redeposition of soils; breaks up ions (OH -) from water (H 2O). This occurs when a fat or oil is
clumps of particles by deflocculation; saponifies soils; provides cor- hydrolyzed to make soap as in saponification (see other definitions)
rosion inhibition; and improve the handling, flowing, and storage or when an enzyme breaks down a protein.
characteristics of the cleaner. A typical builder is sodium polyphos- IC—ion chromatography.
phate.
ICH—International Conference on Harmonization.
CFR—code of Federal regulations.
Ion-free cleaner—a cleaner that has no metal ion ingredients.
cGMP—current good manufacturing practice. Typically an ion-free cleaner will contain nonionic surfactants and
Chelating Agent—a cleaner ingredient that is an chemical with at other ingredients that are not metallic salts. An ion-free cleaner
least 2 available sites on the molecule to bind with metal ions in a does not contain sodium or other metal salts.
water based solution to form a ring compound with metal. Typical IQ—installation qualification.
examples of chelating agents include sodium polyphosphates and
ethylene diamine tetra acetic acid (EDTA). Many chelating agents LOD—limit of detection (signal to noise S/N = 3)
are also sequestering agents (see other definitions). LOQ—limit of quantitation (signal to noise S/N = 10)
CIP—clean in place. Micelle—is a sub-microscopic aggregate of molecules. In the context
Cleaner—a chemical or blend of chemicals designed to clean. These of cleaners these molecules are surfactants usually arranged in
may be solvents, acids, bases, detergents, and/or water based sphere or rod shapes with the hydrophilic end of the surfactants
blends. facing outwards into the water solution with the hydrophobic ends
of the molecules facing toward the inside of the aggregate. Micelles
Degreaser—a cleaner that is designed to remove oils and greases. are able to hold hydrophobic oil molecules inside them and create
These are typically heavy duty cleaners that are designed to remove stable emulsions.
gross amounts of oil and grease leaving a visually clean surface
rather than light duty fine cleaners that are designed to remove Neutral cleaner—a cleaner that has a pH near 7, typically in the
lower or trace levels of oils that leave a measurably or analytically range of 5.5 to 8.5. These cleaners tend to rely more on emulsifying
clean surface. Most degreasers are either high alkaline aqueous and dissolving rather than aggressive chemical attack on soils that
cleaners or solvent based cleaners. are possible with acid or alkaline cleaners.
Detergent—a blend of ingredients intended for cleaning that include Nonionic cleaner—a cleaner that contains nonionic surfactants. The
at least a surfactant (see other definitions) to give at least emulsify- term does not mean an ion-free cleaner. A nonionic cleaner may
ing or dispersing and a builder (see other definitions) to inhibit easily contain nonionic surfactants blended with many ionic
water hardness precipitation from calcium and magnesium salts. In builders that are sodium salts or other metal ion salts. (see ion-free
some industry usage, the word detergent is used when the word cleaner).
surfactant is meant. Nonionic surfactant—a cleaner ingredient that is a surface active
Dispersant—a cleaner ingredient that reacts with water insoluble agent(see other definitions) that has a no charge on the organic
particulates to overcome electrostatic attraction by the particulate portion of the molecule. The charge on the surfactant determines
to a hard surface to create a liquid solid mixture in the form of a the charge of the cleaner or detergent. An nonionic detergent con-
suspension. A typical dispersant is sodium polyphosphate. tains nonionic surfactants. A nonionic detergent is not necessarily
ion free (see other definitions). A nonionic detergent may contain
Dissolve—a cleaning mechanism that relies on a cleaning fluid to be many ionic salts, just the surfactant is not ionic and does not have
able to form a stable mixture with individual soil molecules. In an electrical charge. Nonionic surfactants can be and usually are
aqueous cleaners, one of the cleaning mechanisms is for the water emulsifiers (see other definitions) and dispersants (see other defini-
to dissolve water soluble soils. tions). Typical nonionic surfactants include organic ethoxylates.
Emulsifier—a cleaner ingredient that lowers the interfacial tension The most common anionic surfactants are alcohol ethoxylates and
between immiscible liquids such as oil and water thereby allowing alkylphenol ethoxylates.
them to mix. A typical mechanism for emulsifying is for the emulsi- OQ—operational qualification.
