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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 found increasing application in a wide range of industries as an environmentally benign alternative to ozone-depleting compounds and hazardous solvents. This book distills and presents practical information covering the history of such cleaners—what they are, how they work, and how to make best use 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 training and professional experience in chemistry. Both are employed by Alconox, Inc., a New York firm which has been a leading developer and supplier 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 earned his M.A. in Chemistry from Columbia University. 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.
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.
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
All rights reserved under Pan-American Copyright Conventions. Published in the United States by AL Technical Communications, LLC, White Plains, NY Unauthorized reproduction of this book is forbidden by law. International Standard Book Number 0-9723478-0-1 Library of Congress Catalog Card Number 2002110614
v ix 1 9 19 41 51 65 97
What Is an Aqueous Cleaner?
The Chemistry of Aqueous Cleaning
Special thanks to Peter Levin, Elliot Lebowitz, and 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.
Selecting an Aqueous-Cleaning Detergent
Testing and Selecting a Detergent and Cleaning System
Industrial Cleaning Applications
Standard Operating Procedures
White Plains. Inc. contact Alconox. The international Montreal Protocol treaty and the U. will donate one dollar to American Forests to support forestry conservation and tree-planting projects. NY 10603. they worked. CFCs would replace petroleum-based chemicals known for their health hazards. The introduction of hydrochlorofluorocarbons (HCFCs) as secondary replacement chemicals reduced but did not eliminate this danger. including VOC (volatile organic Foreword v I II III IV V Clean Air Act Amendments Cleaner Types from Alconox. CFCs and HCFCs also increase global warming by interfering with the atmosphere’s natural ability to radiate heat away from the planet. CFCs were relatively inexpensive. USA. Alconox. fax 914-948-4088. Inc. Inc.com. Clean Air Act Amendments govern the usage and production of most of these compounds. readily available and most importantly. The reaction is catalytic with the potential for one (1) Cl atom to destroy thousands of O3 molecules. iv The Aqueous Cleaning Handbook . Detergent Selection Guide Glossary of Essential Terms Application Case Histories Optical Substrate Metal Valves Pharmaceutical Equipment Glass Filter Membranes Wine Tasting Glasses Laboratory Pipets VI Index Most For every book printed. This exacerbates the Greenhouse Effect most noticeably impacted by fossil fuel burning.alconox. cleaning@alconox.CHAPTER EIGHT Cleaning Validation CHAPTER NINE 119 129 141 155 162 163 164 165 171 171 172 173 174 175 176 177 179 Wastewater Treatment and Cleaner Recycling CHAPTER TEN Measuring Cleanliness CHAPTER ELEVEN Environmental Health and Safety Considerations APPENDIX Foreword cleaning practitioners are familiar with the story: the scientists who developed chlorofluorocarbons (CFCs). www. first as refrigerants and then as solvents. inert materials.com.S. 30 Glenn Street. What the researchers did not know was the impact these chlorine-containing substances would have on the ozone layer: that portion of the atmosphere responsible for shielding the earth from some of the solar system’s most harmful ultraviolet (UV) rays. For information. had struck upon what they thought were safe.. 914-948-4040. Chlorine (Cl) atoms participate in the destruction of ozone (O3) as they randomly make their way into the upper atmosphere. American Forests has been promoting protection and sustainable management of forest ecosystems since 1875.
Like the CFC and HCFC designers.. The constituents and mechanisms of aqueous cleaners must be understood. Methods of extrapolating test data as well as gender and age differentials require review. There are challenging opportunities for advancement. The principle represents a radical departure from conventional thinking that may be lost on those not directly involved in the chemical industry Thousands of new chemicals enter the market each year while little is known about the vast majority of existing chemicals. It is no wonder. Early partnering with stakeholders may ameliorate the mistakes historically associated with the discovery process. should be expanded (negative impacts from low-dose exposures include hormone mimickers and endocrine disrupters). The occurrence of the words “test data unavailable” or “unknown” on many of these documents helped set the stage for other environmental initiatives. drying and inspection owe their economic feasibility to regulatory drivers. Risks may simply be shifting from the site of usage to the chemical’s production plant (or power plant) rather than real progress being made. And once a substance was deemed safe. who would be liable for any errors that are sure to occur? It remains to be seen whether American society. Inc. Nor do they fully consider the drain that chemical manufacture can place on natural resources and raw materials. all matter to the concerned scientist. steeped in litigation. EPA’s Toxic Release Inventory (TRI) provides a powerful tracking tool for looking at the places and the reasons hazardous chemicals are used. Most government policies focus on chemical handling and use.” The translation: sell no product whose environmental. alkaline builders and the dependence on water and energy (increasingly precious resources in an over-populated world). Chemical exposures effect workers. consumers and communities. bear more investigation. the only universal solvent truly non-toxic to both humans and the environment. Initiatives in northern Europe have begun to reflect the precautionary principle. Alconox. can rise to the occasion. Environmental Protection Agency’s (EPA) Significant New Alternatives Policy (SNAP) identifies acceptable substitutes. health and safety concerns have not yet been elucidated. The U. This transpired against a back drop of Right-to-Know legislation and chemical accidents culminating. This is the EH&S equivalent to the Hippocratic medical oath. These laws purposefully devastated organic and chlorinated solvent markets while fostering research and development. toxic-free analytical techniques for surface evaluation will be invented that are superior to those now in use. This would no longer be tolerated under a system that demands thorough environmental and health information before exposure (as opposed to after a potential. They do not necessarily take into account a chemical’s life cycle or environmental fate. “First do no harm.S. Furthermore. Chemical manufacturers would have stronger stewardship responsibilities. This is no time for intellectual arrogance. deserves much credit for its self-imposed vi The Aqueous Cleaning Handbook Foreword vii . rinsing. Testing parameters other than those based on the cancer paradigm need to be determined.compound) emitters. Surfactants and emulsifiers. unknown disaster). in no small measure. This is especially worrisome in light of environmental justice issues. then. Other problems remain. Hundreds of companies specializing in surface preparation.S. leading to better job security and overall quality of life. the U.* pursuit of this vision minimizes or eliminates environmental impacts and health and safety risks linked to many industrial cleaning applications.e. In addition. today’s formulators will undoubtedly push aqueous (i. that many industries are rediscovering water (H2O) as the ideal cleaning medium. These objectives support a more sustainable business plan. It is possible to envision the day when manufacturers will no longer be forced to use hazardous materials for surface cleaning in the production of quality goods and services. Based on the cornerstones of pollution prevention and cleaner production. with the inception of Material Safety Data Sheets (MSDSs). The effects of chemical mixtures. individually thought to be benign. Products would take longer to reach the marketplace. cleaning. water-based) cleaners to the scientific limits of the day. The study of chemicals’ effects at low concentrations. One suspects that not all aqueous cleaners are created equal.
In many cases aqueous cleaning is also the best available technology and provides a viable long-term solution to environmental issues. — Carole LeBlanc Toxics Use Reduction Institute University of Massachusetts • Lowell Introduction Today . corrosive chemicals. It can also include cleaning applications in industries such as chemicals. food and beverage. It is important that these cleaners not contain high concentrations of volatile organic compounds or solvents due to their air-pollution and ozone-depletion potential. aqueous cleaning represents an economical. and metal piping and processing equipment. the terms precision or critical cleaning include any cleaning process where residue can cause a failure in the function of the surface being cleaned. Current practice for critical cleaning includes the use of volatile solvents. They should also be formulated to minimize worker hazards yet still deliver critical-cleaning performance in the intended application. This handbook is designed to help laboratory and plant personnel select aqueous cleaners and systems more wisely ix *The term cleaner production refers to safer. In that regard. glass. however. pharmaceuticals. viii The Aqueous Cleaning Handbook Introduction . greener. and aqueous detergents. and cosmetics where solids and liquids come into contact with plastic. prepare to learn well from this Handbook. many companies are closely examining their use of volatile-solvent and corrosive-chemical cleaners. In general industry this includes electronic component cleaning and surface preparation of metals prior to coating or bonding. Readers. In today’s hazard-sensitive workplace. and more sustainable manufacturing methods and materials and not the production of chemical cleaners.mission to educate the public about aqueous cleaning. environmentally benign alternative.
and scientific reasons. please feel free to contact our technical services department at Alconox. M. Inc. This handbook also contains critical information on how to select an aqueous cleaner and make the most of the cleaning potential of an aqueous-cleaning system. — Alan S. or attached to a substrate surface—for esthetic. If you have any questions that are not included in this handbook. (Chapter Two of this handbook provides a thorough discussion of these ingredients. In fact. To make it easy for you to find important information. McLaughlin. x The Aqueous Cleaning Handbook What Is An Aqueous Cleaner? 1 . While by no means exhaustive. • Solvents—which use solvency to remove soils by dissolving them with the solvent to form a homogeneous mixture.and maximize their cleaning performance. many ideas for new aqueous-cleaning compounds have come from such contact. a leading developer and supplier of aqueous-cleaning detergents. Typically an aqueous cleaner contains a surface active agent (surfactant) and builders to help the surfactant. The surfactant will usually also act as an emulsifier to help form emulsions with waterinsoluble oils.D. M. (877-877-2526). Malcolm M. In its pages you will find handy. we hope you find this handbook helpful. easy-to-read summaries of what aqueous cleaning is and how it works—its chemistry and mechanical properties. and you’ll find our technical service staff ready and willing to help with your questions or concerns. CHAPTER ONE What Is an Aqueous Cleaner? An aqueous cleaner is a blend of ingredients designed to enhance the cleaning ability of water. medicinal. The surfactant acts as a wetting agent to allow the cleaning solutions to penetrate into crevices and around and under soils. it represents the culmination of more than 50 years experience with aqueous-cleaning technology by the staff of Alconox.A. Zisman. Inc.. Inc. cleaning considerations for each industry are also presented.) 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. The builders usually react with dissolved metal ions in the water to help stop them from interfering with cleaning. Whether you have used aqueous cleaners and systems for some time or are just now considering switching to aqueous cleaning. Alconox. social. 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.
The chlorocarbons have good cleaning properties but unfortunately have toxic vapors. the common name for about 13 species of deciduous or evergreen trees in the soapberry family whose fruit contains a soapy substance called saponin—a natural cleansing agent produced by the reaction of an alkali. were found to have solvating powers. and hydrochlorofluorocarbons (HCFCs). The HCFCs were developed as less hazardous replacements for CFCs. the most common application for industrial solvents is to put dirty solid matter (parts.• Synthetic solvents—which use manmade hydrocarbonbased compounds such as CFCs. clay tablets in Mesopotamia contained a recipe for soap that included potash—potassium carbonate—and oil. typically sodium hydroxide (NaOH) and animal fat or vegetable oil. usually with a narcotic effect. the ancient Romans shared their knowledge of soap formulation (sapo.) into the solvent where foreign matter on the surface is dissolved into the solvent. “trike. A solvent is usually a liquid substance that is capable of forming a physical. which is highly related to its boiling point.) The second-century writings of the Greek physician. The principle of ‘like dissolves like’ was discovered early in human history by simple observation. In cleaning substrates. and chlorine based solvents. Chlorocarbons are carbon-chlorine based solvents. Solvents that have reasonably low boiling points are more volatile and can be more readily removed from a reaction mixture by distillation or evaporation. fluorine. while others are soluble only up to a specific percentage and any excess precipitates out of the solution. or “Perc”). but unfortunately their vapors contribute to ozone depletion in the atmosphere which can also contribute to glob- 2 The Aqueous Cleaning Handbook What Is An Aqueous Cleaner? 3 . The chlorofluorocarbons (CFCs) are less toxic than chlorocarbons. It is very important to match the solvent character of your soil or foreign matter to the type of solvent with which you are cleaning. A given solvent will be “like” some soils and “unlike” other soils where it will not be able to dissolve and clean as well as a solvent with like properties. Chlorofluorocarbons (CFCs) are carbon. Galen. Synthetic Solvents—Nonaqueous solvent cleaners include chlorocarbons. natural organic compounds occurring in the essential oils and oleoresins of plants (lemon. The vapors also contribute to smog formation. Manufacturing methods were crude. The most common example used in cleaning is CFC113. HCFCs. Solvents—To understand solvents and their strengths and liabilities as cleaning materials. homogeneous solution. medicinal product that helped to cure skin ailments. bromine. the Latin word for soap is still used to describe the saponifiers often added to today’s synthetic detergents) and by the Middle Ages commercial soapmaking centers were established in such European countries as France and Spain as well as in England. Its use dates at least from the third millennium BC. • Aqueous cleaners—which use blends of detergent compounds with surface active agents together with other cleaning chemicals that use detergency to lift soil from a surface by displacing it with surface active materials that have a greater affinity for the surface than for the soil. Halocarbons are halogen-carbon compounds (chlorine. and iodine). however. and perchloroethylene (PCE. products. The most common examples used in cleaning are carbon tetrachloride. (In fact. The substrate is then removed from the solvent-dilute-foreign-matter mixture which evaporates and deposits a relatively much smaller amount of foreign matter left over from the dilute mixture—leaving a proportionally clean substrate. and PFCs. fluorine. pine). it’s important to understand “solvency”—the ability to dissolve. Later. Chlorocarbons are volatile organic compounds (VOCs). trichlorocarbon (TCA. Another important aspect of a solvent is its volatility.” or methylchoroform). orange) and conifers (balsam. etc. referenced soap as a cleansing. chlorofluorocarbons (CFCs). Soaps—A name stemming from the soapberry. In this trial-and-error process some terpenes. Hydrofluorochlorocarbons (HCFCs) are modified CFCs with the addition of hydrogen. until discoveries by Nicholas LeBlanc in the 1800s and a century later by Michel Chevreul made it possible to make predictable soap formulations. Some materials are soluble in certain other materials in all proportions.
on September 16. some of which exhibited excellent characteristics as a solvent and cleaning agent. This is accomplished by combining a surfactant with a low-volatility hydrocarbon such as a terpene. semiaqueous cleaning involves using its organic components to dissolve soils and its water component to What Is An Aqueous Cleaner? 5 4 The Aqueous Cleaning Handbook . brominated hydrocarbons. are also used for cleaning. they have ozone depleting potential (ODP) and they have global warming potential (GWP). Today. During the following 50 years. and perfluorocarbons (PFCs). In addition to the above-mentioned compounds. and have less ozone depleting potential than the CFCs. In its simplest form. in particular limonene and pinene (citrus or pine in origin). In an effort to continue the use of CFC-related compounds. In the 1890s Swarts discovered that the carbon-fluorine bond could be formed with antimony fluoride and the addition of trace quantities of pentavalent antimony as a fluorine carrier to form chlorofluorocarbons (CFCs) from chlorocarbons such as carbon tetrachloride. chlorofluorcarbons (CFCs). This agreement known as the Montreal Protocol on Substances that Deplete the Ozone Layer was signed by 24 countries. dibromomethane (for example. nonflammable solvent for fats and oils. although on a much smaller scale. Carbon tetra-chloride is also a volatile organic compound (VOC). nor is it restricted to a constant boiling composition.. the chemical precursor of CFCs—and led to the development of the first commercial refrigeration systems some thirty years later. to form a cleaning blend. cleaning with semiaqueous cleaners does not rely on boiling liquids. methylene bromine). stimulated the development of new. Unlike traditional vapor degreasing. initially used as a degreasing and cleaning agent in the dry-cleaning and textile industries—was first produced in Germany in 1839 and marketed as a grease remover. hydrochlorofluorocarbons (HCFCs). Through his work. halocarbons. The calculation of the amount of VOC in a particular product or process is important since ozone. Terpenes are homocyclic hydrocarbons and have a characteristic strong odor. Semiaqueous cleaning incorporates the principles of aqueous and organic cleaners. asphalt. Semiaqueous cleaning involves cleaning with a solvent or solvent/water mixture followed by rinsing with water as in traditional aqueous cleaning. continuous reactor processes were developed to control the degree of fluorination of the carbon molecule for the manufacture of refrigerator coolants. In addition to immersion. Evaporating into the atmosphere at ambient conditions. coupled with the negative environmental impact of second-generation HCFC substitutes. There are a number of carbon-derived cleaning compounds. are highly toxic. SEMIAQUEOUS CLEANERS The acute and chronic toxicological profiles of the aforementioned organic and first-alternative CFC cleaners. Its vapors. vapor degreasers are often employed with these types compounds in industrial cleaning. bitumens and gums. turpentine is an illustrative solvent that is a mixture of terpenes. but their mechanical action can be viewed as secondary because of their excellent solvating properties.al warming. The CFCs are ozone depleting substances (ODS). These are generally less toxic than chlorocarbons. is affected by VOC emissions. more than 160 countries have signed the Protocol. carbon tetrachloride also became known as tetrachloromethane. Nonetheless. the primary component of smog. the HCFCs have sufficient ozone depleting potential and global warming potential to be of concern to end users. Manufacture of ozone-depleting compounds was phased out after a world meeting among industrial and developing nations to restrict their use and manufacture. The history of halocarbon chemistry played an important role in the development of solvents and synthetic industrial solvent cleaners—and was used to eventually foster development of aqueous cleaners as a replacement for environmental reasons.S. they all have built-in environmental liabilities—CFCs. Carbon tetrachloride (“carbon tet”)—an important. however. hydrofluoroether. rubber. VOCs include almost all synthetic and plant-derived solvents as well as fuels. HCFCs and PFCs are believed to contribute to global warming. hydrochlorofluorocarbons (HCFCs) were developed. however. 1987. including the U. including hydrocarbons. While each has its own cleaning advantages. innovative cleaning techniques and a rebirth of aqueous and semiaqueous cleaning.
these ingredients are discussed in the next chapter. not all soils dissolve readily in water.” is an important component of aqueous cleaners because it dissolves many types of soils. Water— which may be municipal tapwater. One can think of the oxygen as being a large. sometimes referred to as synthetic soaps. Figure 1A H (∂+) H (∂+) Partial Positive Charge Dipole Moment Partial Negative Charge AQUEOUS CLEANERS The first aqueous cleaners were soaps as discussed earlier.remove blend-based residues and any other water-soluble soils. considered by many to be the “universal solvent. The development of complex phosphates used to soften water following the Second World War increased the cleaning power of these detergents.” This directional net-negative charge towards the base of the “V” is called a dipole moment. Aqueous cleaners start with water as their basic “solvent” and add ingredients that enhance the ability of water to hold soils. This gives the entire water molecule an overall net negative. and cleaning mechanisms for. This dipole moment is important because it allows stable solutions of other dissolved polar-soil molecules to become arranged in more thermodynamically stabile alternating positive and negative ends of molecules (fig. Surfactants are used when the water-solubility of the solvent is limited or to improve the emulsifying properties of the cleaner. (The chemistry of. electron-rich end at the base of the “V” (d-) and an electron-poor positive end (d+) of the molecule towards the hydrogen top of the “V. 1B). aqueous detergent cleaners are complex mixtures specifically formulated to create greater chemical and mechanical cleaning action. or deionized or distilled water based on the cleaning application—also functions as a carrying medium for detergent compounds. The ability of water to undergo hydrogen bonding is relatively unique among solvents. 6 The Aqueous Cleaning Handbook (∂-) Water Molecule (H2O) O The electronegativity that attracts electrons toward Oxygen (O) and away from Hydrogen (H) gives water an electrical polarity or dipole moment Figure 1B H (∂+) H (∂+) O H (∂+) Water (∂-) (∂+) (∂-) O H (∂+) Water (∂-) Dissolved Polar Soil Simplified three body model showing possible stabilized arrangement of polar soil molecule with water molecules with dipole moments arranged negative to positive In addition to having a desirable dipole moment that helps dissolve other polar soils. For this reason. Detergents. Water is a polar solvent that is good at dissolving a wide range of polar soils. water is capable of bonding to soils by a mechanism called hydrogen bonding. Water. dense electron rich atom.) What Is An Aqueous Cleaner? 7 . Polar molecules such as water have a dipole moment. Water has a unique “V” shaped structure with two hydrogen atoms at the top of the “V” and an oxygen at the bottom (see figure 1A). 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 magnesium and calcium ions. But while water is capable of dissolving many inorganic and some organic contaminants. Aqueous cleaners are synthetic detergent cleaning agents used in a water solution. This additional bond capability gives water significant additional ability to dissolve soils as compared with other solvents.
alconox. Toxics Use Reduction Institute. Davidsohn and B. L. Report of the Technology & Economic Assessment Panel (1991). Materials Handbook. Lowell. September 5.colin-houston. Clauser. SC: 212–94). or hazardous chemicals and without appreciable ozonedepletion potential. that are RESOURCES www. HCFCs and Cleaning (University of Massachusetts.cleantechcentral. MA 01854-2866. Surfactants are often emulsifiers. and rinsing. Vol. 249 (6 July 1990). wetting. 1996). Lowell. (SAGE. it is important to understand how aqueous cleaning works. 1991). Toxics Use Reduction Institute. A. Shell Solvents: The VOC Challenge (Houston. Hands On Cleaning and Degreasing Workshop. 1993).S. Precision Cleaning. 173 (Thursday. and additives for corrosion inhibition. TX. Many aqueous cleaners now offer comparable or better cleaning performance to solvent-cleaning systems without using volatile solvents. Acad. Toxics Use Reduction Institute. wetting agents. Manzer. SC-2. The alkylbenzene portion of the molecule is the hydrophobic/oleophilic end of this surfactant and the negatively charged sulfonate molecule is the hydrophilic end of the molecule. aqueous agents are used in the same wide range of industry applications as solvent cleaning systems. Focus (April. 309 (1892). The Evolution of Cleaning Solvents. May 1997. No. REFERENCES C. Handout. National Center for Manufacturing Sciences.S. 24. and penetrating. 1993). Belg. and cationic. By switching to appropriate aqueous cleaning technologies now. Surface Cleaning Series Fact Sheet NO. Anionic surfactant—This is a surfactant that has a negatively charged end of the molecule that gives it the hydrophilic part of the molecule. H.Today. Synthetic Detergents. version 2. United Nations Environment Programme.com 8 The Aqueous Cleaning Handbook The Chemistry of Aqueous Cleaning 9 . it is possible to both eliminate ozone-depletion potential and eliminate changes which may be required under volatile organic compound (VOC) restrictions associated with The Clean Air Act Amendments and state or local VOC restrictions. Noether. CHAPTER TWO The Chemistry of Aqueous Cleaning Before reviewing the technologies and processes involved in aqueous cleaning. KEY DEFINITIONS OF AQUEOUS-CLEANER INGREDIENTS Surfactant—Short for “surface active agent. F. U. p. The most common surfactant is sodium Linear Alkylbenzene Sulfonate (called LAS for short). 11–16. Aqueous cleaners are typically composed of surfactants for emulsifying. Swarts. U. MA 01854-2866. nonionic. sulfates. LeBlanc. 1996). Thirteenth Editor (McGraw-Hill.S. and this begins with the cleaner itself. builders for neutralizing water hardness interference. Lowell. The class of surfactant determines the class of the cleaner. Encyclopedic Dictionary of Chemical Technology (VCH Publishers. R.” it is an organic molecule with a hydrophobic (water-hating/oil-loving) end and a hydrophilic (water-loving) end. anti-redeposition. (University of Massachusetts. These negatively charged parts of the molecules are usually sulfonates. 61. or carboxylates. Surfactants are typically classified as anionic. Science. Vol.1). The CFC-Ozone Issue: Progress on the Development of Alternatives to CFCs. Solvent Alternative Guide. Surface Cleaning (University of Massachusetts. 1996). and dispersants (see other definitions).com www. D. Bull. Milwidsky. MA 01854-2866. Environmental Protection Agency. 1996). SC-1. chelating of inorganic soils.com www. and saponification of natural oils. Federal Register. Surface Cleaning Series Fact Sheet No. chapter on Development of the Detergent Industry.
usually neutralized by positively charged metal cations such as sodium or potassium. Examples include sodium alkylbenzene sulfonates, sodium stearate (a soap), and potassium alcohol sulfates. Anionic surfactants are ionic and are made up of two ions—a positively charged usually metal ion and a negatively charged organic ion. Nonionic surfactants—These are surfactants that have no ions. They derive their polarity from having an oxygen-rich portion of the molecule at one end and a large organic molecule at the other end. The oxygen component is usually derived from short polymers of ethylene oxide or propylene oxide. Just as in water chemistry, the oxygen is a dense electron-rich atom that gives the entire molecule a partial net-negative charge which makes the whole molecule polar and able to participate in hydrogen bonding with water (as discussed in the first chapter). Examples of nonionic surfactants are alcohol ethoxylates, nonylphenoxy polyethylenoxy alcohols, and ethylene oxide/propylene oxide block copolymers. Cationic surfactants—These are positively charged molecules usually derived from nitrogen compounds. They are not much used as cleaning agents in hard-surface cleaners because of the tendency of the cationic positively charged molecule to be attracted to hard surfaces (that usually have a net-negative charge). Many cationic surfactants have bacteriacidal or other sanitizing properties that are useful in creating disinfectants that leave a cationic disinfectant film on the surface. Cationic surfactants are usually incompatible with anionic surfactants, because they will react with the negatively charged anionic surfactant to form an insoluble or ineffective compound. Amphoteric surfactants—Those surfactants that change their charge with pH. They can be anionic, nonionic, or cationic depending on pH. Usually, any one amphoteric can be any two of the three charge states. Dispersant—This is a cleaner ingredient that helps disperse or suspend solid particles in solution. Dispersants include watersoluble surfactants or water-soluble polymers (long-chain
organic molecules) that are electrostatically attracted to particulates, creating a bridge between the water and the water insoluble solid particulate (in some cases even repelling the solid surface to help lift the particles into suspension). Emulsifiers—These cleaner ingredients help emulsify waterinsoluble oils into solution by helping to create a liquid-liquid mixture. Surfactants that use their hydrophobic (water-hating or repelling) or oleophilic (oil-loving) end of their molecule to mix with water-insoluble oils and their hydrophilic (water-loving) end to mix with water create a bridge to emulsify waterinsoluble oils into solution. The specific structure of the bridge is called a micelle that can be thought of as a hollow, oil-filled round ball with a skin made of surfactants with their hydrophilic ends facing out in contact with the water solution and the hydrophobic ends facing in to the oil-filled ball. Wetting Agents—These are surfactants that lower the surface tension of water and allow the cleaning solution to wet surfaces and penetrate into, under and around soils and surface crevices. They create a bridge between the water and any hydrophobic (water-hating or repelling) surface. You can think of a wetting agent as having one end of the molecule attracted to the surface while pulling the water solution towards the otherwise water-repelling surface, allowing the water solution to be in contact with more of the surface that needs to be cleaned. Builders—These cleaner ingredients react with interfering calcium, magnesium, or iron ions that may be present in the water solution. They stop them from reacting with soils and other detergent ingredients to form water insoluble and difficult-to-clean calcium, magnesium, or iron salts. These metals are present to varying degrees in all water, particularly tap water. Builders are usually alkaline salts, chelating agents, and/or sequestering agents. Alkaline salt builders—These are inorganic salts such as sodium carbonate or sodium phosphates. They react with calcium, magnesium, or iron to form water soluble or water dispersible compounds that tie up the calcium, magnesium, and iron.
The Aqueous Cleaning Handbook
The Chemistry of Aqueous Cleaning
Chelating agents—These are negatively charged or oxygen containing molecules that react with positively charged metal ions to form a stable complex. They have multiple locations in the molecule to react with multiple positive charges that may be present on multivalent metal ions that have more than one positive charge on them. An example of a chelating agent is EDTA, ethylene diamine tetraacetic acid. EDTA has four acetic acid groups giving it a potential for four negatively charged acetates to bond with up to four positively charged sites in metal ions with multiple positive charges, such as calcium which has two (2) positive charges associated with it. Sequestering agents—These are chelating agents (see above) that bind particularly tightly with metal ions and sequester or separate them from reacting with other compounds. Detergents use both chemical and physical action to clean, which are affected in turn by temperature, time, type of mechanical action, cleaner concentration, and additives. Mechanical action is provided by immersion, spray, or ultrasonics. The detergents’ chemical action saponifies certain oils, producing water-soluble soap material. The surfactants used in a cleaning formulation then work to physically reduce the surface tension of the solution, in the process emulsifying and lifting soils away from the substrate being cleaned. These surfactant molecules can be both free and aggregate forms called micelles, and their ratio is based on the type of surfactant, its
HOW ALKALINE CLEANERS WORK
concentration, and the temperature of the cleaning formulation. The surfactant lifts oils off the metal surfaces to form a suspended oil-water-surfactant emulsion which is then removed by rinsing. Typically, immersion cleaning involves submerging parts in a bath and providing air agitation, turbulation, and mechanical brushing or ultrasonics to realize desired levels of cleanliness while spray cleaning uses a pressurized wash stream to create even higher soil-removal rates. Cleaning is then followed by water rinsing. In most aqueous cleaning systems, more water is used in rinsing than in cleaning. Also, rinse water must be purified by a recycling system to a higher level than the detergent solution. Rinse water also requires different separation equipment, since the rinse water is the last solution to touch the surface being cleaned. The chemical and mechanical action involved in aqueous cleaning is actually a number of processes. These can be described as: • Solubilization—a process whereby the solubility of a substance is increased in a particular medium • Wetting—to lower surface and interfacial tensions so that the cleaner penetrates small spaces while getting under the soil to lift it from the substrate • Emulsification—creating an oil/water mixture by coating of oil droplets with surfactant to keep them from recombining and migrating to the surface of a cleaning bath (see previous emulsifier discussion) • Deflocculation—breaking down soil into fine particles in order prevent agglomeration by dispersing them through the cleaning medium • Sequestration—reacting with ions such as calcium, magnesium, or heavy metals to prevent the formation of insoluble byproducts (such as soap scum) • Saponification—alkaline hydrolysis of fat by the reaction of fatty acids with alkalies to form water-soluble soaps To encourage such chemical and mechanical cleaning (unlike organic and chlorinated solvents, aqueous cleaners may not depend on solvent penetrability for their cleaning effi-
The Aqueous Cleaning Handbook
The Chemistry of Aqueous Cleaning
ciencies), aqueous cleaners may include a number of the following ingredients, formulated to provide maximum cleaning effectiveness for specific for various types of substrates and soils by reducing surface tension, forming emulsions, and suspending insoluble particles for removal in the cleaning bath: • Surfactants—alkaline surfactants that react with fatty acids to form soap. They improve cleaning action by reducing the water’s surface tension which also allows for greater penetration or wetting of the liquid onto the part surface. Used to either emulsify a soil from a substrate or increase the surface’s wettability. Substances with both hydrophilic (water soluble) and lipophilic (oil soluble) groups that may be cationic, anionic or nonionic depending on the charge of the hydrophilic end. Anionic surfactants are generally poor cleaners because of their negative charge. Cationic or positively-charged surfactants are water soluble and are commonly used in immersion cleaning. Nonionic surfactants with no charge are used for surface cleaning when a lower-foaming detergent is required. A class of synthetic compounds, nonionic surfactants are prepared by attaching ethylene oxide molecules to water-insoluble polymers, but are usually biodegradable in aqueous cleaners. In addition to wetting, surfactants can also enhance the emulsifying and dispersing properties of a cleaner. • Builders—inorganic salts that provide alkalinity and buffering capacity common to almost all aqueous cleaners (pH may be alkaline >7, neutral ~7, or acidic <7). Alkalinity may be provided by hydroxides, carbonates, borates, silicates, phosphates, or zeolites (crystalline hydrated aluminosilicates). Builders also soften water or help with saponification or deflocculation. • Emulsifiers—substances that can form liquid-liquid mixtures (e.g., oil and grease) that do not dissolve in water. Emulsifiers are useful for low soil loading, but their concentration in a detergent limits bath life. Separation of soil and cleaner may be accomplished by making the emulsion unstable by lowering the pH and/or temperature. They are chemically similar to the semiaqueous cleaners described below.
• Saponifiers—Alkalies that react with fatty acids in oils to form soaps. Chemistry may be mineral (sodium or potassium) or organic-based (such as solutions of ethanol amines). • Solvents—Aqueous or organic chemistries designed to enhance the removal of oily soils by dissolving them (e.g., glycol ethers, ethylene [Butyl Cellosolve], and propylene compounds). • Additives—act primarily as contaminant dispersants, anti-redeposition agents, brighteners, viscosity modifiers, antifoaming agents, and corrosion inhibitors or they may have special detergency on a specific soil type. Examples include enzymes, amine compounds, and various polymers. • Sequestering agents—produced as powders or liquids to combine with calcium, magnesium, and other heavy metals in hard water. They form molecules in which these ions are held securely, or sequestered, so that they can no longer react undesirably with other species in solution. Polyphosphates and polyacetates are commonly used. • Chelating agents—employed to solubilize hard water salts so that they remain in solution. Produced in both powdered and liquid forms, they do not degrade or lose their potency at elevated temperatures, which make them ideal for aqueous cleaning. However, they can interfere with the ability of other chemicals to remove emulsified oils and dissolved metals from solution, which can lead to waste disposal problems. In addition to EDTA, nitrilo tri acetate (NTA) is also used. • Corrosion Inhibiting agents—are often added to aqueous cleaners to minimize their effect on metal substrates. They are used for cleaning at high pH and as rust inhibitors to prevent the rusting or oxidation of cleaned parts (or cleaning equipment that is not constructed of stainless steel). • Stabilizers—added to extend the shelf life of detergent ingredients and to maintain the uniformity of detergent blends. For example, dilute cleaner solutions may have a tendency to grow microbes. The presence of biocidal
The Aqueous Cleaning Handbook
The Chemistry of Aqueous Cleaning
water may be added to a concentrated cleaner.additives in a formulation may be indicative of a formulation that is not concentrated (assuming the cleaner is not designed as a biocidal cleaner). Most cleaners are alkaline in nature since hydrolysis—and the chelation and dispersing of soils— typically occurs most effectively at alkaline pH levels.5. as we’ll see in later chapters) is how fast it needs to work. since these types of extenders do not improve detergency and also increase packaging and handling costs. or inert powders may be added to dilute a concentrated powder cleaner. natural greases. There are also semiaqueous cleaners which form neutral solutions upon dissolving or emulsifying in water. coupling agents and hydrotropes that are included in detergent formulations are indicative of highly concentrated formulations because these are used to increase the solubility and costability of various active detergent ingredients.5 could be formulated to remove carbonaceous soils. fats. For example. some types of food products. As a rule of thumb. Each detergent formulation has maximum effectiveness at a specific pH value. oil. However. fingerprints. temperature. one needs to be careful not to purchase a cleaner that is diluted with excess. and soluble metal complexes Light oils. proteins Heavy grease/soils TYPES OF AQUEOUS CLEANERS It is important to keep in mind that a cleaner’s pH value can have a direct effect on cleaning effectiveness.) Time. cheap inert powder. Technically speaking. a pH value of less than seven is considered acidic. it is best to use the mildest cleaner possible. heat scale. The first issue in selecting a cleaner on the basis of pH (there are other factors. to aid in cleaning.” This means that the higher the pH. particulates. small particulates Oils. the higher the pH the more corrosive the cleaner: TYPE OF CLEANER Mineral-acid cleaner Mild acid Neutral Mild alkaline Alkaline Corrosive alkaline pH RANGE 0-2 2-5 1/2 5 1/2 to 8 1/2 8 1/2-11 11-12 1/2 12 1/2-14 SOILS REMOVED Heavy scales Inorganic salts. and higher than seven. • Extenders—fillers which are added to detergent that do not improve detergency (and which also tend to increase the packaging and handling costs associated with the cleaner itself). water. the greater the increase in hydroxide concentration and the faster hydrolysis— the breaking down of a natural fat or oil into a soap—occurs. rust. Thus. Neutral cleaning solutions include alcohols and other water-soluble formulas. Aqueous cleaners are classified according to pH value as being neutral. The Chemistry of Aqueous Cleaning 17 . and generally contain detergents or other surfactant additives 16 The Aqueous Cleaning Handbook Alkaline cleaners work best when the soil can be hydrolyzed (typically natural oils and fats. But while maximum detergency is achieved at high temperatures with high agitation over long periods of time. with a pH of 7 being neutral. and grease. or alkaline on a scale of zero to 14. acidic. the substrate must be robust since corrosion is also a factor. It is occasionally necessary to add a small amount of inert powders as process aids in order to improve the freeflowing characteristics of a powdered detergent. pH is the “negative log of the hydrogenion concentration. films Oils. alkaline. Less foam is generally produced with the use of a neutral cleaning agent. And an alkaline (basic) solution with a pH of 13. and agitation also play important roles in cleaning. However. (Workers should use personal protective equipment with handheld sprays. In contrast. An acidic solution with a pH of 4. for example. and protein residues). would be effective for removing metal oxides or scale prior to pretreatment or painting. The cleaning process should be enclosed to avoid exposure hazards.
set up and cross link • Stored in a dirty environment • Stored in a humid or corrosive environment. May. Alternatively.com www. 1997. Lowell. Toxics Use Reduction Institute. M. Closed-Loop Aqueous Cleaning. Drying method 8. G. 5. 4–5.com www. 1997. Soils can be more difficult to clean if they are: • Allowed to dry. Postcleaning handling The way parts and substrates are handled prior to cleaning can have a significant impact on their degree of difficulty in cleaning. Rolchigo. “Synthetic Detergents. Precleaning handling 2. July/August. Agitation 4. Witter Publishing. Temperature 5. Cleaning time 6. The major variables in cleaning using aqueous methods include: 1.” Precision Cleaning. 7th Ed. Fairfield. p. Seelig. Ibid. pp. May. MA. Witter Publishing. Ibid. Quitmeyer.”Making Aqueous Systems Work. P.S. University of Massachusetts at Lowell. Ibid.M. parts can be placed in protective packaging. New York. “Water Works. As a rule. “All Mixed Up: Qualities of Aqueous Degreasers. 5. University of Massachusetts.¸” CleanTech ’97 Proceedings. p. S..” CleanTech ’96 Proceedings. No. 1994. 10. No. pp. “The Fundamentals of Recycling Alkaline Cleaners Using Ultrafiltration. it is important to clean parts as soon as feasible after they are soiled. Membrex. 1995. 1987 CHAPTER THREE Aqueous-Cleaning Processes Before testing aqueous cleaners. 3–5. RESOURCES www. p.pilotchemical. 1997. Vol. 1. 1996 Davidson A S & Milwidsky B. Rinse used 7.REFERENCES Personal interview. Salinas. it is important to understand a few basic processes regarding their use.” Longman Scientific and Technical copublisher John Wiley & Sons.rhodia-ppd. 9. Cleaner 3..stepan.com www. NJ.com 18 The Aqueous Cleaning Handbook Aqueous Cleaning Processes 19 . 6. and Savage. 2. J.” Parts Cleaning. Vol. Alkaline Cleaner Recycle Handbook. Toxics Use Reduction Institute.alconox. 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. September. Inc.. 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.