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- pH—a measure of how acidic or basic a solution is defined as the
fier is in contact with the water and the entire surrounded droplet inverse log of the hydrogen ion concentration in water. In practical
or micelle is dissolved in the water. Emulsifiers are surfactants (see terms, pH 7 is neutral, below 7 is acidic and above 7 is basic or
other definitions). alkaline.
Excipients—fillers, non-active pharmaceutical ingredients. ppb—parts per billion (ug/liter, microgram/liter).
GC—gas chromatography ppm—parts per million (mg/liter, milligram/liter).

166 The Aqueous Cleaning Handbook 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, 153 134, 138-139, 151, 153, 155-
160, 165-166, 168
Acid cleaners, 44, 46, 84, 165
Aqueous cleaner, iii, vii, ix-x, 1-2,
Acrylic, 86, 91 4, 6-9, 13-16, 19-20, 27, 41, 46,
Activated carbon, 130-132, 135 48-49 51, 61-62, 67-68, 87-91,
Additives, 9, 12, 15-16, 75 93, 95, 127, 155-160, 165-166,
ADI carryover, 123 168
Aggressive, 22-23, 38-39, 42, 46- ASTM, 142, 145, 153
47, 56, 90, 134-135, 167 Atomic absorption (AA), 145
Agitation, 13, 17, 19-20, 22, 23, Atomizer, 141, 143, 146
28, 30-31, 34, 38, 39, 43, 52, 54, Automatic syphon washing, 81
55, 56, 57, 62, 68, 77, 80, 92,
97, 101, 103, 108, 116, 171-177
Air knife, 26, 59, 107, 174
B
Batch cleaning, 35, 78
Air pollution, 52
Bath dumping, 46
Air/solution interface, 20, 28, 80
Bath life, 14, 34, 37, 130, 135,
Alkaline, vii, 11-13, 14, 16-18, 37, 172
44-46, 56, 66, 68-69, 80, 82-85,
89, 90-94, 107, 137, 139, 158, Bench-scale, 54, 57-60, 63
159, 163, 165-167, 173, 175 Bench-scale testing, 57-60
Alkaline cleaner, 17, 46, 165 Bioburden, 122, 124, 165
Alkaline salt builders, 11 Biodegradable, 14, 45, 48, 156-
Aluminum, 34, 39, 42, 44, 60, 66, 157
78, 88, 91, 107, 110, 164 Biotechnology, 78, 128
Aluminum foil, 110 Blender, 71
Amphoteric surfactant, 10 Blood, 65-66, 78, 80, 83, 164
Analytical method, 119-120, 125- Blood-born pathogens, 66
126 Blow-drying, 26
Anion, 135, 151 BOD, 129, 131, 162
Anionic surfactant, 9-10, 125, Body fluids, 65-66, 78, 80, 164
165, 167 Builder, vii, 1, 9, 11-12, 14, 135,
Anodized part, 88 165-167
Anti-redeposition, 9, 15, 20
Aquatic toxicity, 157 C
Aqueous, iii, vii-x, 1-2, 4-9, 13- Calcium, 6, 11-13, 15, 24, 32,
16, 18-20, 23-25, 27, 31, 39, 41- 135, 166, 168, 174
44, 46, 48-49, 51, 61-62, 65, 67- Carbon, 3-4, 86, 121, 124-126,

178 The Aqueous Cleaning Handbook Appendix 179


130-132, 135, 142, 150 Cleaning validation, iv, 67, 78, D Electronics, 24, 39, 44, 84-85, 87,
Carbon coulometry, 142, 150 95, 117, 119, 120, 124-125, 127- Deflocculation, 13-14, 166 164
Carcinogens, 82 128 Electrostatic repulsion, 71
Defluxing, 87
Cationic surfactants, 10 Clean-in-place, 22, 28-29, 36, 44, Emulsification, 13, 137
57, 67-68, 71, 80, 81-82, 91-92, Deionized water, 23-24, 30, 32,