cleaners with a nonfoaming surfactants. foam may get sucked into recirculation pipes causing problems with pumps in the machine. These surfactants have a unique property of coming out of solution at elevated temperatures and forming an oil slick on top of the solution. They only work prop20 The Aqueous Cleaning Handbook erly if the temperature is hot enough. a high emulsifying and wetting detergent for manual cleaning. In particular. Foam is formed by the presence of agitation at an air/solution interface when a foaming agent is present. There are some particularly critical aspects to understand in selecting and using a low. Many soils are foaming agents. Finally. In addition. a low-foaming detergent should be used for spray or machine cleaning. Foam will also build up on the substrate and interfere with the mechanical cleaning energy of the spray. Remember that foam forms in the presence of an agitated foaming agent where air is present. It is very important to not have foam when cleaning in or with a machine that relies on spraying for mechanical agitation. Surfactants are often foaming agents. especially for presoaking. It is critical that the detergent be scientifically formulated to clean effectively and to rinse away without leaving interfering residues. A surface tension below 35 dynes per centimeter for the cleaning solution as used is often sufficient for the surfactant to contribute to good rinsing. very hot water should be used (over 65°C). there are controlled foam cleaners that usually have limited foam suppressing capabilities. You should only clean nonfoaming soils with surfactant-free cleaners. These certificates document each lot of detergent to assure consistency and quality control from lot to lot in order to control for potential cleaning failure due to inconsistencies in manufacturing or unannounced formulation changes. typically. A surfactant-free cleaner will not protect against foam formed by soils.or controlled-foam surfactants. The detergent should be widely available and economical to use (for optimum economy. soap formed by saponifiers in electronic solder flux cleaning is a foaming agent. the detergents should be manufactured with appropriate quality-control procedures. a good anti-redeposition detergent for soak and ultrasonic cleaning.or nonfoaming detergent for spray or machine washing.CLEANER The cleaner or detergent used should be matched to the desired cleaning method. This oil slick is a barrier to air contact which stops foam from forming or being stable. A nonfoaming cleaner usually has a nonionic polymer surfactant. The detergent concentrate should be diluted according to the manufacturer’s instructions. You need to know the minimum temperature at which to use these cleaners. and the surface and types of soils being cleaned. and cleaners with low. and degree of agitation should be strong enough to remove the soil to the desired level of cleanliness without harming the substrate being cleaned. and the recommended detergent concentration doubled. For difficult soils. These cleaners will suppress foam from soils. The surfactants themselves do not foam excessively. but they will not be able to control much foam that results from soils. In many critical-cleaning applications it is desirable to choose a detergent that has lot number tracking and can be supplied with certificates of analysis from the manufacturer. A scientifically formulated detergent will typically have appropriate surfactant ingredients and nondepositing rinse-aids. The surfactant should have sufficient surface tension lowering properties to assist in proper rinsing. There are three basic types of aqueous cleaners that are suitable for machine washing: cleaners with no surfactant. For instance. Ambient temperature water may be acceptable. warm (about 50°C) or hot (about 60°C) water is used. a concentrated detergent is typically used at 1:100 to 2:100 dilutions). Most aqueous cleaners have surfactants in them. temperature. Foam may build up and spill over from the machine creating a mess. There are important differences among these types of cleaners. Nondepositing rinse-aids can help complete a formulation to meet the rinsing requirements of critical cleaning. And finally. The detergent. Aqueous Cleaning Processes 21 . It is desirable to choose a detergent from a manufacturer that maintains quality control on their raw materials and in turn keeps retained samples of each lot of detergent that is used to be able to respond to concerns about a particular batch.
It is always desirable. and spray cleaning might even take seconds. and penetrating are time-dependent. spray cleaning (a dishwasher. or temperature cannot be increased—perhaps because the substrate is too delicate or the proper equipment is unavailable—then one must be prepared to use longer cleaning times to achieve the desired cleanliness. Many cleaning mechanisms such as emulsifying. and detergent. For smaller numbers of batch or batch-continuous quantities of parts. or swelling. TEMPERATURE In general. While manual cleaning may take minutes. the more thorough the cleaning. A thorough rinse will remove soils which have been cleaned from the surface and any residue from the detergent itself. Many soak. the greater the need for rinse water purity. If large numbers of parts must be cleaned quickly. detergent. and ultrasonic cleaning methods work best. Cleaning time can be accelerated by increased agitation. manual. whenever possible. more aggressive detergents. The optimum cleaning time should be chosen relative to the specific substrate. It is not always necessary or practical to clean at the optimum temperature. temperature. In general. particularly if soils are dried or baked onto the part to be cleaned. Higher levels of cleaning may require the exclusive use of deionized or distilled water and in some cases more than three times the volume of rinse water. or performed through manual (cloth. dissolving. the last thing to come into contact with the cleaned surface is the rinse water. or even overnight. of course. to clean prior to soils becoming dried or baked onto surfaces.AGITATION Agitation can be a form of nonagitation (such as soaking). Many spray washing techniques work best at 60˚C to 70˚C. high-agitation method such as spray washing often is used with an aggressive detergent. CLEANING TIME In general. a spray washing cycle of five minutes should be followed by three rinse cycles of five minutes each in a spray washing machine). soaking for hours. RINSE USED With aqueous cleaning. and by increasing temperature. brush). suspending. You may have both waxy and particulate soils present. or the part being cleaned may not be able to withstand the optimum temperature. the longer the cleaning time. for example). Whatever contaminants are present in the rinse water to begin with can be present after rinsing. there is typically an optimum temperature for a given combination of cleaning variables. it is desirable to have two counterflow-cascade rinse tanks with dripping “over the tank” for reduced dragout. The important consideration is to remove whatever contamination or residues are present to levels that will not interfere with the further use of the parts or equipment. In practice. A thorough tap water rinse followed by a deionized water or distilled water rinse is usually sufficient. weakening. and high-pressure spray cleaning. tanks and tubes). There are some instances when long cleaning times may promote substrate corrosion. ultrasonic. (for example. for example. the longer they’re employed. the more effective the cleaning on bulk soils. the more stringent the cleaning requirement. flow-through clean-in-place (for pipes. higher-temperature cleaning solutions result in better cleaning. • Standard critical cleaning. If agitation. may be required to reach similar levels of cleanliness. These are. In soak or ultrasonically agitated rinsing. a thorough rinse means rinsing with at least three times the amount of rinse water as the cleaning solution used. at 50˚C to 55˚C. Cleaning often can be enhanced by presoaking. the more cleaning is accomplished. Up to the point where cleaning has been completed. the more agitation. ultrasonic soak cleaning with a milder detergent may be used. cleaning method. Therefore. Different agitation methods are often chosen with (1) time required and (2) number of parts being cleaned as the major considerations. In general. sponge. Waxy or oily soils are more easily cleaned at somewhat higher temperatures. broad generalizations. 22 The Aqueous Cleaning Handbook Aqueous Cleaning Processes 23 . then a fast. Particulate soils tend to be more easily cleaned at slightly lower temperatures.
the use of deionized rinse water reduces the likelihood of depositing calcium. and absorption. and other water-spotting salts. Chemical drying includes solubilization (using a water-soluble solvent to dilute the water) and displacement (using a surfactant-based solvent that is insoluble in water). Physical drying consists of evaporation. leaving conductive residues. poor paint adhesion.• Electronic component and circuit board cleaning. In all cases. forceful drying. This last step in the manufacturing process is important both to the end user and detergent supplier since the performance of an 24 The Aqueous Cleaning Handbook Aqueous Cleaning Processes 25 . can be corrosive to metal substrates during heated and air drying. aqueous-cleaner solvent replacement system is evaluated on the basis of the drying process. As with evaporation drying. Multiple rinsing chambers with hot ultrapure water may not be sufficient to remove these residues and would add significantly to the time and cost involved. There are two basic methods for drying substrates in aqueous cleaning: physical drying and chemical drying. For most cleanroom. Deionized water is preferred rather than tap water or distilled water because deionized water has less potential for metallic cation deposition which leave conductive residues on sensitive electronic components. an important consideration is that any contamination contained in the water will be left behind on a cleaned surface. This method is ideal for removing trapped water from blind holes and crevices but may also deform the part. and problems related to cross-contamination in food. beverage. With aqueous systems. Removing water by evaporation is the oldest and simplest physical drying process. particularly high-purity rinse water. Mechanical systems for physical drying may be classified by the following types: • Vacuum drying—similar to convection drying—requires a negative pressure to be applied. they are not inherently environmentally safe. to be efficiently dried by convection oven. Water. With soak or ultrasonically agitated rinsing. On metal parts. particulates sticking to surfaces. • Some types of parts are heat sensitive and others may be too big or too dense. requiring large amounts of energy. The use of physical removal or drying techniques or the addition of corrosion inhibitors (with the tolerance of corrosion inhibitor residues) to the rinse water can help minimize such corrosion. Also. and pharmaceutical processing. magnesium. Two problems are inherent with such drying solutions: • Convection or microwave ovens are not always applicable due to space and time constraints or lack of automation. the use of deionized rinse water reduces the likelihood of depositing calcium. running water or otherwise agitated rinse is better than a static soak-tank rinse. deionized water is preferred over either tap or distilled water because of its lesser potential for metallic cation deposition on sensitive electronic components. and circuit board cleaning. Wet parts are placed into an oven and heat is applied to remove the water. Equipment cost and processing speed are also factors when large volumes of ultrapure rinsewater are required to remove small amounts of residue. it is desirable to have two counter-flow cascade rinse tanks with dripping “over the tank” to reduce dragout. short-circuiting of electronics. On metal parts. shorter drying times are balanced out by higher energy requirements. magnesium. Convection ovens do just that. Higher levels of cleaning may require the exclusive use of deionized or distilled water and in some cases more than three times the volume of rinse water. or other water spotting salts. While these are usually faster than physical methods. adequately drying any remaining water from a part is critical to avoid corrosion of metals. proper operation must be followed to realize cost savings and ensure health and safety. In addition. DRYING METHOD Drying can affect residues and corrosion since impurities from rinse water can be deposited during evaporation. electronic component. This causes a decrease in the water’s boiling point in order to “suck” away the moisture. or a combination of these.
this approach is difficult to automate and delicate parts may be damaged. DETERMINING PART DRYNESS Inspection is probably the most common method for determining dryness. the observation of no visual wet spot constitutes a “dry” part. dry air through a long. or blow-drying—a relatively old concept for removing water. 26 The Aqueous Cleaning Handbook • Absorption—Moisture absorbing materials (corncobs. A more thorough test for measuring remaining water involves using reagents found at any chemical supply house. Air knives dry relatively fast compared to most physical methods of drying. • Centrifugal drying—uses gravitational forces to remove water. Typically. As with selecting an aqueous cleaner. however. resulting in wet parts. however. environmentally safe. Forced drying is environmentally safe and can handle large volumes of work. Forced/filtered gases can be used to effectively dry parts. If any solvent is present. the wet spot will disappear very quickly. They are usually tumbled with the cleaned parts to increase contact with the water. and performing a relatively simple titration. Parts. complex geometries with blind holes cannot be dried adequately. POSTCLEANING HANDLING The way in which parts and surfaces are handled after cleaning can impact their cleanliness. Delicate parts may be damaged during tumbling and the drying agents themselves may further contaminate the parts. Also. Complex geometries. For this reason it is important to consider how parts are handled and stored to ensure that the purpose of the cleaning process is maintained. it may be advisable to make provisions for a clean storage place or conditions. In humid situations. nestled parts. It may be appropriate to determine how long a surface or part will stay clean while stored to determine if it needs to be re-cleaned prior to use. • Forced or filtered hot gas—combines convection heating with an air knife and offers the advantages of evaporative and blow-drying actions. simple. but batch processing is more difficult for this type of drying system. Parts on a conveyor system pass under this intense stream of air and the water is simply blown off. narrow chamber onto the substrate. solubilizing the water in methanol. however. They can also be economical and allow for automation. moisture can condense on the substrate. Depending on the environment. and high production volumes are also difficult problems. and reusable for many drying applications. This same principal can be used in a separate drying chamber in which a dry gas is also used to evaporate the water and sweep any water vapor away from the parts. and noise may also be of concern. The important thing to remember here is that not all drying processes are applicable in every situation. Large volumes of clean and dry air are required for drying to be successful. the right drying process must be carefully assessed based on the parts being cleaned and manufacturing volume.• Forced-air. Particular attention should be paid to the quality of the gas being used. A more advanced method is the use of an “air knife” that forces clean. must be angled just right for water-soluble residues to be removed and streaking to be avoided. particularly in batch process systems where cleaning tanks are employed. Automation may be easily accomplished. Tapping the parts on a brown paper towel will immediately indicate if there is trapped water. After a tank is drained it contains wet parts where dry gas (such as dry nitrogen. drierite) are cheap. CLEANING METHODS There are ten types of mechanical cleaning methods used in aqueous cleaning and each is employed—sometimes in combiAqueous Cleaning Processes 27 . Large volumes of parts and blind holes are handled easily. filters are employed on the incoming gas—with a filter size appropriate to the size of particulates which must bee exclude from the surface. or even heated dry nitrogen) is forced through the closed chamber to dry the parts. For most precision cleaners.
28 The Aqueous Cleaning Handbook Aqueous Cleaning Processes 29 . it assures clean systems without disassembly. The article should be completely submerged to prevent any deposits or etching at the air/solution interface. tanks. To clean manually. Small articles should be grouped in baskets to prevent dislodging by spray. • Machine—Machine washing is used for cleaning large quantities of components. or pad can be used for cleaning. spray clean in place uses far less solution and can be more efficient. it consists of a pressurized tank with hot water and/or steam that is connected to a hand-held wand. For spray clean-in-place. however. a detergent recommended for soaking should be used.nation—for specific types of substrates. There are two main clean-in-place methods: • Circulate clean-in-place—which involves filling a tank and system with solution and circulating it through the system. • Power Spray Wand—Commonly called a power washer. Narrow-necked parts should be placed in the center of the racks. the cleaning solution is circulated slowly for at least one-half hour—with several hours required for large systems. For nonabrasive scouring. A thorough rinse follows. A thorough rinse follows. To clean by soaking. and the machine run for several minutes to degas the solution and allow the heater to reach the correct temperature. A thorough rinse follows. the machine should run 2–10 minutes until parts are clean. as its name implies. • Spray clean-in-place—which involves partially filling the system and circulating the cleaning solution through spray nozzles. parts. It requires. Typically. wash-cycle water (approximately 60˚C) is used. • Clean-in-Place (CIP)—Clean-in-Place is used to clean pipes. dried-on residues. a solution is made up in a separate container. The wand will have a trigger to release the hot water or steam and usually has a detergent metering device or injection device to meter in detergent during spraying. and cleaning volume factors. Displace the cleaning solution by pumping in one full system capacity of water. the article to be cleaned should be wetted either by immersing it in the detergent solution. sponge. A cloth. preferably on specifically designed spindles with spray nozzles directed into the necks. The machine’s directions should be consulted for details on proper use. Of the two methods. 10 g or 10 mL of detergent per liter of hot. this may take several hours. undiluted detergent should be poured onto a wet cloth or sponge for scrubbing. In general. Its chief advantage is that. irregularly shaped articles aligned so that the long axis faces the ultrasonic transducer (usually the bottom). brush. Typically. good circulation for effective cleaning. Small articles should be placed in racks or baskets. Soiled parts can be placed in a soak tank until such time that they can be washed. It should be used as a pretreatment to prevent soils from drying onto a part. the parts are loaded on racks with open ends facing the spray nozzles. Only low foam detergents designed for these machines should be used. • Ultrasonic—Ultrasonic cleaning is used for larger numbers and repetitive batches of parts. and filtration systems. • Immersion/Soak—Soaking is used to clean small items and the insides of larger vessels. Soils should be soaked until they are removed. or by using a soaking cloth or sponge. Then complete rinsing by circulating and draining at least two times the systems water capacity. a low foaming detergent is used. They include: • Manual—Manual cleaning is used to clean small batches of parts and surfaces. Protective gloves and eye protection should be worn if recommended or required. followed by rinsing and flushing thoroughly. the ultrasonic tank filled. Avoid loading parts touching each other where possible. To clean in an ultrasonic tank. Some soils may require additional agitation or wiping in order to remove them. and a detergent soak solution made up according to the directions. Soaking is also effective to clean or pretreat very difficult.
or brush agitation may be acceptable for items that are small in volume and size. Examples: • Small items—Cleaning by hand with cloth. IMPROVING PERFORMANCE BY CONTROLLING EFFICIENCY VARIABLES By choosing an appropriate cleaning method. 2. Precleaning handling As a general rule. then varying the cleaner. If it is a parts washer which relies on spray agitation or pressurized spray as in a glassware washer or washer sanitizer. The cleaning method. concentration. 1. dictates the type of agitation available. While very large items or large quantities of items with less critical throughput requirements may be handled in large dip tanks. As glassware washers. an optimized aqueous-cleaning system can be achieved. Getting the greatest performance in aqueous critical cleaning requires controlling the eight important variables that affect cleaning performance. reliable. or proper packing of parts by the parts supplier.• Washer/sanitizer—A high temperature washing machine usually larger than a home dishwasher. They are usually available in small under counter sizes that are approximately the size and dimension of a home dishwasher. using the right rinsing and drying process. to immersion soak tanks. or a variety of larger floor standing models for cleaning higher volumes of glassware. Agitation/cleaning method Usually the cleaning method is selected first—depending. critical items—and their volume— will determine the type of cleaning procedure. upon the practical considerations of your cleaning problem. • Parts washers—Parts washers are a class of washing machinery used in industrial cleaning that covers a wide variety of types of cleaners. it has racks where devices to be cleaned are placed with very hot water used during cleaning to give some thermal sanitation. Aqueous Cleaning Processes 31 . of course. temperature. then you need a low-foaming detergent. • Glassware Washers—Glassware washers are used for washing laboratory glassware. parts and surfaces must be cleaned promptly after becoming soiled to avoid drying and setting up the dirt on them. to variations on the washer sanitizers or glassware washers as discussed above. in turn. can make it easier to successfully clean parts or surfaces. Clean storage conditions for parts. There is a class of PC board washer that is called a conveyorized or continuous washer that has a conveyor belt that carries the boards past a series of washing spray stations and rinsing stations. and floor standing models for larger numbers of boards or larger sizes of boards. • PC Board Washer—Like glassware washers these typically come in under counter sizes. Versions of these machines that are used in cleaning medical instruments may even have pressure seals and use high pressure steam to achieve higher temperatures for higher degrees of disinfection. If you are dealing with a machine called the parts washer it can be important to determine which kind of parts washer it is. These are usually spray wash machines that have racks mounted inside them with spray nozzles to dis30 The Aqueous Cleaning Handbook pense detergent and rinse water. These vary from ultrasonic washers which were discussed previously. these will often be connected to a deionized water source in order to be able to rinse with the deionized water. If it is a ultrasonic cleaner or an agitation under immersion cleaner you may be better off with those detergents suitable for those kinds of cleaners. to elaborate agitation machines having immersion tanks with bubbles running through them or with some kind of inert media that is vibrated inside them with a solution. In laboratory cleaning it is often critical to have a deionized water rinse to prevent any residue left from the rinse water. and time. • Important items—You may want to clean in ultrasonic immersion tanks for items requiring more controlled. sponge. and reproducible cleaning that is less subject to human error.
the faster and more efficient the cleaning. 3. heat drying. Physically removing by wiping. purified-water rinse. Agitated or running water is always preferable to stagnant soak rinsing. however. the higher the temperature. Choose a cleaner with the appropriate combination of cleaning functions for your soil that will perform well with your cleaning method. If the purified water is expensive to use. High temperatures also help remove soils such as wax or silicon oil that typically can only be softened at temperatures above 170˚F in conjunction with a high-emulsifying cleaner. They must be balanced against a commensurate increase in corrosion. Be aware that the rinse water is the last thing to touch the item you are cleaning. Rinse procedure Rinsing methods are usually dictated by practical considerations that are compatible with the cleaning method you have chosen. optical. Another way to minimize rinse water deposits is to dry by a water-removing method rather a waterevaporating one. It is important to choose rinse water that is free of problem residues. for higher level cleaning three or more volumes of rinse water are usually required. two volumes of rinse water for every volume of wash water may be sufficient. 6. medical device. Evaporation drying methods such as air drying. It’s important to note. Drying method You can dry by physically removing rinse water or by evaporating rinse water. and coating applications—Use organic-free distilled or reverseosmosis water for organic. batch-parts washers. deionized water. • Pharmaceutical. 5. Note that vacuum drying can evaporate a wide range of impurities that are nonvolatile at room temperatures. film-sensitive compounds or parts. Examples: • Electronic components—Use ion-free deionized water for components that are conductive ion sensitive. The substrate and application for your parts also help determine the type of rinse water. • Manufacturing—Use low calcium/magnesium soft water. 4. Such methods avoid precipitating out any impurities or salts that may be present in the rinse water. saponifying. 32 The Aqueous Cleaning Handbook Aqueous Cleaning Processes 33 . • Very large quantities—Parts with rapid throughput requirements may require conveyor-type spray washers. Generally. For cleaning mechanisms that have firstorder reaction kinetics (such as emulsifying. High temperatures are particularly important in machine/spray washing where a droplet of solution only has a split second to react with the soil before the next droplet of cleaning solution displaces it from the surface. centrifuging. Cleaner type and concentration Detergents should be compatible with the cleaning method and effective on the soils you are removing—one that will not damage the substrate you are cleaning. It is also important to use sufficient rinse water to assure complete soil and detergent removal. that high temperatures are not always desirable. and dispersing). drying fluids.• Large quantities—May also dictate the use of ultrasonic immersion cleaning. or distilled water to avoid calcium/magnesium water spot deposits. or mechanical washers. For basic crude cleaning. Whatever is in the rinse water can end up on your surface. and vacuum drying can potentially deposit any nonvolatile impurities present in the rinse water. Temperature Changing this variable gives the most dramatic results. an increase of 10˚C (18˚F) will double the rate of cleaning. blowing. or other physical removal techniques will remove the rinse water before it has a chance to evaporate. you can often get by with an initial regular tapwater rinse followed by a final.
concentration. • Ultrasonic cleaning—particularly effective on small parts with blind holes and crevices that are inaccessible by spray cleaning. possibly even including ultrasonic agitation. bracket the cleaner manufacturer’s recommendation and then increase or decrease the time. Examples include plastics. To optimize your system. The following are the predominant cleaning methods: • Manual cleaning—typically chosen for small-volume batch cleaning. some form of high-volume spray cleaning application will be required. 8. As the volumes or quantity of the parts or surfaces being cleaned increases. doubling the cleaning time may only give a 10% increase in ability to remove soil. doubling the detergent concentration may only give a 10% increase in ability to remove soil and a 25% increase in bath life.Also. Soaking is not labor intensive. Ultrasound helps with dispersing and mass transfer of the cleaner and the replenishing of fresh cleaning solution to the surface of the parts being cleaned. Cleaning time and concentration Above a certain minimum concentration of detergent. soaking is best suited to small volumes of robust parts where time is not terribly important. 34 The Aqueous Cleaning Handbook Keep in mind. rigorous operator training and retraining needs to be considered. SELECTING A CLEANING METHOD The choice of cleaning method is determined by the quantity of parts to be cleaned. Care should be taken in choosing a soak method of delicate parts are being cleaned. Well-written cleaning procedures and training procedures should be provided for—even going go so far as to certify operators in different cleaning methods with periodic recertification. Beyond a certain minimum cleaning time. at a smaller volume. Ultrasonic cleaning involves more expensive equipment and is typically suitAqueous Cleaning Processes 35 . and the budget available for equipment. For consistent manual cleaning. switching from an immersion. This process is essentially soak cleaning enhanced by ultrasonic sound energy. aluminum not above 60˚C (140˚F). and proteins not above 55˚C (130˚F). many materials require using only the highest temperature that will cause no harm to a substrate. As the parts and volumes increase further still. the cleanliness level that needs to be achieved. Due to the longer times involved in soaking. immersion cleaning system. manual cleaning for small volumes. Often a cleaning method choice is based on volume. for example. This greatly accelerates the speed of cleaning and can greatly improve cleaning in small spaces or crevices. 7. The levels of cleanliness that can be achieved by manual cleaning are actually very high. their configuration. may require reconsidering the choice of detergent. may be indicated. and agitation according to your needs. which often cannot be cleaned above 70˚C (160˚F). agitation. In many cases dropping the temperature significantly can result in cleaning performance decreases that cannot be made up for by increasing time. This can be important in a validated cleaning environment—where a future change in cleaning methods will also add additional concerns for validation. or cleaner concentration. although the operator determines the consistency of cleanliness. there is also more time for corrosion due to interaction between the surface being cleaned and the solution used to clean it. • Soak cleaning—usually chosen for small quantities of parts when there is sufficient time in which to clean them. if this level of output is anticipated. The minimum concentration and the minimum length of cleaning time may be around 25% of a typical conservative recommendation from a detergent manufacturer. Therefore. it is often wise to use a cleaning method that can be scaled up to high-volume manufacturing. As a result. Postcleaning Handling Providing for clean storage or clean packaging in which to put your clean parts or surfaces can help maintain them in a clean state.or manual-cleaning method to a spray-cleaning method. temperature. although it is typically a slow process. however. recognizing that decreasing any one of these variables may require increasing the others.
(Also. Therefore. requiring additional manual cleaning. Bath life can also be extended by adding one half as much detergent of the initial load after partially depleting the cleaning life of a bath.able for somewhat larger volume batches where a higher level of cleaning is required. a pH change of 1 pH unit towards neutral indicates an exhausted cleaning solution. under-counter. for example. • Spray clean-in-place—typically used in larger tank systems where the efficiency achieved by less solution usage warrants the cost of installing the spray system. Free alkalinity titration can also be used to control bath life of alkaline cleaners where the soil being cleaned depletes free alkalinity—as is often the case with oily soils. For industrial critical cleaning applications high levels of cleaning can still be achieved with extended bath life. you should investigate spray under immersion. whereby parts are placed on a conveyor and are cleaned with spray nozzles as they pass through the conveyor cleaning system. The process: • Titrate a fresh solution to determine new-solution freealkalinity. it may be wise to consider using a spray-cleaning detergent that will also perform adequately in soaking operations. try adding 25 ml of cleaner concentrate to recharge your solution. For very high-volume parts washing. an immersion cleaning system may have difficulty cleaning the top of a tank. In general. detergent solutions can rarely be used more than a week even with these bath life extension techniques. a conveyorized system. if it is anticipated that a process will ultimately be scaled up to a spray clean-in-place system. pH and.) Perform a new free-alkalinity titration to confirm the recharge the first few times this recharging method is used to be sure that the detergent being used is linear with respect to free alkalinity depletion. % solids by refractometer can be used to control bath detergent concentration. • Clean-in-place by circulation system—typically used for piping or small tank systems where a spray clean in place system can not used or in filtration systems where the filters being cleaned can not be accessed by spray nozzles. the depletion of those conductive salts can be measured. Fresh solutions must be made up periodically. (For example if the initial solution is made up with 100 ml of cleaner concentrate and a 25% drop in free alkalinity is observed. By knowing the conductivity response of the detergent. • Add more detergent to the bath to bring the free alkalinity back to the new solution free alkalinity. For instances where you have higher volumes of parts where it makes sense to use spray cleaning. 36 The Aqueous Cleaning Handbook BATH-LIFE EXTENSION AND CONTROL For the highest levels of critical cleaning only freshly made up solutions should be used for cleaning to avoid any potential for cross contamination. very large parts (where an operator can physically move around the part. The choice of a cleaning machine depends on the batch and size of the pieces being cleaned. sludge will eventually form. • Titrate the used solution to determine the percent drop in free alkalinity. For cleaning very. Spray cleaning systems are very good for parts and surfaces that are readily accessible to the spray. vehicles or very large assemblies) it makes sense to use a power spray want or handheld pressure spray device to clean part exteriors. This form of bath life extension cannot run indefinitely. or floor standing washer. which are detectable by conductivity. complete coverage of the tank. Aqueous Cleaning Processes 37 . may be appropriate. Conductivity. Bath life can also be extended by physical filtration of particulates and cooling and settling of sludge and skimming of oils. Under frequent daily use. it often makes sense to employ some form of cabinet.) One must keep in mind when choosing which method to use for cleaning tanks that a detergent that performs well for soak cleaning may not perform as well in spray cleaning. Bath lives can be controlled to extend them by using conductivity. As batch volumes move up from those that may be best addressed by ultrasonics. They are not as good at dealing with blind holes and small crevices. Most cleaners have conductive salts in their ingredients. The spray cleaning of tanks can also give more reliable.
51 13. the bath will ultimately reach a point where it forms sludge (or where some other failure mechanism occurs).250% 0. The following table gives specific examples of concentration vs. 1. In general.60 63. Alconox Guide to Critical Cleaning. aggressive chemicals. Using the data below one can derive the concentration of detergent from measured conductivity. detergent depletion and dilution by make-up water can be determined.275 2. it was found that flash rusting could be avoided by using 120°F rinse water in place of the 150°F rinse water.71 22. Variables and Vitals of Metal and Electronics Aqueous Cleaning article by Malcolm McLaughlin.6 8. p.8 Liquinox 0.63 Citranox 0. use less contact time. INC CLEANERS AT 22 DEG C Concentration 0.Many cleaner manufacturers can supply the curves of detergent concentration versus conductivity. and shorten cleaning time and agitation.6 Terg-a-zyme 1. metal corrosion can occur during rinsing and drying.475 0. lower pH detergents.65 24.org 38 The Aqueous Cleaning Handbook Aqueous Cleaning Processes 39 .55 20.21 4.08 3.6 Alcojet 1.70 41. The time to dump the bath and start over is often defined as being after a certain number of parts or length of time as determined using some sort of cleanliness measurement.corrosionsource. time.alconox.682 0.48 6.47 Detergent 8 (uS) 21. For best results.rti.011 1.747 1. use lower cleaning temperatures. Keep in mind. With mild steel one can have “flash rusting” when rinsing with hot water and drying with hot air. Vol.3 Alcotabs 1. In some instances. Note that conductivity is very temperature dependant and detergent solutions do not have the same slope as many default settings on temperaturecorrecting conductivity meters.51 4.500% 1. allow hot detergent solutions to cool to a consistent temperature for comparison.36 11. use the mildest pH detergent to limit metal corrosion.17 REFERENCES Alconox Cleaning Solutions Newsletter.00 29. Typically this kind of measure and recharge can be carried out through several iterations. By adapting these curves to your conditions and measuring the conductivity.com www.1 7.327 0.402 0. and finally.000% 4. Appropriate Drying Technology Completes Successful Cleaning from Precision Cleaning.912 3. For instance. With aqueous cleaning. whether depleted or not. www.cleanersolutions.05 9. Precision Cleaning. To reduce metal corrosion concerns (in approximate RESOURCES www. however.99 12. January 1994.108 0.354 2.34 15. Forced air drying and air knives that physically remove rinse water can also minimize corrosion.136 2.125% 0. Higher pH detergents may have metasilicate corrosion inhibitors that often allow it to be used successfully to clean soft metals such as aluminum.clean.000% Alconox 1.com www. The conductivity will typically not detect the point of cleaning failure.38 2. in a case where flash rusting on mild steel had been occurring due to using 150°F rinse water and ambient air drying. as well as drying with hot oxygen-free gas such as nitrogen.58 5.org. use less agitation. at which time the bath must be dumped and a complete batch of new cleaner employed. conductivity for some specific Alconox-brand cleaners. 37. Cleaning Procedures section.195 0. Drying Systems.987 1. Keeping the surfaces cleaned hot by using hot rinse water and by using rapid heat or vacuum drying can accelerate drying and minimize metal corrosion. to reduce plastic corrosion.000% 2. lowering the water temperature or drying temperature can help avoid corrosion on mild steel.30 87. but will only detect concentration of cleaner present. use less aggres-sive cleaners that have less solvent or surfactant character or use lower concentrations of those cleaners.02 26.83 6. order of importance) use less heat.60 106.68 18. CORROSION INHIBITION Corrosion during cleaning is accelerated by the same things that accelerate cleaning: heat. Number 3 “Improving Performance—Controlling the 6 Big Efficiency Variables. This determination can be used to figure out how much detergent to add to the cleaning solution to restore cleaning performance. TABLE CONDUCTIVITY (Ms) VS CONCENTRATION OF ALCONOX.614 1. In general.184 2. Corrosion inhibitors can be added to rinse water provided that any associated inhibitor residue does not interfere with the surface being cleaned. and agitation.40 Det-o-jet 0. December 1997.213 0.
In practice. In addition. precision parts. Current corrosive mineral acid or caustic cleaners may present worker exposure hazards and environmental disposal problems.CHAPTER FOUR Selecting an Aqueous-Cleaning Detergent The major requirement in cleaning electronic parts. The use of appropriate aqueous cleaners can replace the use of volatile organic and ozone. The cleaning method should be noncorrosive to the component and the detergent chosen should exhibit exceptional free-rinsing qualities. (See Table 4A) Key considerations include: 40 The Aqueous Cleaning Handbook Selecting an Aqueous Cleaning Detergent 41 . assemblies. Current solvent cleaners may have ozone-depleting potential or Clean-Air-Act-Amendment-regulated volatile organic compounds (VOCs). 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. suitable aqueous cleaners can be milder and easier to dispose of than mineral acid or caustic cleaners.depleting compounds for cleaning. Critical cleaning requires careful selection of cleaning chemistry and methods to ensure adequate performance without sacrificing either worker safety or benign environmental impact. and metal surfaces is that there be no residues that interfere with further use or processing of the cleaned surfaces.
• Type of substrate—Metal (ferrous/nonferrous), glass, plastic, rubber. For example, substrates such as magnesium, aluminum, and similar metals may be attacked by some types of chemicals. Stainless steel alloys, on the other hand, often have a high resistance to both acids and alkalies. • Type of soil—What type of soil is it? Heavy or light, organic or inorganic, oil or particulate matter. This is perhaps the single most important question to ask when you are selecting an aqueous detergent. Heavy soils require heavy-duty detergents or cleaners to re-move them. The detergent should have a high concentration of cleaning ingredients to give it a high capacity for removing soil; typically heavy soils require very aggressive cleaners. A heavy soil may often be best handled by a high dispersing cleaner that is able to move bulk quantities of soil without having to react chemically with each individual molecule of soil. Light soils require a detergent that matches the exact type of soil in order to be able to most completely remove them. If you have a light soil it is more important to know more about what kind of soil it is so that you can go from a surface that is almost clean to a surface that’s extremely clean or meets your level of cleanliness. For example, many organic soils have limited water solubility. These oily soils are often best cleaned by a high emulsifying cleaner. An inorganic soil again may or may not be water soluble, but if it is not water soluble it is often able to be removed by chelation using a detergent 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.
Finally, particulate soils are best removed by dispersant cleaners that can lift them into solution and form a suspension. Very small particulates, for example submicron particulates, need to be cleaned by a very high wetting, low surface tension cleaner that has the ability to lower the boundary layer between the surface and the solution down to submicron distances to allow the agitation in the cleaning solution to access the submicron particulate. • Part complexity—Are there severe undercuts, blind holes, or numerous part cavities? Higher-powered wetting detergents with low surface tension may be required. • Level of cleanliness required—If the part being cleaned or the manufacturing process does not require exceptionally high technical specifications for cleanliness, harsh, toxic cleaning agents can often be avoided. • Manufacturing process—For example, if a part arrives wet at the cleaning station, an aqueous chemistry may be best. • Cleaning efficiency—As a rule, cleaning efficiency increases with time, temperature, and agitation, though each may affect other important considerations such as foaming, costs, health, or safety. • Environmental considerations—The environmental impact of cleaning operations can often be minimized or reduced by selecting the most appropriate aqueous cleaning agent, and appropriate cleaning and/or recycling system.
The Aqueous Cleaning Handbook
Selecting an Aqueous Cleaning Detergent
TABLE 4A DETERGENT CLEANING APPLICATIONS AND METHODS
Application Key Concerns Metalworking and Precision Manufacturing
Clean parts, avoid volatile solvents, strong acids, and other hazardous chemicals.
Articles Cleaned/Soil Removed
Glass, ceramic, porcelain, stainless steel, plastic, rubber. Oils, chemicals, particulates. Aluminum, brass, copper, and other soft metal parts. Oils, chemicals, particulates. Inorganics, metallic complexes, trace metals and oxides, scale, salts, buffing compounds. Silicone oils, mold-release agents, buffing compounds. Metal oxides, scale, salts. Metal brightening.
Manual, Ultrasonic, Soak, C-I-P* Machine washer, power wash Manual, Ultrasonic, Soak, C-I-P* Parts washer, power wash Manual, Ultrasonic, Soak, C-I-P* Parts washer, power wash Manual, Ultrasonic, Soak, C-I-P* Parts washer, pressure spray Manual, Ultrasonic, Soak, C-I-P* Parts washer spray
Mild alkaline Low-foam alkaline Mild alkaline Inhibited low-foam alkaline Mild acid Low-foam mild acid High-emulsifying, mild alkaline Low-foam alkaline Mild acid Low-foam mild acid Nonmetal-ion, Nonionic Low-foam nonmetal-ion, Nonionic Mild alkaline Low-foam alkaline
Avoid conductive residues, avoid CFCs, pass cleaning criteria.
Circuit boards, assemblies, screens, parts, conductive residues, resins, rosins, fluxes, particulates, salts. Ceramic insulators and components.
Manual, Ultrasonic, Soak Machine washer, power spray board and screen washers Manual, Ultrasonic, Soak Parts washers
*Clean-in-Place by circulating, for spray clean-in-place see machine washer detergents.
Today’s aqueous critical-cleaning detergents are blended for specific applications—substrates, degrees of soil load, and cleaning process used. Here are a few questions to ask about a detergent brand to ensure that it meets your specific cleaning needs: 1. Does it have good detergency on the types of soils that you need to remove? A broad range of organic and inorganic soils are readily removed by mild-alkaline cleaners that contain a blend of surfactants and sequestering agents. Metallic and inorganic soils are often readily solubilized by acid cleaners. Proteinaceous soils are effectively digested by protease enzyme cleaners. 2. Is it free-rinsing? Will it rinse away without leaving interfering detergent residue? A properly formulated detergent will contain rinse aids to help the rinse water remove the detergent and soil solution. Rinsing is a critical part of high-performance cleaning. The detergent
44 The Aqueous Cleaning Handbook
usually loosens all the soil from the surface and then the rinse water needs to sweep it away. In residue-free cleaning it is important to use a nondepositing rinse aid. Many rinse aids are positively charged compounds that are attracted to a surface that repels the water from the surface. This can leave what appears to be a nice clean surface, but in fact it will be covered with the hydrophobic water repelling rinse aid. 3. Is the detergent recommended for the desired cleaning method? (See previous discussion.) 4. How hazardous is it? For example, is it highly alkaline or acidic, presenting a personal health hazard? Is it corrosive? Does it present a reactivity hazard with soils? Is it a flammable or volatile solvent? These considerations can be evaluated by reviewing a Material Safety Data Sheet for the agent. Preferably, it should not contain any hazardous ingredients listed on the OSHA standard and Hazardous Substance List 29CFR 1910 subpart Z. 5. Can it be disposed of easily? Any detergent chosen should be readily disposable and biodegradable, containing no RCRA Hazard Classification or EPA Priority Pollutants designation. Otherwise, the use of hazardous cleaners may require special, expensive waste-handling treatment. 6. Is it environmentally friendly? Considerations include ozone depletion potential and volatile organic compound (VOC) content regulated by the Clean Air Act Amendments. Approval under anticipated future restrictions should be weighed as well. 7. How economical is it? The detergent should be widely available and affordable. For optimal economy, a concentrated detergent is typically used at 1:100 dilutions. In choosing an appropriate detergent, one must consider the equipment it is being used to clean; the level of cleanliness and residue removal that is necessary; the cleaning method that is to be used; and the performance of the detergent. Key questions to ask about selecting a cleaner are: • Does it have fillers? There are a number of ways to tell
Selecting an Aqueous Cleaning Detergent
whether the powder or liquid brand you’re considering 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 compounds which do not perform a useful cleaning function but merely add to volume and weight (and shipping costs). Liquids: With liquid detergents, the most common filler is water. It is important, however, that no more water is used than necessary to ensure a good solution, maintain stability, and prolong shelf life. — What is the concentration? Powders: It is rare that a detergent will require more than a 1 percent solution of detergent to water (1:100). Liquids: A typical alkaline cleaner should not need to be used at a dilution of more than 1:100. And, semiaqueous or solvent-containing cleaners may reasonably need to be used at dilutions of 2:100 or more. • What are the operating costs? Operating costs for aqueous cleaners are generally low since these cleaners are usually concentrated—typically using only one to five percent of cleaner solution to water. Also, aqueous cleaning baths last a relatively long time without recycling. Strong acid cleaners generally require constant system maintenance since their aggressive chemistry can attack tank walls, pump components, and other system parts as well as the materials to be cleaned. (Inhibitors can be used to reduce such attack.) Another disadvantage of strong acid cleaners stems from soil loading— particularly metal loading—which requires frequent decanting and bath dumping, leading to relatively high operating costs compared with alkaline cleaners. In contrast, alkaline cleaners are often more economical compared to acid chemistries, because they do not cause excessive maintenance problems.