Cavitation, 56-57, 105-106, 116 54, 58, 82, 98, 104, 106-107, Emulsified oils, 15, 129, 134
94, 114-115, 164
Centrifugal drying, 26 145, 149, 171-174 Emulsifier, vii, 1, 9, 11, 13-14,
Cleanroom, 24, 88 85, 165-169
Ceramic, 44, 60, 80, 84-85, 88, Detection limit, 123
Closed-loop, 18, 131, 132, 138, Endoscopes, 66
90-91, 164 139 Detergency, 2, 15-17, 44, 52, 69
Certificates of Analysis, 21, 127 Detergent concentration, 21, 34, Endotoxin, 68, 79, 122, 124
COD, 129, 135, 162
CFC(s), v, vii, 2-5, 8, 44, 85, 87, 37, 38, 61, 147 Environmental and water test-
Computer parts, 88 ing, 82
162 Detergent solution, 13, 28, 37-38,
Concentrated cleaner, 16 68, 80, 98-100, 105, 107, 116, Environmental considerations,
Chamber flexibility, 73
Concentration, vi, ix, 12-14, 16, 132-133, 137 43, 48
Change control/maintenance, 21, 31, 33-34, 37-39, 42, 46, 58,
119 Dipole moment, 6-7, 85 Enzymatic detection, 121
61-62, 70-71, 79, 90, 97, 108-
Chelating, 9, 11-12, 15, 42, 85, 109, 111, 122, 133, 136, 147, Disinfectant, 10, 103 Enzymatic hydrolyzing, 55
90, 93, 166, 168 151-152, 157, 167, 172, 177 Dispersant, 9-10, 43, 92, 165-167, Enzyme, 15, 44, 65-66, 68, 80,
Chelating agent, 9, 11-12, 15, 42, Concentration gradient dissolv- 169 84, 94, 114, 125, 163, 167, 175
85, 90, 93, 166, 168 ing, 58 Dispersing, 13-14, 17, 33, 35, 42, EPA Priority Pollutants, 45, 48
Chemical drying, 25 Conductive residue, 24, 84 56, 94, 137, 166 Equipment "blanks", 83
Chlorocarbon, 3 Conductivity, 37-38, 72, 97, 111, Displacement, 25, 58 EU, 67, 125
Chlorofluorocarbon, v, 3-4 121, 125, 135-137 Disposable, 45, 48, 67, 78, 79 Eutrophication, 157, 158
Circuit board cleaning, 24 Contact-angle, 54, 146, 149 Disposal, 15, 41, 52, 79, 103, 129- Evaluation method, 51, 54
Circulation system, 36 Contaminant, 6, 15, 23, 52, 83, 130, 134, 137 Evaporation, 3, 24, 25, 33, 116,
Clean Air Act Amendment, iv, v, 84, 85, 86, 93, 99, 105, 129, Dissolved inorganic solids, 129 130, 136, 141, 145
8, 45, 48 130, 131, 132, 134, 135, 143, Dissolved organics, 129 Evaporators, 130
144, 146, 148, 150, 151 Dissolving, 1, 6, 15, 17, 22, 55,
Cleaner concentration, 12, 34, Extenders, 16
71, 147 Contaminant dispersants, 15 167-168 Extraction, 141, 143-145, 151
Cleaner recycling, iv, 129, 131, Controlled foaming, 56 Distilled water, 6, 23-24, 32, 81-
139 Corrosion, 9, 15, 17, 23, 24, 33, 82, 98, 104
35, 38, 39, 60, 65, 71, 84, 86, Drying, vi, 19, 24-29, 31, 33, 39,
F
Cleaner type, iv, 33, 161, 163 FDA, 67-68, 73, 121, 125, 128,
88-89, 93, 109, 166 51-52, 54, 58-59, 61, 75, 80-81,
Cleaning efficiency, 43, 69 164-165
Corrosion inhibiting agents, 15 88-89, 97-98, 100, 102, 105,
Cleaning method, 20, 22-23, 27, 107, 112-114, 116, 124, 174, Ferrous, 42
31-35, 41, 45, 51, 54, 57, 59, 61, Corrosion inhibition, 9, 38, 166
177 Filler, 16, 45, 46, 68, 166
63, 78-80, 156, 163 Corrosion inhibitor, 15, 24, 39,
71, 88 Drying method, 19, 24, 33, 51, Filter, iv, 26, 36, 67, 75, 78, 84,
Cleaning performance, ix-x, 8, 54, 58, 59 88, 94, 114, 122, 129, 131-135,
31, 34, 38, 47, 54, 62, 105-106, Corrosivity, 47, 52, 138
141, 144, 156, 164, 175
138, 171 Cosmetic, ix, 88, 92, 148, 164
Cleaning process, iii, ix, 17, 19, Counterflow-cascade, 23, 58
E Flammable, 45, 94, 159, 160
27, 44, 52, 54, 62, 95, 99, 105, Economic factors, 137 Flash point, 47, 132, 138
Counterflow-cascade rinse, 23
117, 119, 124, 126, 128, 133, Economy, 21, 45 Flocculent, 129
135, 147, 155, 156, 157, 159, Coupling agent, 16
EDTA, 12, 15, 166 Flow-through clean-in-place, 22
177 Coupon sampling, 121, 122
Electron spectroscopy, 142, 150 Fluid processing, 93-94
Cleaning process design, 119, Cross-contamination, 24, 65-67,
Electronic component, ix, 24, 32, Foam height, 136-137
126 82-83, 95
84, 138 Foam suppressing capabilities,
Cleaning time, 19, 22-23, 34, 39, Cycle time, 56, 73
Electronic solder flux cleaning, 21
52, 55, 63, 117, 147 20 Foaming agents, 15, 20

180 The Aqueous Cleaning Handbook Appendix 181


Food and beverage processing, 143, 145-146, 148, 167-169 Low-foaming detergent, 20, 30, 167
83 Hydrotropes, 16 81 Nonpolar, 85
Forced-air, 26, 39, 59 Hydroxide, 2, 14, 16, 69, 136, 168 Low-power microscope inspec- Nonvolatile Residue Inspection
Forced-air drying, 39 tion, 142 (NVR), 141, 143
Free alkalinity, 37, 135 I Nuclear, 93, 164
Free-rinsing, 41, 44, 58, 79, 176 ICH, 67, 125, 167 M
FTIR, 54, 135, 142, 151 Ignitability, 138 Machine cleaning, 20, 81 O
Immersion, 5, 12-14, 28, 30-32, Machine washing, 20, 29, 81 Oil evaporation, 141, 145
G 34-36, 55-57, 63, 79, 84, 90, 92, Magnesium, 6, 11, 13, 15, 24, 32, Oil viscosities, 61
Gas chromatography, 126, 142, 116, 172 42, 135, 166, 168, 174 Oleophilic, 9, 11, 133
151, 166 Immersion cleaning, 13-14, 32, Manual, 20, 22-23, 28, 34-36, 44, Operating cost, 46, 131
Glass, iv, ix, 42, 44, 59, 61, 65, 34, 36, 55-57, 79, 84, 90, 92 47, 57, 63, 55-67, 68, 71, 76,
80, 82-83, 85, 91-94, 97, 98-102, Operational Qualification (OQ),
67-69, 70-71, 74, 79-80, 82-84, Ingredients, 1, 7, 9, 11, 14-16, 21, 119, 167
87, 90-91, 100, 102-103, 107, 37, 42, 45-47, 67, 75, 83, 87, 92- 163-164, 173, 176
Manual cleaning, 20, 23, 28, 34, Optical microscopy, 141, 144
122, 144-148, 150, 164, 174 3, 111, 121, 124-125, 155-159,
165-167 35, 36, 47, 57, 63, 80, 83, 99- Optically stimulated electronic
Glassware washer, 30 emission, 142, 151
Inhibitor, 15, 24, 39, 46, 71, 88 100, 102, 173
Global warming, v, 3-5, 162 Optics, 91-92, 164
Inorganic, 6, 9, 11, 14, 17, 42, 44, Manual surface cleaning, 98
GMP, 66, 72-78, 111, 113, 119 Organic, v, vi, ix, 1, 3, 4, 5, 6, 8,
60, 82, 90-91, 114-115, 129, Mass displacement, 58
GMP washing machines, 72 9, 10, 11, 13, 15, 32, 41, 42, 44,
131, 136, 143, 145, 151, 164, Mass spectrophotometry, 142
Gravimetric, 54, 141, 145 173 45, 48, 60, 82, 84, 85, 86, 88,
Master validation plan, 119 90, 94, 121, 124, 125, 126, 129,