46 The Aqueous Cleaning Handbook
MONEY SPENT ON CLEANING AGENTS PER YEAR
Under $10,000 46% $10,000-$50,000 35.5% Over $50,000 18.5%
Source: Precision Cleaning Magazine, December, 1996.
Human health and safety considerations include detergent toxicity, corrosivity, reactivity, and flammability. These considerations can be evaluated by reviewing a Material Safety Data Sheet for the solvent, chemical, or detergent with which you intend to clean. The detergent(s) you choose for your application preferably should: • be formulated to minimize health-safety concerns while still offering outstanding cleaning performance • not contain any hazardous ingredients listed on the OSHA standard and Hazardous Substance List 29CFR 1910 subpart Z • not have flash points or stability hazards. Many detergents strong enough to remove fingerprints, can remove oils from skin and, therefore, have the potential to dry out skin and cause “dishpan hands.” This is especially true of detergents designed for machine spray washing which, in order to perform in the limited contact time afforded during spray cleaning, are considered to be aggressive cleaners. Protective neoprene, butyl, rubber, or vinyl gloves are recommended for any extensive manual cleaning operation. In addition, many detergents are potential eye irritants, and should not be used without eye protection. See Chapter Eleven,
Selecting an Aqueous Cleaning Detergent
” for further discussion. Again.cleanersolutions.alconox. regulations are enacted and products are being designed and marketed. 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. has not faded entirely.com www.” environmentally speaking.com www. In fact. public environmental awareness has increased markedly in recent years. sometimes without adequate comprehension of the scientific disciplines that are required. and contain no RCRA Hazard Classification or EPA Priority Pollutants.rti. ENVIRONMENTAL CONSIDERATIONS Environmental considerations include concern over volatile solvents with ozone-depleting potential and volatile-organic compound content that is regulated by The Clean Air Act Amendments. formed over three decades ago. or at least to a position that compares with spirituality. Surfactants are not generally viewed as a menace to the environment. Precision Cleaning ’97 Proceedings. too. Both the issues of health and environmental safety are important and extremely complex. A large portion of the public wants to “do the right thing. To this end.or poorly-biodegradable surfactants which are no longer used in modern aqueous cleaner formulations. for a more complete description for health. This foam resulted from non. Any detergent chosen should be biodegradable and readily disposable. Nonetheless. We have entered the age of environmental marketing and are forming attitudes about environmental attributes. 22.clean. their environmental attributes often receive as much attention as their technical properties and economic aspects.org 48 The Aqueous Cleaning Handbook Selecting an Aqueous Cleaning Detergent 49 . REFERENCES Aqueous Cleaning Chemistries. Then. safety and environmental issues see Chapter Eleven. RESOURCES www. Precision Cleaning.org www. December 1996. environmentalism has transcended from a social attitude to an almost metaphysical level. One reason may be the mental image most people have of foaming streams and rivers. p. Selecting An Aqueous Cleaner by Malcolm McLaughlin.cleantechcentral.“Environmental Health and Safety Considerations.
Select a test substrate for cleaning. Identify the key reason you are developing the system. Perform tests and optimize your selected system. 7. Select an aqueous cleaner for evaluation. rinse method. T 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 system is desirable. 2. 5. and a drying method. 6. The following table outlines some of the reasons for setting up new systems and the kinds of parameters that must be evaluated for each. Select a test cleaning system that includes a cleaning method. 4. 3.CHAPTER FIVE Testing and Selecting A Detergent and Cleaning System esting and selecting an aqueous cleaning system involves a seven-step process: 1. Select a test soil and method for applying the test soil to the test substrate. Select an evaluation method that will allow determination that key cleaning criteria are satisfied. 50 The Aqueous Cleaning Handbook Testing and Selecting a Detergent and Cleaning System 51 .
ehnr. ventilation.org) (www. use of existing equipment may be desirable Organizational considerations—Having identified what is being cleaned.nc. purchasing. cleaning time labor. In short. supervisors.clean. hazards. and drying conditions Lower cost Review recurring costs of chemistry. These resources should be used to help narrow your search for types of systems and cleaning chemistries.state.cleantechexpo. and cleaner chemical characteristics to see that they fit the type of soil and substrate being cleaned Improved cleaning speed Review temperature. and quality control. utilities.cleantechcentral.com (62 Route 101A. marketing.gov) (turi. who and what will be affected by the system? It is important to consider production personnel. Information sources—In order to help identify options and those systems which may work best for you. thresholds (TLVs). public relations. Forming a team with influential representatives from within these groups will help with the ultimate success of the adoption of the new cleaning process. NY 10603) (WPC Expositions. the contaminants being cleaned.partscleaningweb.TABLE 5A REASONS FOR NEW CLEANING SYSTEMS AND THEIR CORRESPONDING NEEDS FOR EVALUATION Reason Key Considerations Waste treatment concerns Estimate quantity and characteristics of discharge. flammability. waste treatment.precisioncleaningweb. Inc. NH 03031) (Alconox.metalfinishing.uml. safety.com) (www. reporting status. Flemington. Suite 3. we must next consider the organizational implications of the new cleaning system. permits needed Air pollution concerns Estimate quantity and characteristics of volatile solvents. 30 Glenn St.owr. agitation. maintenance.us/ref/00023. 84 Park Ave. regulatory compliance. chemistry. current and expected regulatory status Worker safety Review equipment design and chemical characteristics.com) (www.cleaningsolutions. worker training needed Improved detergency Review equipment design.alconox.org) (www. Amherst. rinsing and drying procedures. TABLE 5B Internet Alconox detergent selection and use procedures Precision Cleaning Web Parts Cleaning Web Toxic Use Reduction Institute Research Triangle Institute US EPA Pollution Prevention Gems Finishing Waste Reduction Publications Cleantech (www. NJ 08822) 908-788-0343 www. engineering.com) (www. and capital costs New process Prioritize and evaluate all of the above.epa. disposal. Look for information that correlates with your reasons for cleaning and the resulting key considerations.. you may wish to consult some of the following sources of information.htm) A2C2 Alconox Guide to Critical Cleaning Conferences Cleantech (Witter Publishing. and the reasons for changing or creating a new cleaning process. need for protective devices. toxicity. White Plains. 84 Park Ave. environmental compliance.com 52 The Aqueous Cleaning Handbook Testing and Selecting a Detergent and Cleaning System 53 . It is also helpful in getting a new process adopted to be able to identify key benefits to each affected group in a manufacturing organization.rti.edu/P2GEMS/) (www.com) (www. Flemington. corrosivity. NJ 08822) 908-788-0343 www.
) Often visual inspection is sufficient for initial development work. safety. a small. Other reflective analytical techniques require special equipment to be used such as Optically Stimulated Electron Emission (OSEE) as well as Grazing Angle Fourier Transform Infrared Spectroscopy (FTIR). 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 it to see if simply soaking will achieve a modest amount of cleaning.) This is an acceptable bench test only when developing an immersioncleaning system. this is often impossible. methods for evaluating the success of the new method must be chosen. High-agitation spraying mechanisms need a cleaner that relies on kinetically faster Testing and Selecting a Detergent and Cleaning System 55 54 The Aqueous Cleaning Handbook . In evaluating a cleaner. (See Chapter Eight for methods to measure cleanliness. TABLE 5C MISTAKES TO AVOID IN EVALUATING A CLEANER AS PART OF CLEANING SYSTEM DEVELOPMENT Mistake Result Use immersion in small A high emulsifying gentler tanks or beakers to test cleaner will work best. The following table outlines some mistakes when evaluating a cleaner using a benchtop cleaning system. testing of a cleaning system should be achieved using full-scale conditions with actual dirty surfaces. Immersion cleaning techniques can use cleaners that rely on kinetically slower mechanisms such as emulsifying. A system that cleans by soaking in a beaker may not work in a spray washing machine. and environmental concerns. First. after soiling. and after cleaning to determine percent soil removal is effective as a measure of cleaning performance as long as the substrate is impervious to the cleaner. Cleaning performance must also be evaluated through test cleaning. a rinsing and a drying method must be considered. and dissolving. The cleaning mechanisms can be very different in immersion cleaning than from those involved in spray cleaning. it is particularly important to mimic the time. determine a baseline level of cleanliness and a way of measuring that baseline. circulated or the spray system poured cleaning solutions to mimic spray cleaning Match temperatures Only use available cleaning times Use a substrate to mimic the scale-up surface—perhaps take flat plates pressed together Try to use similar soils for testing Use a soil that does not represent the real soil The wrong cleaner may be chosen SELECTING THE TEST CLEANING SYSTEM Ideally. along with a variety of methods that involve extracting soils from the surface and then performing an analysis of the extract. temperature. In mimicking the actual cleaning conditions for the process cleaning method. the simplest method that will provide suitably sensitive results should be employed. Problems often occur with this approach when the ultimate intent is to use a spray washer or mechanical washer in the scaled-up process.SELECT AN EVALUATION METHOD Once the key reasons for testing and evaluating a new cleaning system are determined. In practice. and agitation that will be available in the scaled-up cleaning process. (Sometimes people also add heat and agitation so they can get more cleaning from their system. As a rule of thumb. however. A relatively simple gravimetric analysis involving weighing a clean substrate before soiling. The literature available about the cleaner under consideration should be reviewed for any health. Surface contact-angle of deionized water on a flat surface can be used. enzymatic hydrolyzing. but cleaners that will be used in will fail in the spray agitation spray cleaning environment system Use a higher temperature than will be available in scale-up Clean for a longer time than will be practical when you scale-up Use flat substrates when small crevices and blind holes will be present in scale-up A milder cleaner will give adequate cleaning that fails at lower temp A milder cleaner will give adequate cleaning that fails in shorter time A system with inadequate agitation will work on flat surfaces that fails on crevices Correction Use a Water Pik®. benchscale system which mimics the full-scale system must often be created. Accordingly.
In these very high agitation cleaning systems you may need a nonfoaming cleaner. which results in a cascade of solution running down the surface to be cleaned. possibly. The first involves gently spraying a high volume of cleaning solution over the surface of a substrate. and where the foam may burst the seals of the cabinet (and. 56 The Aqueous Cleaning Handbook The cleaner may not be appropriate for the higher agitation system. cause cavitation in the circulating pumps). higher-boundary layer conditions. Even spray under immersion can allow for some of the kinetically slower immersion cleaning mechanisms to work. in particular. there is much greater turbulence and more mechanical energy with cleaning solution bouncing off the surfaces with less cascading and sheeting action down the surface. The following table outlines bench scale cleaning methods and how they mimic larger-scale cleaning: TABLE 5D TYPICAL BENCH-SCALE CLEANING SYSTEMS AND THE SCALE-UP SYSTEMS THEY MIMIC CLEANING METHODS Bench-Scale Full-Scale Manual cleaning with tool Manual cleaning with tool Immersion in a small tank Immersion in a big tank Small tank with stirrer A clean-in-place. thus. It is possible to test a cleaner that will perform only marginally in immersion cleaning but performs excellently in a spraywashing environment. penetrating. in simplified terms. It is also very possible (and even likely) that a cleaner that performs excellently in immersion cleaning will be very ineffective in a spray washing environment. There is another more subtle difference in spray cleaning systems where. Spray cleaners need to be more aggressive and faster acting since they have but a fraction of a second to do their cleaning before the next droplet of spray sweeps them from the surface. mimic the drenching of a surface by pouring or gently pumping cleaning solution over a surface in order to mimic high volume/low pressure cleaning. although there is much more movement in the cleaning solution that occurs during spray under immersion and. There is the high volume/low pressure method of spray washing and the low volume/high pressure method of spray washing.cleaning mechanisms such as alkaline or acid hydrolysis. This results in a more nearly laminar flow at the surface with a smaller boundary layer that allows for a wider range of cleaning mechanisms and. when performing bench-scale testing for spray cleaning systems it is important to mimic the characteristics of the actual cleaning system. agitated big tank Small ultrasonic tank (be sure to use Bigger ultrasonic tank same frequencies and power densities) Gently hosing or pouring High volume/low pressure washer onto a surface Power spray onto surface Low volume/high pressure washer Testing and Selecting a Detergent and Cleaning System 57 . In particular. Again. or mimic the blasting of a surface using a pump and nozzle or Water Pik®. Immersion cleaning can have minutes or hours of contact time. In low volume/high pressure spray washing. It is important to stress that although ultrasonic cleaning can result in very high localized agitation from the cavitation caused by the sound waves. one is dealing with two major kinds of agitation. high-foaming cleaners that can work very well in immersion do not perform well in enclosed spray cabinet washers where the foam can create a barrier to the mechanical energy of the spray. It is not unusual for what is called a low-foaming or controlled foaming cleaner to perform well in such high volume/low pressure washers. and dispersing. or the particle sizes of the soil may not be as easily cleaned in higher-turbulence. For instance. wetting. the agitation occurs under immersion where immersion cleaning mechanisms are still effective. the occurrence of greater small-particulate dispersion. kinetically less time available for slower immersion cleaning mechanisms. A problem that sometimes occurs is when a perfectly successful 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.
Select rinsing and drying conditions—In any bench-scale cleaning system it is also critical to understand how the rinsing and drying processes can affect cleaning results. Also. • Concentration gradient dissolving—where the high concentration soil/solution mixture at the surface being cleaned dissolves into the rinse water. rinsing. In a static soak-tank rinse.) Tap water rinses are often sufficient to show in bench-scale that a cleaning system 58 The Aqueous Cleaning Handbook can remove a particular soil from a surface. For bench-scale testing first choose a cleaning system and then go on to test the system with a given cleaner. concentration gradient dissolving is the dominant rinsing mechanism. for example. one that might allow the use of a less free-rinsing cleaner to perform adequately in the bench-scale process. For example. When cleaning plastics. or even a slow counterflow cascade rinse tank setup. the same type of water should be available for scale-up. a running water rinse may represent a more effective rinse. of course. In benchscale cleaning. the surface considerations are more critical. For many soils it is not critical what the substrate is. in which case similar materials should be employed. The cleaner loosens all the soils and prepares them to be rinsed away. Often. since some plastics will have particular Testing and Selecting A Detergent and Cleaning System 59 . In a running water rinse system. this is not possible. If lab-grade deionized water is used for bench-scale rinsing. The same level of rinsing. however. mass displacement is the dominant rinse mechanism. mimic the rinsing that will be used in scale-up. It is also desirable to use the same quality of rinse water that will be used in scale-up. The following table shows typical bench-scale cleaning methods that are used to make up a cleaning system of cleaning. when using a series of dip tanks or counterflow-cascade tanks in scale-up. it may be practical to use copious quantities of running water for rinsing. Rinsing relies on essentially two types of mechanisms: • Mass displacement—where the rinse water physically replaces the soil/solution mixture. Sometimes. it is often possible to use tap water rinses in bench-scale testing—even though water spots will result that can be eliminated by using deionized water rinses with water removing—as opposed to water evaporating—drying methods. small stainless steel coupons or glass slides are often used for bench-scale cleaning development. creating a uniform low-concentration mixture with a resulting low concentration of soil present near the solution/surface interface. Ideally. must be duplicated in scale-up. simply putting cleaned parts under running water at a sink will be both acceptable and a highly effective rinsing technique. actual parts or surfaces with actual soils that will be cleaned should be used. and drying: TABLE 5E BENCH-SCALE RINSING AND DRYING METHODS AND THEIR CORRESPONDING SCALE-UP METHODS RINSING METHODS Bench-Scale Scale-Up Static soak static soak Overflowing dip tank counter flow cascade tanks Running water running water or efficient counter flow cascade tank series DRYING METHODS Bench-Scale Scale-Up Air dry Air dry Oven dry Hot air dry Hair dryer Hot directed forced air Compressed air nozzle Air knife Volatile solvent rinse Volatile solvent rinse SELECT THE TEST SUBSTRATE Once a cleaning method is selected for testing. and for many cleaning mechanisms “a surface is a surface”—whether it be glass or metal. however. the next step in developing a cleaning system is to select a substrate and a soil to clean. but cause failure in the scale-up process. When testing bench-scale rinsing. (Conversely. A running water rinse is far more effective than static dip-tank rinsing.
soil. try to match the characteristics of the soil.htm Metaspec CO 790 West Mayfield Boulevard San Antonio. Match the particulate sizes. Match the cleaner to the desired cleaning method.q-panel. when removing salts or inorganic soils from metals it is often important to use the exact metal that will be cleaned when a process is scaled-up. There are several suppliers of standard coupons that are more commonly used with corrosion testing. and surface being cleaned. and drying. P. temperature. rinsing. or solution of the soil. Inc. but may become very difficult to remove if it dries on the surface for several hours. It can be very useful to work with standard clean coupons. 152 Metal Samples Rd.com/msc. The same is true for porous surfaces—such as gold and some ceramics—which may require use of the same substrate for bench-scale testing in order to develop a reliable cleaning system. This is especially true for aluminum. it can also be very important to use the same surface for testing in order to be sure that the cleaning system will not corrode or damage the surface. Pay careful attention to how dried-on the soil will be in the actual process. TX 78211 (210) 923-5999 Q-PANEL LAB PRODUCTS 800 Canterbury Road Cleveland. If the objective is to find a way to absolutely clean a soil— rather than compare cleaning systems—simply smearing or applying some soil to the surface for visual inspection that some soil is present can suffice. try a cleaner at different time. SELECT A TEST SOIL It is often more important to pay attention to the soil than the surface during cleaning system development—using the same soil in bench-top testing as in scale-up.alspi. One approach is to create a uniform slurry.O. oil viscosities. do not use a natural oil to mimic a synthetic or petrochemical oil and vice versa). (Soiling the substrate on the heavy side can be helpful in designing a robust cleaning system. it may be critical to develop a way of uniformly soiling a surface in order to get significant reproducible results that are suitable for comparing cleaning systems. paste. Some suppliers include: Metal Samples Corrosion Monitoring Systems A Division of Alabama Specialty Products. A freshly applied soil may be very easy to remove in bench-scale 60 The Aqueous Cleaning Handbook PERFORM TEST CLEANINGS It is advisable to perform at least three cleanings using each set of conditions to help minimize anomalous results. and detergent concentrations to determine if the system will work. it is desirable to perform at least six repetitions of each set of conditions. SELECTING AN AQUEOUS CLEANER After establishing combinations of cleaning. chemical character (for example. Review the information in Chapter Four on Detergent Selection to make sure you are testing a cleaner that has a reasonable chance of success. Try to apply the soil to the surfaces in the same manner and quantity that will be present under actual cleaning conditions. For critical-cleaning system development.) In addition. AL 36268 (256) 358-4202 http://www. (If possible. Testing and Selecting A Detergent and Cleaning System 61 .) If using the exact soils that will be present during actual cleaning is not possible. wax melting points. OH 44145 PH: (440) 835-8700 http://www. but that can be adapted for use in cleaning testing. Similarly. it may be wise to try to avoid allowing soils to dry onto a surface in the actual cleaning conditions. then using a glass rod with spacers to spread a uniform film of soil onto a coupon to achieve uniform reproducible soil levels. Also. possibly employing a volatile solvent carrier to apply the liquid mixture to surface. Box 8.com processes. Munford.affinity for organic soils.
org 62 The Aqueous Cleaning Handbook Testing and Selecting A Detergent and Cleaning System 63 . March 1997. Number 3. This may provide a sense for how robustness of the cleaning process. A good. For example.clean. or a maximum safe cleaning temperature while optimizing the other variables. concentration. 140˚F(60˚C) for spray clean systems Practical cleaning times Once you have determined an “overkill” system that will work and a “minimal” system that probably partially fails. Decide when to stop benchscale optimizing and when to move on to pilot-scale or fullscale use of the cleaning system. 60˚C (140˚F) with a 10-minute soak. if a cleaner is recommended for use at 1% in water.com www. One can then choose some combination of time. an optimum system can be identified.rti. Developing a System. concentration. RESOURCES www.2%. less-than-minimum starting point might be 20% of a conservative recommendation from the cleaner’s manufacturer. Vol 1. REFERENCES Guidebook of Part Cleaning Alternatives. temperature. One can also hold any one or more variables constant. It is a good idea to start by using an “overkill” combination of time. then vary the temperature and concentration within the two-minute time constraint. 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 combination that failed) until satisfied that the system has been sufficiently optimized for the specific cleaning needs. Based on these results. from Alconox Cleaning Solutions. temperature. For example. John LaPlante. try a combination based on a guess of what might be slightly above the minimum requirements. 40˚C (105˚F) and a two-minute soak.cleanersolutions. Finding the minimums—Having proven that the system can work. the next step is to try a combination of what one might guess is slightly less than minimum time. the process is the same.Whether selecting an aqueous cleaner and cleaning system for a new manufacturing or processing application or switching to an aqueous cleaner. and concentration above the minimum based on how poorly the system failed to perform. if one needs to be able to clean a batch of parts in two minutes. and agitation than might typically be required in a bench-test scenario to first prove that the system you are using is capable of delivering the cleanliness required. Karen Thomas Massachusetts Toxics Use Reduction Institute.org www. TABLE 5F Typical cleaner test conditions Overkill Double the recommended dilution of detergent Maximum practical temperature Maximum practical cleaning time Minimum 20% of the recommended detergent dilution Room temperature Very short cleaning time Optimized Recommended dilution 120˚F (50˚C) for immersion or manual cleaning methods. temperature. and agitation to get some idea of where the system starts to fail. one might try and see how badly it fails at 0.alconox. Alan Buckley Massachusetts Office of Technical Assistance. such as a maximum practical length of time.
prolong their working life. 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. Although healthcare instruments themselves are often made up of robust plastics or stainless steel.CHAPTER SIX Industrial Cleaning Applications oday. It is very important to have a clean surface with no dirt on it so that when a sterilization process is carried out you do not wind up sterilizing the dirt—leaving unsterilized surfaces beneath the dirt. and reduce medical waste. and metal components. and precision manufacturing of glass. This chapter describes key considerations in aqueous cleaning for each of these industries. In short. The ideal detergent for getting reusable items clean has a neutral-range pH. the trays they are 64 The Aqueous Cleaning Handbook Industrial Cleaning Applications 65 . metalworking. healthcare. new applications for aqueous cleaning are found in a wide range of industries—laboratory science. plastic. effective sterilization requires effective cleaning. When proteinaceous soils from blood or body fluids must be cleaned. pharmaceuticals. T HEALTHCARE The ultimate goals of healthcare cleaning procedures are to keep instruments and equipment clean and sterile. Cleaning in a healthcare setting often means preparing a surface for sterilization. in order to prevent corrosion or other surface degradation. minimize cross-contamination. food-and-beverage processing.
• Suspensions—Aqueous cleaners also eliminate intensive scrubbing and human contact in cleaning large stainless steel tanks (even 2. The types of residues that need to be cleaned range from easy to clean water-soluble excipients to difficult petrolatum/metal oxide mixtures. For a discussion of the cleaning validations required under these regulations see the chapter 8 on cleaning validation. TABLE 6A DETERGENT SELECTION GUIDE FOR HEALTHCARE CLEANING Application Key Concerns Healthcare Effective preparation for sterilization. to name a few. blood and other body fluids. 316L stainless steel. pharmaceutical manufacturers will use disposable seals. Teflon. Articles Cleaned/Soil Removed Surgical. Catheters and tubes. Soak Machine washer. Reduce waste. making tablet presses and dies difficult to clean. It is also desirable for these cleaners to be effective on a wide range of residues used in a wide range of cleaning techniques. For examples of the types of standard operating procedures (SOPs) used in pharmaceutical process equipment cleaning see the Chapter 7 on cleaning procedures.000 gal) used in manufacturing liquid suspensions. tissue on instruments. Most healthcare instruments that come into contact with blood or body fluids are disposed of so as to completely eliminate. Therefore. sani-sterilizer Recommended Detergent Mild alkaline Inhibited lowfoam alkaline Enzyme Inhibited lowfoam alkaline Healthcare instruments that are cleaned are usually examining instruments of one kind or another. the risk of cross-contamination from blood-born pathogens. as well as firms that manufacture medical devices. These facilities will typically use large batch washer/sterilizers to perform their cleaning. and the International Conference on Harmonization (ICH). longer instrument life. the EU (European Union). sani-sterilizer Manual. All share the need to clean and document to government regulated standards. There are regulations that need to be complied with 66 The Aqueous Cleaning Handbook from the US FDA. to large-scale central cleaning found in hospitals and large medical centers. Some reusable examining and probing instruments (such as endoscopes) actually come in contact with blood or body fluids and must be cleaned very carefully. and examining instruments and equipment. In control cleaning. and silicon elastomers used in seals.handled in as instrument kits and are cleaned in are often made of light-duty plastics or aluminum. sustained-release product residues come clean quickly with appropriate aqueous cleaners. from manual. Even stubborn. the cleaning agents chosen must not damage the light-duty plastic or aluminum instrument-handling trays. or substantially reduce. Today many leading drug companies. Cleaning Method Manual. To simplify regulatory compliance. Examples: • Capsules and tablets—Some pharmaceutical ingredients resist going into solution. Ultrasonic. polypropylene. soak and ultrasonic cleaning to clean-in-place spray systems. Soak Machine washer. are finding that aqueous cleaners provide the same kind of scrupulous cleaning required for processing healthcare products. In some cases. It can be safer and more cost effective to use some equipment once rather than clean it. There is no more demanding application for precision cleaning than pharmaceutical manufacturing—where crosscontamination can be costly in lost product and the creation of risk to human and animal health. the instruments in the entire facility are grouped in trays and sent to a central cleaning or central sterilization facility. The materials of construction that typically need to be cleaned are glass. it is desirable to use as few cleaners as you can to remove the entire range of residues encountered. Difficult proteinaceous soils. anaesthetic. PHARMACEUTICAL Pharmaceutical process equipment cleaning includes everything from bench scale lab production for trial use to full scale manufacturing of bulk pharmaceuticals. These standards are commonly called GMP (good manufacturing practice) or the update as cGMP (current good manufacturing practice). pipes and filters to avoid having to validate their cleaning. Ultrasonic. Minimize cross-contamination. Industrial Cleaning Applications 67 . Cleaning healthcare instruments varies from cleaning small groups of instruments—such as what may be found in an individual doctor’s office or clinic—that are handled in small soak trays and sometimes cleaned ultrasonically.
. U/F membranes. soak.• Intermediates—Aqueous cleaners are ideal for cleaning glass-lined chemical reactors used in processing pharmaceutical intermediates such as powders. 1 Inorganic residues. Moving to a higher or lower in pH will shift the effective surface charge or electron density in a negative or positive direction. Packaging Drugs and Pharmaceuticals. and polymer components for benchtop labware as well as for difficult-to-clean pilot processing equipment such as bioreactors and fermentation systems. and other chemicals. Examples: • Steel—typically has an isoelectric point of 8. glass. In research and development. R/O. Inc. The isoelectric point of a surface is the pH at which the surface’s electric charge is neutral with regard to its acid/base and electron donor-acceptor reactions. Pyrogen Control. and Cr2O3 on the surface of the metal and the hydrates and hydroxides formed in aqueous solutions. Lancaster PA. Soak. Inc. Pyrogens are endotoxins or cellular debris that can cause fevers if people are internally exposed.. A recent article (Hallie Forcinio.. pigments. bases.The favored method of removing pyrogens form stoppers is washing. many stopper makers now offer prewashed stopers. Far less well known. however. The cleaner Liqui-nox (Alconox.. for spray clean-in-place see machine washer detergents. Ultrasonic. or ultrasonic agitation followed by a thorough rinse with WFI (pyrogen free water— water for injection) and post cleaning handling in a pyrogen controlled environment or packaging can give adequate pyrogen control. salts. metallics. all of which can have their electrical charges manipulated by pH.Pharmaceutical makers can render plastic containers pyrogen-free by washing the containers with an alkaline (ie pH 9-10) cleaning agent on a machine integrated with the filling line. Jenkins and K R Osborn. C-I-P* Recommended Detergent Mild alkaline Low-foam alkaline Mild acid Enzyme Pyrogens on packaging materials can be controlled by heating alone or in combination with alkali or strong oxidizing solutions or by washing with detergent (1). Soak. aqueous cleaners have long been used in cleaning metal. Controlling Pyrogens—One of the considerations in pharmaceutical process equipment for parenteral product cleaning is controlling pyrogens. Protein/ferment residues. When washing is the pyrogen-removal method of choice. power wash Manual. catalog number 1104) are used to depyrogenate heat sensitive surfaces (as well as those treated by standard heat treatment). C-I-P* Machine washer. C-I-P* Manual. March 2001 Pharmaceutical Technology p38) made reference to controlling pyrogens with the following: Liqui-nox is certainly a detergent that is used in pyrogen control. Fe3O4. As standard cleaning with 1% 120 deg F (50 deg C) Liqui-nox by manual. Since like charges repel. 1 W. Ultrasonic. Articles Cleaned/Soil Removed Product-contact surfaces. *Clean-in-Place by circulating. In aqueous critical cleaning there are numerous wellunderstood factors in detergency affected by pH. p 28. catalog number 1201) and Alconox (Alconox. 1993. TABLE 6B DETERGENT SELECTION GUIDE FOR PHARMACEUTICAL CLEANING Application Key Concerns Pharmaceutical Passing cleaning validation for FDA good manufacturing practices. Cleaning Method Manual. Stoppers for injectables are cleaned using Alconox powdered detergent solutions. which are treated to reduce endotoxin levels by 3 logs. Stainless Steel Cleaning—Since stainless steel and glass are common substrates cleaned. and amphoteric proteins. Technomic Publishing Co.. it is worth taking a closer look at some of their surface properties and how that effects cleaning and how to optimize thermodynamics of cleaning by controlling the pH of the cleaning solution. 68 The Aqueous Cleaning Handbook Industrial Cleaning Applications 69 .A. Most laboratories that do LAL testing for pyrogens use Liqui-nox to clean their glassware and testing equipment. Soak. is the role pH can play in harnessing electrostatic affects to improve cleaning efficiency. fillers. choosing a cleaner of appropriate pH relative to the isoelectric point of the surface and the pKa (inverse log of the acid dissociation constant. Ultrasonic.. see table 1) of the residue makes cleaning far more efficient—especially when cleaning residues such as acids. any cleaning agent residue must be adequately removed.5 associated with the reactivity of the oxygen in the oxides Fe2O3. Pyrogens are often controlled using heat. binding agents. plastic.
In addition to material surfaces. If the stearate ion is a residue on steel and the pH is as high as 8. when cleaning acids it is desirable to use a cleaning solution with a pH above the isoelectric point and the pKa of the acid. with a pH above the isoelectric point of the surface where the surface will take on a repelling negative character.5 and above.0-2. The pKa is about 5. wash and rinse solutions on the uppers surfaces at pumping rates equivalent to 2.5 Gpm per foot of circumference for vertical vessels. Parts of the following discussion on CIP cleaning is paraphrased from the website operated by Dale Seiberling—the self proclaimed CIP Evangelist (www. for basic residues. As systems become larger it can be worthwhile to install clean-in-place (CIP) systems. it is desirable to choose a cleaner with a pH that will not etch or corrode the surface—for stainless steel. thereby increasing the concentration of the negative conjugate base. If the residue to be remove also has a negative charge at that pH.) Clean-in-place (CIP) Cleaning—As pharmaceutical processes go from R&D to pilot scale to manufacturing. The steel and the stearate ions repel each other. but also steel surfaces that are negative in character by virtue of their being at a pH above the isoelectric point. This means that at a pH of 5 and above. Industrial Cleaning Applications 71 . it is important to also consider the corrosive effect of pH on the surface being cleaned. Typically. thereby converting stearic acid to negatively charged stearate ion.2-0. the cleaning techniques and equipment can change to fit the needs of the scale of manufacturing. For most acids. and for glass.3 Gpm per square foot of internal surface for horizontal and rectangular tanks. however. within the limits of etching. with stearic acid (C17H35COOH).5 associated with the SiO2. or at least a neutral residue and a positive-character surface without attraction. TABLE 2 OPTIMIZING THERMODYNAMIC CLEANING CONDITIONS FOR SURFACE/RESIDUE ELECTROSTATIC REPULSION Acidic residues Akaline or basic residues pH > pKa and isoelectric point of surface pH < pKa and isoelectric point of surface TABLE 1 RELATIONSHIP OF pKA. then the negative surface will repel the negatively charged residue. or at 0.seiberling4cip. CIP cleaning can be accomplished by the action of a cleaning solutions with spray or recirculation under pressure of the initial flush. the conjugate base is the negatively charged stearate ion (C17H35COO-). reversed to be below the pH at the pKa and the isoelectric point of the surface being cleaned in order to achieve a positive-positive repulsion. Raising the cleaner solution pH (past the isoelectric point). wash. then not only do we have negatively charged stearate ions due to being above the pH of 5. many residues can also undergo a change in electrical charge due to a simple change in their pH.com). within the limits of passivation. causes the surface takes on a more negatively charged character. and rinse solutions by controlling time. As in table 2. facilitating cleaning. CONJUGATE BASE AND HYDRONIUM ION CONCENTRATION HA + H2O ➔ H3O+ + A[HA] = acid concentration H2O = water H3O+] = hydronium concentration pKa = –log [H O+ ][A-]/[HA] 3 [A-] = conjugate base concentration For example. the pKa indicates the pH at which the hydronium ions and conjugate base are present in equal concentrations. and rinse solutions at flow rates which will produce a velocity of 5 feet per second or more in the largest diameter piping in the CIP circuit. This results in an increase in the concentration of the negative conjugate base. tanks and blenders can be effectively cleaned by distributing flush.• Glass—has an isoelectric point of 2. A bench scale system can often be adequately cleaned by manual and soak cleaning procedures. (It is important to note that the addition of corrosion inhibitors can also extend the acceptable pH range. temperature and cleaner concentration. these condition would be 70 The Aqueous Cleaning Handbook For any cleaning. Moving higher in pH shifts the equilibrium toward the right. we begin to drive the reaction toward the right. • Piping Systems can be effectively cleaned via recirculation of flush. Thus. wash. • Mixers.
1978) that attempt to bring some clarity to the design concept. glassware. many variations of “lab style” washers have been adapted for this arena with their limitations not evident until long after the purchase and installation. Unfortunately. Service panels should be able to be designed to allow for access to the critical components through mechanical chases or locations that the design of the facility allows. and providing for solution return to the CIP system. One way to set up a monitoring system is to first circulate and flush water through the CIP system with the control system monitoring the valves and pressure to assure and record proper operation. The overall scope of the design criteria is to follow FDA’s rationale that cleaning equipment should “prevent contamination or adulteration of drug products. Freestanding or recessed models must be available to give the facility the product flow characteristics required for their process. With no clear definition.67.• Integrated CIP Design may be applied to combine the cleaning of vessels and piping in one pass in which flush. Final rinses can be circulated to equilibration for rinse water sampling if desired. This concept can accomplish CIP at the minimal capital cost and is highly effective in reducing the post CIP recontamination that often follows conventional cleaning of lines and vessels in separate circuits. possibly using conductivity control to measure and record proper addition of cleaner solution. Effective use of the chassis must allow for service and technician access as well. these regulations leave many areas open for interpretation with respect to specific construction criteria for a GMP Washer. and continues to be. the washer must adapt to the particular features of the room that requires the positioning of the internal components to be accessed by the facilities or validation teams during and after the installation and calibration process. and archive this information for regulatory compliance. materials of construction should be 316L so as to allow for integration into the clean suite arena and be able to withstand the cleaning chemicals used in this arena. This will allow for easy calibration and verification during validation. A CIP monitoring and control system can be installed to ensure that the CIP system works reliably. wash and rinse solutions to the sprays. and part 211. Chamber design should allow for minimal water retention. a struggle for a clear definition of mechanical washer/dryer to properly address the requirements of GMP applications. plasticware and tooling used in pharmaceutical production adhering to GMP compli- ance. The CIP monitoring and control system can document the system’s operation and history. GMP Washer/dryer design—within the pharmaceutical industry there has been. rendering the process vessels and piping molecularly spotless after every product run—or alarm loudly if it fails. GMP Washing Machines—Equipment that is disassembled for cleaning.” Structural Flexibility—The design of the GMP washer has evolved over the past 10 years from a modified laboratory washer manufactured in a common production line. and bench scale production equipment that can be loaded into racks can often be best cleaned in a washer that can do validated cleaning. Within the GMP regs there exists several specifications (Part 133. For the outer shell of the washer. to a specific product division within the most up to date manufacturers. manufacturing tools. effective use of the chamber will allow for a minimization of cycles and a higher throughput of the washer/dryer during the production day. Chamber corners should carry a minimum of 1” radius and all surfaces should be sloped to the drain.4. Chamber Flexibility—for faster cycle times. Many times. There are inherent design criteria required for washer/dryers that will clean parts. proceed to the wash cycle. The washer/dryer must be able to perform a multiuse task while taking into consideration effective utility and floor plan consumption. Temperature and monitoring instrumentation should be able to be removed from their ports via tri-clamped connection and have enough coil length to be able to be placed on a metrology cart outside of the structure of the washer. 1963. Complete separation of tooling and superior welder qualifications are requirements for this range of products as quality control and documentation of the entire construction process is closely recorded and provided as a deliverable in the final documents. flush out the cleaner solutions and proceed to neutralization and rinsing steps. Internal structures of 72 The Aqueous Cleaning Handbook Industrial Cleaning Applications 73 .