Inorganic soil, 9, 42, 44, 60, 90 Material Safety Data Sheet, vi, 130, 131, 135, 143, 145, 150,
H In-situ particle counting (ISPM), 45, 47, 158-159, 162 151, 158, 160, 162, 165, 167,
Hazardous, vi, vii, 3, 8, 44-45, 47, 146 Measuring cleanliness, iv, 141 168, 169
91, 135, 137, 155-156, 158-160, Insoluble oils, 1, 11, 129
164 Mechanical action, 5, 12, 13 Organic-free, 82
Insoluble particles, 14 Mechanical agitation, 20 OSEE, 54, 142
Hazardous chemicals, vi, 8, 155,
159 Installation Qualification (IQ), Medical device manufacturing, OSHA, 45, 47, 159-160, 162
119 78, 122 Outgas, 84
Hazardous substance list, 45, 47
Interfering detergent residue, 44 Metal finishing, 88 Overkill system, 63
HCFC, v, vii, 2-5, 8
Ion chromatography (IC), 142, Micelle, 11-12, 79, 166-167 Ozone depletion, 3, 45
Healthcare, 65-66, 164 151
HEPA filter, 75 Microfiltration, 132, 134-135
Ionic, 10, 85, 86, 87, 135-137,
High emulsifying, 20, 42, 55, 90, 151, 167
Millipore filter measurement, P
92, 136 141, 144 Parenteral medical device, 79
Irritants, 47 Minimal system, 63
High volume/low pressure, 56-57 Particulate, 11, 17, 22, 42-44 56,
High-agitation spraying, 55 Mixer, 71, 84, 114, 116, 123 61, 74, 75, 85, 91, 103, 114,
L Montreal Protocol on Substances 115, 132, 137, 150, 164, 166,
High-foaming cleaners, 56 Laboratory cleaning, 30, 79-81 that Deplete the Ozone Layer, 5 169
HPLC, 121, 126, 135, 145, 167 LD50, 122-123 Parts washer, 30, 32, 44, 85, 91-
Hydrochlorofluorocarbon, v, 3-5
Hydrogen bonding, 7, 10
Limonene, 5 N 92, 133, 164
Lipophilic, 14 Neutral, 14, 16-17, 37, 65, 69, 71, Pathogens, 66
Hydrolysis, 13, 16, 17, 56, 135, Liquids, ix, 5, 15, 46, 149, 151, 84, 91, 93, 137, 163, 167 PC board, 30-31, 85
165 166 Nonferrous, 42 PC board washer, 30, 31
Hydrolyzed, 17, 167 Lot number tracking, 21 Nonionic, 9-10, 14, 20, 85-86, Performance Qualification (PQ),
Hydrophilic, 9, 11, 14, 133, 146, Low volume/high pressure, 56-57 136, 137, 151, 167, 169 119
167, 169
Low-foaming, 20, 29-30, 56,81, Nonionic contaminant, 86 Permeate, 133
Hydrophobic, 9, 11, 45, 133, 142- 92, 163 Nonionic surfactant, 10, 14, 125, pH, 10, 14-17, 37, 39, 65, 69-71,

182 The Aqueous Cleaning Handbook Appendix 183


84, 90-91, 93, 97, 100-102, 109, 129, 131-135, 137-139, 147, 156 Scanning Electron Microscopy Stainless steel, 15, 42, 44, 59, 65,
121, 129, 134, 136-138, 157, Refractometry, 136-137 (SEM), 142, 152 67, 69, 71, 74, 75, 82-84, 91,
165, 167 Regulatory review, 159 Secondary Ion Mass 107, 114, 115, 164
Pharmaceutical, iv, 24, 32, 66-69, Residue, ix, 6, 17, 21, 23-26, 28, Spectroscopy (SIMS), 142, 152 Stainless steel cleaning, 69
71-72, 77, 78, 82, 92, 95, 119- 30, 32, 39, 41, 44-45, 67-71, 78- Semiaqueous cleaner, 5, 14, 17, Standard operating procedure,
122, 128, 138, 164-166, 173 80, 82-90, 92, 94-95, 115-117, 160, 168 iv, 67, 78, 97, 111, 117, 126, 168