the washer itself should be dried entirely and prepared for the next validated cycle. Component Selection—Internal components must be compliant to GMP requirements. Effective use of Teflon and stainless will allow racks and baskets to mate to the chamber of the washer. Drying systems should provide complete coverage to all aspects of the load. and other forms of stainless (except 304L for the frame) should be avoided at all times. The door in the down position provides an effective loading table for the operators to easily access three sides of the rack to place components to be cleaned. particulate free drying process. resulting in costly down time of the production facility. Multiple level loading configurations will allow for maximum utilization of the chamber volume while minimizing the consumption of WFI. Industrial Cleaning Applications 75 . Dead legs should be kept to a minimum of 6 pipe diameters. Additionally. Special attention should be placed with the chemical delivery system. DOP challenge ports should be provided so that the integrity of the HEPA’s can be challenged on a regular interval. Plumbing should utilize orbital welds wherever possible and be finished to a minimum of 25 Ra. Teflon wheels on the racks can provide for a smooth transition into the chamber. (Threaded connections are to be avoided as they are entrapment areas for water and particulate that could lead to cross contamination of the products being cleaned. Spray headers should be positioned at the top and the bottom of the basin to aid in the cleaning of the parts positioned In keeping with design criteria of utility savings and GMP construction. This has been an overlooked area of GMP washer design due to the difficulty and expense of providing for an effective solution. Cold rolled steel. thus adding to the number of accessories in the clean suite. (Internal lights required for their use need gaskets that have maintenance issues and the doors are prone to leakage and service maintenance that may not be possible during a production run. the design of a loading surface should allow for the weight associated with these components. 316L stainless steel should be the material of choice for all metallic areas. Care should be taken with respect to the mating of the inventory systems to the hydraulic circuit. There should be no mechanical attachment required for the accessory racks.the chamber should feature rounded edges with no threads or entrapment areas. Heavy parts can be placed on the door without having to reach into the chamber of the washer. the chamber volume should be sized to match the load configuration required for a specific facility. Care should also be taken to match the items to be cleaned so that an effective load and unload pattern can be established that minimizes operator errors. copper. Nonshedding materials should be used throughout the drying circuit. This design is inherently more expensive but can be justified quickly. Two types of doors are typically available for this application: • Vertical doors—These allow for easy access to the items to be cleaned but make it difficult to provide for a seal to the chamber and require the use of loading trolleys. High temperature rated HEPA filters should be the final point for the air entering the basin or accessories so as to provide for a clean. ) • Horizontal drop-down doors—These provide for an effective loading table that also serve as an effective containment structure for the chamber. Gaskets can be matched to GMP requirements that will allow for complete sealing of the chamber thus allowing for no partic74 The Aqueous Cleaning Handbook ulate migration into or out of the chamber.) Since loads for GMP cleaning can range from glass to plastic to stainless parts. 316L stainless steel finished to a uniform 25 Ra should be a baseline for these washers. Delivery systems must allow for the addition of precise amounts of additives (caustic detergents and acid based products) and must withstand to the harsh nature of the ingredients that is being delivered. Vertical doors typically have a window built in that has become popular with lab-style washers but have no functionality in GMP. a commercial laundry chemical system is used only to be the source of failure months after qualification. Many times. Sanitary diaphragm valves should be available for all areas that come into contact with process fluid. Separate circuits for the basin and the hydraulic circuit (including the internal parts for the loading accessories) will provide for the fastest and most effective cycles.
Once this information is assembled the parts need to be grouped together in the loads that are required by the facility to be cleaned and an idea can then be formulated as to the chamber volume required to complete the task. This challenge requires that the design function of the inventory systems for the GMP washer have a full understanding of the materials that will be cleaned as well as their dimensional aspects. and a spare E-prom • Passivation report • As built drawings • IQ/OQ documentation Cleaning of components utilized in a GMP environment presents obstacles that are not found in generic washing of glassware or parts for the lab or research function. Ergonomics should be reviewed so as to not overload the operator and to maximize the parts/run in order to minimize the utility consumption of the facility. Documentation Requirements—The final part of the package for a GMP washer is the associated documentation that will give the validation teams the information whereby a complete qualification of all aspects of the system can be implemented. the inventory is often the most overlooked aspect part of the project. their dimensional information. A clear understanding of the items to be cleaned. Ergonomics of the load and rack must be addressed at this point so as to make the additional design and steelwork feasible. Most often. It is this point that a clear definition of the cleaning cycle parameters can begin to come into focus.Inventory Systems—As important as the construction of the chamber. and regulatory constraints add to the difficulty of this operation. With these considerations. chassis. D. Industrial Cleaning Applications 77 76 The Aqueous Cleaning Handbook . and internal components are to the overall performance of the washer. Additional challenges such as materials of construction. An understanding of the soiling that will be on the parts to be cleaned. load configurations. Load patterns must then be addressed. This definition is paramount to the success of a validated system in that the operator must load and unload in specific steps so as to maintain the validation of the cycle. weight and specific cleaning requirements. Parts can then be arranged on a CAD drawing to illustrate the functionality of the rack and determine if there are going to be any load/unload problems to overcome. B. soiling of active pharmaceuticals. Any active pharmaceuticals must be addressed and evaluated as to their abilities to be cleaned within the limits of time/temperature/chemical/agitation. it is possible to successfully use a GMP washer to clean pharmaceutical equipment. However. The documentation package should contain (as a minimum) the following components: • User’s manual • Maintenance manual • Instrument list • Electrical diagram • Piping and instrumentation diagram • Spare parts list • Exploded view • Welding report and welder certificate • Source codes are provided in the form of a written copy. manufacturers are criticized for the mating of the inventory system to the chamber and to the parts to be cleaned. C. This aspect of the project involves a complete inventory of the components to be cleaned. a floppy disc. Programming aspects of the PLC or microprocessor can then take into account the requirements of the washer to perform the task to clean the items in the chamber. this task can be easily transitioned and implemented. In many applications specific components must be kept together during the cleaning phase so as to maintain their validated status in the scope of the process. when properly managed. A typical procedure for the understanding and evaluation of a wash protocol would include the following: A. System monitoring and data transfer to other monitoring locations will occur at this point and will play a part in the design.
cracks. LABORATORY CLEANING Despite the increasing use of disposable plastics in the laboratory. To solve these problems. Endotoxins or pyrogens are fever-causing cell debris or cell-waste products widely present in the environment. This. The principal concern for any scientist or technician working with laboratory glassware. The cleaners used must not leave interfering residues that inhibit culture growth or unacceptable levels of batch-to-batch contamination. reusable glass labware is still widely employed. As in pharmaceutical process equipment cleaning. careful consideration must be given to the materials from which these devices are composed. cross-contaminate batches. blood. Other parts of the device are exterior to the human body and may be made of less sturdy plastics or aluminum. coupled with the fact that cleaning operations typically remove only light oils from 78 The Aqueous Cleaning Handbook Industrial Cleaning Applications 79 . or body fluids. equipment must be cleaned thoroughly and any interfering residues removed. a milder detergent should be selected. Medical devices are usually assembled under fairly clean conditions. and filters. Good medical device design entails creating devices that do not have small crevices. This type of water is often called water for injection (WFI). GMP procedures must be followed. and equipment is that they be free of interfering residues. MEDICAL DEVICE MANUFACTURING The cleaning done during medical device manufacturing is performed in preparation for sterilizing and sterile packaging of medical devices. there are instruments and equipment. This is due to environmental concerns (recycling issues and disposal problems associated with plastics). must be reused. a key consideration is that there be no endotoxins or pyrogens present on the surface. even at R&D pilot scale for trials. This requires that an appropriate laboratory detergent be selected and an effective cleaning method used (Table 6C). and difficult-to-clean or reach places. particularly the example given on cleaning fermentation equipment. See chapter 8 on cleaning validation and Chapter 7 on standard operating procedures. instruments. followed by rinsing with pyrogen-free or endotoxinfree water. they can erroneously accelerate or decelerate rate dependent experiments by causing localized high concentrations of reactants inside micelles. WFI is very high purity water derived from high-purity water filtration systems. For example.BIOTECHNOLOGY When biotechnology goes into production for biopharmaceuticals and gene-therapy products. Often. The residues that need to be cleaned are often complex mixtures resulting from fermentation and cell culture. a light-duty cleaner is usually selected to remove light quantities and types of soils. and cause nonreproducible results. Cleaning these pyrogens or endotoxins requires the use of a high-emulsifying cleaner combined with heat. If these less sturdy materials are present. In some instances. lending themselves to batch-cleaning operations. These often unseen residues can cause invalid analytical results. When selecting a detergent. which for scientific or economic reasons. seals. For parenteral medical devices designed to be implanted inside the body. processes—or small particulates that are present in the relatively clean manufacturing environment—requires selecting extremely free-rinsing detergents suitable for immersion cleaning. As a result. The GMP washers described in the preceding section are often used for biopharmaceutical cleaning. the cleaning requirements can be very similar to pharmaceutical needs. They can inhibit culture growth. disposable single use items may be used for piping. medical devices are manufactured in modest quantities. Ultrasonic cleaning is a common cleaning method in medical device manufacturing. one portion of the device is intended to come into contact with skin. Usually medical devices are made of fairly robust materials that can withstand corrosive blood and body fluids. In addition. When pharmaceuticals are manufactured. and because the vast majority of procedures require glass.
Manual. Ultrasonic. cagewashers Tubes. Manual. an effervescent tablet cleaner is dropped into the washer. C-I-P* Proteinaceous soils. Soils should be soaked until they are removed. C-I-P* Machine. mild alkaline Low-foaming alkaline. safety equipment. a detergent recommended for soaking should be used. tissue. warewasher Trace metals. Keep laboratory accreditation. reusable pipets. fermentation residues Glassware washer Tablet Mild alkaline Phosphate-free. animal cages. and the machine run for several minutes to degas the solution and allow the heater to reach the correct temperature. extending equipment life. Soak. powerspray. 80 The Aqueous Cleaning Handbook 3. labware washer Radioactive equipment/contaminants. Handling of the labware in the racks should be kept to a minimum. Ultrasonic. A thorough rinse follows. labware washer. Ultrasonic. Some soils may require additional agitation or wiping in order to remove them. clean rooms. Typically. To clean by soaking. To clean manually. Small articles should be placed in racks or baskets. Soaking is used to clean small items and the insides of larger vessels. Soaking is also effective to clean or pretreat very difficult. wash-cycle water (approximately 60˚C) is used. A soak tank should be kept at the laboratory bench for immersing used labware until such time that it can be washed. plastic labware. A thorough rinse follows. This may take as long as an hour. no interfering residues. Rinsing is an often overlooked and very important part of laboratory cleaning. For machine cleaning. For nonabrasive scouring. tubing. irregularly shaped articles aligned so that the long axis faces the ultrasonic transducer (usually the bottom). 5. When ready to clean. Soak. Machine washing is used in laboratories for cleaning large quantities of reusable labware. Narrownecked flasks should be placed in the center of the racks. 1. this may take several hours. Ultrasonic cleaning is used for larger numbers and repetitive batches of labware cleaning. the labware is loaded on racks with open ends facing the spray nozzles. Soak. Cleaning Method Recommended Detergent Mild alkaline Low-foaming alkaline Manual. the pipets are placed in a holder. benches. the ultrasonic tank filled. C-I-P* and other body fluids. Soak. Protective gloves and eye protection should be worn if recommended or required. It should be used as a pretreatment to prevent soils from drying onto labware. a solution is made up in a separate container. EPA procedures. Automatic syphon washing is an effective way to clean reusable pipets. the pipets are placed in a holder over the tablet. preferably on specially designed spindles with spray nozzles directed into the necks. Soak. tissue culture. 4. a final rinse in deionized or distilled water may be required. or pad can be used for cleaning. the article to be cleaned should be wet either by immersing it in the detergent solution. dried-on residues. along with guidelines for eliminating interfering residues. C-I-P* Stopcock grease. For analytical use. scale. Siphon-type washer-rinsers Water and environmental sampling. The pipets should be placed completely covered in a detergent soak solution as soon as is practical after use. It is the most commonly used laboratory cleaning method. 2. Machine washer. ceramics. low foam High emulsifying. un-diluted detergent should be poured onto a wet cloth or sponge for scrubbing. Laboratory safety. alkaline Mild acid Enzyme Cleaner Low-foaming alkaline *Clean-in-Place by circulating. Articles Cleaned/Soil Removed Glass. or by using a soaked cloth or sponge. A cloth. and a detergent soak solution made up according to the directions. there should be at least three Industrial Cleaning Applications 81 . Manual. Small articles should be grouped in baskets to prevent dislodging by spray. C-I-P* Phosphate-sensitive labware. Only low-foaming detergents designed for these machines should be used. metal. To clean in an ultrasonic tank. washer-sterilizer. Machine washer. high emulsifying. The machine’s directions should be consulted for details on its proper use. metal oxides. In general. A thorough running water rinse that contacts all surfaces of an article for at least ten seconds per surface may be required. bio-wastes. for spray clean-in-place see machine washer detergents. blood Manual. porcelain. 10 mL of detergent per liter of hot. The following are common laboratory-cleaning procedures. This prevents soils from drying onto the pipes. Manual cleaning is used to clean small batches of labware equipment and benches.TABLE 6C DETERGENT SELECTION GUIDE FOR LABORATORY CLEANING Application Key Concerns Laboratory Reproducible results. Ultrasonic. 6. A thorough rinse follows. bioreactors. Filling and emptying small vessels with rinse water at least three times is a good rinse procedure. The article should be completely submerged to prevent any deposits or etching at the air/solution interface. and the ma-chine should run 2–10 minutes until parts are clean. and the cold or warm water is turned on at a rate that will fill the washer to cover all of the pipets and allow them to drain thoroughly. sponge. Ultrasonic. brush.
it will not leave phosphate residues. milkstone. pressure washers Manual. such as with soil or water testing the purpose of the test is to determine general water quality. In some instances. C-I-P* Machine wash. where one is often testing for the presence of phosphates.rinse cycles after cleaning. for spray clean-in-place see machine washer detergents. mild alkaline Low-foam. salts. TABLE 6D DETERGENT SELECTION GUIDE FOR ENVIRONMENTAL CLEANING Application Key Concerns Environmental No interfering residues.) Other trace analyses focus on inorganic compounds—typically trace metals due to their toxicity including metals such as mercury. containers. for spray clean-in-place see machine washer detergents. In food-and-beverage processing. Trace organic analytical ware should be rinsed in distilled or organic-free water. tubing. C-I-P* Manual.) FOOD AND BEVERAGE PROCESSING In food and beverage processing one is faced with hard surfaces that are fairly robust and can stand up to the corrosive environments typical of this industry. orange juice is fairly acidic. For example. Proteinaceous soils. Ultrasonic. (Note: Alconox is a phosphate-containing detergent. 2. or injectable water rinsing. When rinsed thoroughly. Perform equipment “blanks” by cleaning glassware or handling and sampling equipment and then performing an analysis on the glassware or equipment to determine whether it has any contaminants. Ultrasonic. counIndustrial Cleaning Applications 83 . Ultrasonic. Trace inorganic analytical ware should be rinsed in deionized water. and known toxic organic compounds. Following these procedures diligently may help to ensure that one’s research is not fraught with the problems associated with interfering residues on the surfaces of reusable labware. Articles Cleaned/Soil Removed Bailers. food-contact equipment. and zinc. pressure spray Recommended Detergent Phosphate free. should follow to assure that there is no such cross-contamination: 1. Environmental Protection Agency protocol calls for the use of phosphate-free laboratory grade detergents such as Alconox or Liqui-Nox. It has been used for cleaning phosphate analysis labware for many years. Filter membranes. Cleaning Method Manual. C-I-P* Recommended Detergent Mild alkaline Low-foam alkaline Mild acid Enzyme *Clean-in-Place by circulating. Pharmaceutical and clinical research labware may require sterile. Cleaning Method Manual. alkaline TABLE 6E DETERGENT SELECTION GUIDE FOR FOOD AND BEVERAGE CLEANING Application Key Concerns Food & Beverage Avoid interfering residues on foodcontact equipment. rubber. Soak. ENVIRONMENTAL AND WATER TESTING Typically trace analyses—usually for trace organics—are conducted for pesticides. *Clean-in-Place by circulating. manual cleaning is often employed for benches. stainless steel. In such cases. trace metals. For tissue culture and general analytical ware. Quantitative analysis is used for drinking water as well as in determining soil quality for farming or gardening. Use a laboratory-grade cleaner that does not contain any of the types of ingredients that can be analyzed to eliminate the possibility of any detergent residue that can cause cross-contamination. teflon. There are two procedures one 82 The Aqueous Cleaning Handbook Oxides. Good process design should eliminate the cracks and crevices and difficult-to-clean places in a properly designed food or beverage processing plant. or equipment. Soak. instruments. C-I-P* Machine wash. Soak. scale. cadmium. Even meat that contains blood can be fairly corrosive. while other foods have their own tendencies to attack hard surfaces. Phosphate free. known carcinogens. Ultrasonic. depending on the work being done. trace analysis is often performed for toxins. a deionized or distilled water final rinse should be used. samplers. phosphate free.S. The key consideration for cleaning is to make sure all sampling and handling equipment as well as glassware that comes into contact with the soil or water does not have any cross-contamination from the any previous soil or water tests. augers. a U. Final or all rinses in water of suitable purity should be used for analytical labware to remove any tap water residues. this procedure eliminates the potential risk of cross-contamination from phosphates. (The EPA can provide a list of types of organic compounds which might reasonably be testing for. Soak. Phosphate-free cleaners are specified because in water analysis. Articles Cleaned/Soil Removed Stainless steel. glass. pyrogen-free.
particulates. Articles Cleaned/Soil Removed Circuit boards. They may be either polar or nonpolar (as discussed previously). potassium. typically salts such as sodium. and activators are typi- GENERAL ELECTRONICS CLEANING Electronic components are usually made of metal due to their conductive nature and their ability to be bonded by soldering. board and screen washers Manual. as well as metal oxides formed on vacuum components. To clean these. causing a condition known as bio-fouling or bio-film. • Nonpolar—having no dipole moment. Ultrasonic. an undesirable contaminant since it is not only unsightly but acidic. or even ceramic surfaces.ters. salts. in the sense that “like dissolves like. TABLE 6F DETERGENT SELECTION GUIDE FOR ELECTRONICS CLEANING Application Key Concerns Electronics Avoid conductive residues. and processing equipment. power spray. fluxes. and chlorides. avoid CFCs. thus causing corrosion of electronic components.” which tend to solvate ionic residues leading to the concerns previously discussed. resins. typically an organic film with insulating and adhesion interfering properties for bonding or marking. This type of fouling is often effectively removed by an enzyme-based cleaner. Ultrasonic. Ceramic insulators and components. assemblies. One of the unique surfaces found in food or beverage processing plants are filtration membranes used to filter various process streams of food or beverage products. In meat or poultry processing plants where proteins are present it is advisable to use an enzyme cleaner. rosins. These include light bulbs and vacuum tubes where residue can “outgas” into the vacuum. Low-foam Mild alkaline Low-foam alkaline Additional types of soils encountered in electronics cleaning are solder flux residues. A special consideration in electronics cleaning involves components that rely on a vacuum to create an insulator. metal oxides are frequently better removed by an acid cleaner with high chelating or sequestering capacities. It is important to note that since some membranes are delicate and cannot face harsh alkaline or acid cleaners. While organic residues usually require some type of emulsifier for their removal. mixers. Soak Parts washers Recommended Detergent Ion-free Ion-free. This calls for cleaners that are effective in immersion cleaning. difficult-to-clean filter membranes which are often very expensive filters with high value. This type of cleaning requires a thorough understanding of the soils present on the part in order to choose a detergent that will be effective . metal oxides may be found on frame holders. It is important to clean the surface completely in order to preserve their insulating properties. For example. mobile residues. extruders. degrading it and the performance of the vacuum part. it is crucial to select a detergent which will not cause membrane damage. positive or negative ends or poles). Machine wash. • Nonionic—organic compounds that have no ionic charge and are not salts. Effective cleaning maximizes their useful life and returns their performance to high rates of throughput. screens. Cleaning Method Manual. Soak. Such processes often result in highly fouled. PC BOARDS A wide variety of contaminants can remain on the completed assembly surface if they are not properly cleaned. These are of particular concern because they are potentially conductive. Examples include juice and decaffeinated coffee processing as well as cheese manufacturing. • Polar—having a dipole moment (a molecule with partially charged. Oils or other conductive residues or particulates must often be removed. Other types of electronic components are glass or ceramic insulators. Soldering involves the use of flux. Since the foods being filtered are by definition foods or nutrients. you need high-emulsifying cleaners where there is a significant amount of organic food residue. parts. these membranes are also frequently fouled by biocontamination that grows on the nutrient value of the food. pass cleaning criteria. 84 The Aqueous Cleaning Handbook Industrial Cleaning Applications 85 . etching salts. These contaminants can be: • Ionic—those with an ionic charge. Enzyme-based cleaners are also desirable because they often can be made with a neutral or nearneutral pH that won’t damage the membranes. conductive residues. The types of hard surfaces found in these environments are typically stainless steel or robust plastics such as high density polyethylene. mold release agents. Salts such as plating salts.