Phosphate, 83, 125, 158, 164 120-127, 141-145, 148, 164, Separator, 130, 134 Steel, 15, 39, 42, 44, 59, 65, 67-
Physical drying, 24-26 168, 176-177 Sequestering agent, 11-12, 15, 71, 74, 75, 77, 82-84, 91, 103,
Physical filtration, 37, 132 Residue acceptance criteria, 121- 44, 166, 168 107, 114-115, 164
Physical separation, 133 122 Sequestration, 13, 165 Sterilization, 65-66, 103-104
Pilot scale, 63, 71, 78 Residue detection method selec- Sessile drop technique, 149 Sterilizing, 65, 78
Piping system, 71, 94 tion, 120-121 Silicates, 14 Substrate, iv, 1, 3, 12-15, 17, 19-
pKa, 69, 70, 71 Residue identification, 120-121 Skimmer, 130, 134, 139 20, 23-26, 28, 32-34, 42, 44, 51-
Residue-free, 45 52, 54-56, 59-61, 69, 88-89, 92,
Placebo sampling, 121 Soak, 19-20, 22-24, 28, 30, 32, 149, 164
Plastic, ix, 34, 39, 42, 59, 65-66, Retentate, 133 35-36, 44, 58-59, 62, 66-68, 71,
Rinse, 13, 19, 21, 23-24, 28-33, 80-83, 85, 91-93-94, 99, 105, Surface active agent, 1, 2, 9, 165,
68, 74, 78-79, 84, 89-90, 93, 167-169
144, 153 39, 44-45, 51, 58-59, 68, 71-72, 115, 139, 163-164, 172, 177
80-82, 89, 92, 99-100, 106-108, Soak cleaning, 22, 35, 36, 71 Surface contact-angle, 54
Plastics compatibility, 89
111-113, 115-116, 121-124, 132, Soaking, 22, 23, 28, 35-36, 55, Surface energy, 141, 145-146,
Polar, 6-7, 10, 85, 168 134-135, 147, 156, 168, 171-177 148-149, 153
Polar soil, 6-7, 168 65, 80, 93, 99, 105, 177
Rinse aid, 44-45 Soap, 1-2, 6, 10, 12-16, 20, 167- Surface tension, 11, 12, 14, 21,
Polar solvent, 6, 168 Rinse procedure, 32, 81, 99, 106 43, 90, 149, 166, 168
168
Polymerized rosin, 87 Rinse water sampling, 72, 121 Surfactant, vii, 1, 5-6, 9-14, 16,
Soil, 1-3, 5-7, 9, 11-17, 19-23, 28,
Porous surface, 60 Rinsing, vi, 5, 9, 13, 21, 23-25, 32-34, 37, 41-46, 51-52, 54-55, 20, 21, 25, 39, 44, 48, 125, 135,
Postcleaning handling, 19, 27, 29, 31-32, 39, 41, 44, 52, 54, 58- 57-61, 65-66, 68, 78, 80-83, 85, 136, 137, 157, 160, 165-169
34, 97, 112 59, 61, 72, 79, 81-82, 88-89, 92, 89-90, 91-94, 97, 99, 105, 113, Surfactant-free cleaner, 20
Powder, 15-16, 46, 163 98, 102-107, 111, 114, 116, 124, 117, 132-133, 135-138, 141, Suspended solid, 129
Power spray wand, 29 134-135, 155-156, 176-177 143-146, 155-156, 159, 166-168, Suspension, 11, 43, 67, 133, 166
Rosin, 44, 85-87, 164, 168 172-173, 175 Swabbing surface, 121
Power washer, 29
Rubber, 4, 42, 47, 82-83, 89, 91, Solder paste, 87 Synthetic solvent, 2-3
Precleaning handling, 19, 31, 97
102, 107, 164 Solubilization, 13, 25, 42
Presoaking, 21-22, 99, 105
Solution recharge, 133 T
Pressurized spray, 30
Protein, 17, 34, 69, 84, 99, 105,
S Solvent, v, vi, vii, ix, 1-8, 13, 15, Tank, 22-24, 26, 28-31, 36, 46,
Safety based limit, 122, 123 25, 27, 39, 41, 44-45, 46-48, 52, 55, 57-59, 67, 71, 80-81, 93-95,
167
Salt, 1, 11, 14, 15, 17, 24, 33, 37, 59, 61, 87-88, 90-91, 131-132, 97-98, 100-101, 104-107, 110,
Proteinaceous soil, 44, 65-66, 80, 143-145, 151, 158-160, 164,
83, 164, 175 60, 68, 83, 85, 87, 88, 90-91, 94, 114-117, 129-130, 132, 134,
134, 135, 136, 164, 166, 167, 166, 168 139, 172
168, 173 Spray, 12-13, 20, 22-23, 28-36, Tap water, 11, 23, 24, 58, 82, 92,
Q Sampling method, 120-121 44, 47, 55-57, 63, 67-68, 71, 74, 98, 99, 104, 105, 106, 114, 168,
Quality control, 21, 52, 73, 93, 80-83, 85, 91-94, 111, 113, 116- 174, 175, 176
Sampling procedures and recov- 117, 144, 158, 163-164, 174
128, 134, 138, 149
ery, 119 Tape test, 141, 144
Spray agitation, 30, 55
Sanitizer, 30 Temperature, 12-15, 17, 19-23,
R Saponification, 9, 13-14, 167
Spray cleaning, 13, 22-23, 34-36, 29-31, 33-34, 38-39, 42-43, 52,
RCRA, 45, 48, 138, 160, 162 47, 55-57, 158 54-55, 61-63, 71, 73, 75, 77, 81,
Saponifier, 2,15, 20, 168 Spray clean-in-place, 28-29, 36,
RCRA Hazard Classification, 45 86, 90, 92, 97, 99, 101, 105,
Scale, 16-17, 44, 80, 83, 88, 91, 44, 68, 80, 82-83, 91, 94, 164 111-117, 130, 133-134, 136,
Reactivity, 45, 47, 69, 127, 138 115, 164 Stabilizers, 15 171, 175
Recycling, iv, 13, 18, 43, 46, 79, Scale-up, 55, 57-60

184 The Aqueous Cleaning Handbook Appendix 185


Terpene, 3, 5 V
Test, 51, 54, 59-61, 119, 141, 144, Vacuum drying, 25, 33, 39
148 Vapor degreasers, 5
Test acceptance limit, 119 Vesication, 86
Test cleaning, 51, 54, 61 Visual inspection, 54, 61, 141-
Test soil, 51, 60 142, 144
Test substrate, 51, 59 VOC, v, 4, 8, 45, 162
Testing, 19, 54-55, 57-62, 68, 82- VOCs, 3-4, 41
83, 86, 113, 120, 122, 145-146 Volatile, v, ix, 2-4, 8, 41, 44-45,
Testing, iii, vi, 51, 113, 153 48, 52, 59, 61, 91, 156, 158-159,
Time, vii, x, 12, 17, 19, 22-23, 25, 162, 164, 168
28, 31, 34-35, 38-39, 43, 46-47,
52, 54-57, 61-63, 71, 73, 75, 77, W
80, 89, 97, 99-100, 105, 110-
111, 114, 116-117, 124, 132, Wash cycle, 29, 72, 81, 111
139, 147-149, 152, 156-157, Waste treatment, 52, 94,175
171-177 Waste-treatment filtration, 94
Titration, 27, 37, 121, 125-126 Wastewater treatment, iv, 129,
Total alkalinity, 135 130, 131
Toxicity, 47, 52, 82, 88, 120, 122, Water break, 141-143, 146
127, 138, 157 Water drop surface energy test,
Trace analysis, 82, 144-145 148
Trace metals, 80, 82, 164 Water testing, 82
Wax melting points, 61
U Waxy or oily soils, 22
Ultrafiltration, 18, 114, 133-135 Wetting, 1, 9, 11, 13-14, 20, 43,
Ultrasonic, 12-13, 20, 22, 29-32, 56, 90, 150, 153, 169
34-36, 44, 57, 66-68, 78, 80-83, Wetting agent, 1, 9, 11, 169
85, 88, 90-92, 97, 104, 106-108, WFI, 68, 74, 79, 111, 121
110, 146-147, 163-164, 171 White residue, 86-87
Ultrasonic cleaning, 20, 22, 29, Wiping and visual inspecting,
35, 57, 67, 78, 81, 91, 97, 104, 141, 142
106-107, 110, 147
Worker safety, 41, 52, 158, 160
Ultrasonically agitated rinsing,
23
USP, 111, 125 Z
UV, v, 121, 126, 131, 141, 143, Zero-discharge, 156
145, 151, 162, 169
UV spectroscopy, 121

186 The Aqueous Cleaning Handbook

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