This type of phenomenon must be considered detrimental to the finished assembly.g. especially if exposed to alcohol. the white residue appears after the defluxing operation after the defluxing solvent has flashed off. Many of the organic species are nonionic. Both rosin fluxes and rosin pastes are prone to form this type of white residue. especially without the expenditure of mechanical energy. This occurs when atoms of the circuit trace migrate outward across the bare laminate until they bridge the circuit width. a polymeric material such as an epoxy. Nonionic contaminants remaining on the assembly surface can also lead to performance problems. These industries use high purity aqueous cleaners in controlled environment manufacturing settings. These materials are difficult to remove during the defluxing operation. organic acids such as the rosin acids and organic acids used as activators are ionic. tan. In some instances the assembly butter coat is removed. However. sprays. If not cleaned away. If this type of white residue appears. semiconductors. There are several possible causes. These cleaners are made from high purity ingredients with filtration Industrial Cleaning Applications 87 86 The Aqueous Cleaning Handbook . The most detrimental type of contaminant is the ionic type. and it takes place because no conformal coating is 100% effective against moisture penetration. PRECISION ELECTRONICS Aqueous cleaning technology is used to meet the high level cleaning requirements in precision electronics manufacturing of disk drives. This can come about if the solvent used for defluxing has become depleted of alcohol (this is especially true of solvents based on trichlorotribluoroethane or CFC-113). White residue is not always white. Typically. etc. A conformal coating is. These contaminants can interfere with electrical bed-of-nails testing by creating electrical “opens. This can result if too harsh a solvent is used for cleaning. The rosin interaction products are termed tin and lead abietates. it builds up osmotic pressure which causes a lifting of the conformal coating thus leading to the blister or vesicle. An organic molecule by definition is one based on the element carbon. high vibration. there is the phenomenon of white residue (WR). In fact. Another instance of white residue is when activator materials are left behind on the assembly surface. The rosin also interacts with tin and lead salts formed during the fluxing operation by the activator action on the solder oxides. The presence of moisture greatly accelerates the activity of ionic species since water solvates the ions and enables them to become mobile. Mobile ionic species are also responsible for corrosion products being formed on the assembly surface. e. This is especially true when it is heated around 260˚C (500° F) or higher. Another cause of white residue is solder paste. causing an electrical short. Rosin readily undergoes degradation and polymerization (the molecules bond together to form a much larger molecule). polyurethane.cally ionic. Military contractors are required to apply a conformal coating to protect the assembly surface from moisture. beige. This is known as measling. ionic species of contaminants can cause serious problems including leakage currents between traces on a board as well as severe corrosion. or acrylic designed to protect the assembly surface from moisture. In the presence of an applied voltage across circuit traces and moisture. thus revealing the glass weave intersections. However. These thickening agent residues are prone to form a white residue. Exposure to alcohol can come about either from alcohol in the defluxing solvent or alcohol in an ionic contamination tester. Solder paste contains materials known as thickening agents (thixotropic agents or rheological modifiers). It can be gray.” They can also lead to adhesion problems if a conformal coating is being applied. Once the contaminant becomes hydrated. it is necessary to ascertain that the flux (or paste) is truly the source of the white residue and to verify that the white residue does not have another cause. and electrooptics. The polymerized rosin and/or tin and lead abietates are much more difficult to remove by a defluxing solvent because of their more insoluble nature. Ionic materials and some hygroscopic nonionic materials under conformal coatings can also lead to blistering during temperature/humidity cycling. the principal cause of white residue is due to thermal degradation of rosin. or amber in color. what can be done? First. conformal coatings also isolate contaminants and prevent them from migrating or being dislodged during temperature-moisture cycling.. the presence of ionic material or hygroscopic material on the surface under the conformal coating actually acts to promote water penetration since such contamination attracts water. This phenomenon is also called mealing or vesication. shock environments. dendritic growth can occur. Finally. of course. Mobile ionic species speed up this form of growth. In addition.
2 microns at the point of use. PE) Polypropylene (PP) Polyallomer (PA) Polymethylpentene (PMP. Cosmetic factors can also enhance buyer perceptions—with a bright. oxides. For delicate plastics consult the plastic manufacturer regarding their recommendations for cleaner compatibility or use one of the specially formulated plastic cleaners. PLASTICS COMPATIBILITY WITH CLEANERS Generally acceptable with mild aqueous cleaners Polyethylene (LLDPE. Numerous metalworking and metal finishing businesses are finding that aqueous detergents perform as well as or better than solvent cleaners in removing residues but without their harmful environmental side effects. rinsing. high-tech applications for aqueous cleaners are: • Anodized parts—An anodizing shop which produces anodic coatings on aluminum substrate caps for mounting personal computer IC chips with no conductive tail-end residues and no introduction of toxicity or flammability. precision manufacturing with metals involves preparing the surface for bonding. rapid rinsing. PLASTICS Plastics cleaning involves the selection of a mild nondamaging cleaner that is strong enough to remove the soils you are cleaning. many plastics are resistant to attack by typical mild alkaline aqueous cleaners. oxide-free finish serving as visual indicator of product quality. so it is important to use mild cleaners. Unfortunately. TFE. corrosion inhibitors that leave deposits often cannot be used for precision cleaning. TPX) Fluoroethylenes (FEP.2 microns or better requires manufacturing. TEFLON®) Polysulfones (PSF) Polyvinylchloride (PVC) Polystyrene (PS) Polyvinyl fluorides (PVDF) Polyeurethane Ethylene Propylene (EPM) Buna N rubber Nordel® Viton® Noryl® Ryton® Epoxy Clean with caution even with mild aqueous cleaners Polycarbonates (PC) Acetal polyoxymethylene (ACL) Nylon® Polymethylmethacrylate (PMC) 88 The Aqueous Cleaning Handbook Industrial Cleaning Applications 89 . It is also critical to be careful using extremely high purity deionized rinse water that can be so “ion hungry” that it is corrosive to the metal substrate being rinsed. surfaces must be prepared by the removal of debris. PFA. The end-user manufacturers may further filter the cleaners at the point of use. Delivery of finished cleaner that is filtered to 0. Thus it is important to make sure that the metal will not be attacked by the cleaning. or exposure to an environment such as a vacuum or a semiconductor that cannot tolerate interference from residues. LDPE. coating. and salts to achieve extraordinary levels of cleanliness. It is not unusual for a high-purity cleaner to be made in a clean environment where it is filtered to 5 microns and then have further filtration to levels such as 0. and rapid drying to minimize the chance for corrosion to occur. scale. short contact times. • Computer parts—A major manufacturer of thermocouples and wafers used in computers and medical devices must clean ceramics and copper paste in heated (150˚F) ultrasonic baths prior to nickel plating. filtering and packaging in a cleanroom environment. Among new. or drying process. As you can see in the table below. In general.and purification steps in their manufacture. • Aluminum—A manufacturer of heat sinks for cooling computer chips in NASA space shuttles uses aqueous detergents to remove oil and organic debris to eliminate any chance of noncondensable gas formation. ECTFA. PRECISION MANUFACTURING In many of today’s high-tech metalworking applications. ETFE.
contact lens manufacturing 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. chemicals. Oils. the level of cleanliness required is either for appearance only or for suitability for painting. Soak. they often attract and hold inorganic soils such as salts and ions. mold-release agents. Ultrasonic. C-I-P* Parts washer. C-I-P* Machine washer. a mild alkaline cleaner can often be used at modest temperatures. Oils. These must be removed from the surface of the finished product. particulates. A high emulsifying cleaner is often required to remove organic films from cleaners. salts. 90 The Aqueous Cleaning Handbook Industrial Cleaning Applications 91 .) On the consumer-product side. Aluminum. strong acids. (They use a separate. Soak. Ultrasonic. buffing compounds. C-I-P* Parts washer.For more delicate plastics. OPTICS Aqueous detergents have also found application in the manufacturing of scientific as well as consumer optics such as contact lenses. trace metals and oxides. and dimensional characteristics that make them a desirable material for many high-tech manufacturing applications. Ultrasonic. Most plastics are organic in character which makes them attractive to organic film residues. The detergent has also found application in removing the compounds used in grinding rigid gas permeable (RGP) contact lenses. plastic. copper. metallic complexes. Soak. Articles Cleaned/Soil Removed Glass. transparency. Since these are inorganic matrix materials. Ultrasonic. pH-neutral cleaner to brighten the copper and copper alloys that surround these optics. scale. Often. Very dilute cleaner solutions may be needed to clean stressed polycarbonate. particulates. TABLE 6G DETERGENT SELECTION GUIDE FOR PRECISION MANUFACTURING Application Key Concerns Metalworking and Precision Manufacturing Clean parts. Aggressive immersion cleaning using heated ultrasonics with high wetting. *Clean-in-Place by circulating. brass. and other soft metal parts. low concentration. salts. avoid volatile solvents. rubber. Soak. The company’s technicians have found that an alkaline detergent—normally used in lab washers and ultrasonic cleaning systems—was ideal for removing such wax. for spray clean-in-place see machine washer detergents. Aqueous cleaners have been widely adopted in solventreduction programs by metalworking and parts-washing operations. pressure spray Manual. one manufacturer uses machining oils and heavy waxes to grind and polish its scientific optics to exacting tolerances. stainless steel. Aqueous cleaners having good chelating properties or acidic pH are often effective at removing such inorganic soils. power wash Manual. C-I-P* Parts washer. power wash Manual. Soak. Examples of the use of aqueous cleaners in glass and ceramic precision manufacturing include: • Ceramic crucibles—used in semiconductor-grade labs and in manufacturing need to be cleaned of any mobile ion residues prior to sales to semiconductor customers. high emulsifying cleaners has been successful in providing suitable surfaces. It is critical to choose a detergent that is compatible with the type of parts washer being used. porcelain. Ultrasonic. Silicone oils. The most challenging plastic to clean without damage is stressed polycarbonate which is prone to stress cracking on exposure to low surface tension solutions such as solvents and aqueous cleaners. power wash Manual. For example. Metal oxides. Cleaning Method Manual. Inorganics. ceramic. C-I-P* Recommended Detergent Mild alkaline Low-foam alkaline Mild alkaline Inhibited low-foam alkaline or neutral Mild acid Low-foam alkaline High-emulsifying. buffing compounds. chemicals. and short contact times. scale. mild alkaline Low-foam alkaline Mild acid GLASS AND CERAMICS Glass and ceramic have excellent insulating. bonding or coating. and other hazardous chemicals. Metal brightening.
floors. Some of the most difficult to clean are titanium dioxide cremes and silicon oil emollients. Circulated. substrates. spray wand. grids. and components made of metal and plastic—permitting release of cleaned items from controlled areas. NUCLEAR Few industries use more exotic alloys. reflectors. In reactor cavity cleaning. It should also contain no fluorides. end fittings. mirrors. emollients. lowfoam alkaline Nuclear Cavities. titanium dioxide. The key consideration with on-site cleaning is that the detergent contain no chelating agents which can bond chemically to radioisotopes. a specialty chelate-free aqueous cleaner brand has been successfully used during outage procedures at commercial nuclear-power plants and auxiliary buildings for radiological decontamination of floors. Aqueous cleaning detergents are ideal cleaners for silicon. fibers Cleaning Method Manual. TABLE 6H DETERGENT SELECTION GUIDE FOR OPTICS CLEANING Application Key Concerns Optics Avoid optical interface Articles Cleaned/Soil Removed Lenses. and other hard-to-clean residues generated in cosmetics processing. Tap water may be a sufficient rinse and the traces of water spots may be acceptable. spray booth. Less rigorous rinsing is often acceptable. tools. As with pharmaceutical processing. there can be absolutely no residues that could contaminate products and cause eye or skin irritation problems. power spray Recommended Detergent Mild alkaline Low-foam alkaline 92 The Aqueous Cleaning Handbook Industrial Cleaning Applications 93 . CHEMICAL AND OTHER FLUID PROCESSING The three main areas of concern in chemical and fluid processing cleaning are: • Cleaning chemical process equipment—most notably water or other high-purity chemical delivery systems • Oxygen/gas delivery systems—where pipes and tanks need to be kept extremely clean TABLE 6I DETERGENT SELECTION GUIDE FOR COSMETICS CLEANING Application Key Concerns Cosmetics Avoid crosscontamination Articles Cleaned/Soil Removed Product contact surfaces. high foaming cleaners. static. and fasteners used in fuel assemblies for reactor cavities must be absolutely free of oils or other contaminants. personal safety equipment. Soak Spray machine Recommended Detergent Chelate free.For example. mild alkaline Chelate free. tools. and ultrasonic immersion cleaning can be accomplished with high emulsifying. and “waterproof” ingredients. Chelation interference. Soak Parts washers. C-I-P* Parts washers. Titanium dioxide cremes also often require very high temperatures and a cleaner with good emulsifying and excellent dispersants. however. walls. Components such as guide tubes. than precision manufacturing of nuclear equipment. nor have more stringent quality-control requirements in manufacturing. TABLE 6J DETERGENT SELECTION GUIDE FOR NUCLEAR CLEANING Application Key Concerns Articles Cleaned/Soil Removed Cleaning Method Manual. pigments. chlorides. or sulfur ingredients which might cause surface corrosion or intergranular stress corrosion of stainless components. Soak. Cleaning Method Manual. high-agitation cleaning solution machines such as bubble/air agitated immersion. One major manufacturer of nuclear fuel assemblies has found that large parts such as 12-foot guide tubes can be effectively cleaned through manual soaking in a 1:100 dilution of a pH-neutral aqueous detergent and hot tapwater. Ultrasonic. a “no-rinse” process involving merely wiping the parts or air blowing them may be better when highly dilute cleaner solutions are employed. and conveyorized spray machines require the use of low-foaming cleaners. Ultrasonic. Silicon emollients can be removed using very high temperatures above 75˚C (170˚F) and double-strength solutions of a high emulsifying cleaner used in a total immersion cleaning system. machine washers Recommended Detergent Mild alkaline Low-foam alkaline COSMETICS Cosmetic manufacturing involves many oils. No isotopic exchange. For appearance cleaning. coil springs.
.com www. Spray. C-I-P* Circulate.com cleantechcentral.4 Handbook for Critical Cleaning. Fonner. “An Automated System for Cleaning Tanks and Parts used in the Processing of Pharmaceuticals. A. presented at Cleaning Validation and Cleaning Processes. pp. M. Cleaning Printed Wiring Assemblies in Today’s Environment. 9-15. If this separation is done by a filtration system.. Philadelphia. (1977). T and John Chu “Cleaning Solutions in the Semiconductor Wafer Manufacturing Process” in Ch 5. Alconox Inc. Ed. Soak. H. Soak.metalfinising. D. Number 2. Vol. (1990). Griffin.” Pharmaceutical Engineering. T. pp. F. greases. J. Often a high-emulsifying cleaner is used first to remove the oils and greases. the filter membranes need to be cleaned with a highemulsifying and or high-dispersing cleaner to rejuvenate the membranes. p. 12. one is often working with small to medium sized. 2001. L. and Schadewald. 6. Pauli. Alconox Cleaning Solutions newsletter. oil. B.. Guide to Critical Cleaning. Boca Raton. D. 4. 94 The Aqueous Cleaning Handbook Industrial Cleaning Application 95 . No. oils. Detergent Selection Guide. REFERENCES Adams. In waste-treatment filtration.seiberling4cip. Soak. Cleaning Method Manual. tanks. Labib. D. Articles Cleaned/Soil Removed Pipes. membranes. grease. E. proteins. 542-561 Weitzel. C-I-P* Recommended Detergent Mild alkaline Low-foam alkaline Enzyme cleaner Mild acid Mild alkaline *Clean-in-Place by circulating. Vol. C-I-P* Circulate. PA USA (2002) RESOURCES www. Filters.com TABLE 6K DETERGENT SELECTION GUIDE FOR CHEMICAL AND FLUID PROCESSING Application Key Concerns Chemical and Fluid Processing No interfering residues. Mahmood. Jan 14-15. bio-fouling. edited by Les Hymes. clean-in-place cleaning is usually employed where a cleaning solution is circulated through the pipes and then rinsed thoroughly to the desired level of cleanliness with an appropriate rinsewater. or process oils from manufacturing processes need to be separated from waste water in order to have an acceptable plant discharge. 179-186. “Drug companies find aqueous cleaners a sure cure for cross-contamination” and Vol. C-I-P* Circulate.• Waste treatment systems—particularly those involving the use of filter membranes In piping systems. Filters. 1. Number 1. 31.” Bulletin of the Parenteral Drug Association. followed by the use of an acid cleaner to remove particulates such as organic soils and silt. Kanegsberg.. This is quite similar to the kinds of cleaning done with oxygen delivery piping systems. membranes. 1. E.com www. Soak. G. In an oxygen delivery piping system it is crucial to have no residues that would be potentially oxidizable as this could cause a flammable or explosive condition. Steven “Strategies for Simplifying Cleaning Validation” referring Dr.alconox. C. W. in-plant systems where fats. “CIP System Design and Installation. and Agaarwal. Filters. for spray clean-in-place see machine washer detergents.” Grimes. No. June 1992 article “Stopping residue interference on labware and equipment. CRC Press Publishers. silicate. “How Clean Is Clean?” American Laboratory News edition. membranes. published by Van Nostrand Reinhold. 10.
aids in making it easier to train operators so that cleaning is consistent. of course. machine washer cleaning. these standard operating procedures were written for specific detergents and temperatures for specific soils. the 96 The Aqueous Cleaning Handbook Standard Operating Procedures 97 .CHAPTER SEVEN Standard Operating Procedures A large part of successful cleaning relies on having a sound. the surface being cleaned should be identified. the control parameters and equipment used should be defined (such as conductivity or pH) the limits should be defined. The following are sample standard operating procedures for manual cleaning. In some cases. they provide examples of what should be included in a standard operating procedure. The following are lists of the items to consider. 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. However. As a result. reproducible procedure. and large-tank cleaning. they may need to be adapted to meet specific applications. and the eight key variables for cleaning effectiveness should be defined: 1) precleaning handling 2) cleaning chemistry/ concentration 3) time 4) temperature 5) type of agitation 6) rinsing conditions 7) drying conditions 8) postcleaning handling Where cleaning solutions are re-used in baths or sumps. This. ultrasonic cleaning. including in different types of standard operating procedures (SOPs).
Rinse Procedure: a. 5. deionized water. ITEMS FOR A MANUAL PARTS OR MANUAL SURFACE CLEANING SOP 1. if used g. and internal part number as appropriate b. Detergent—define full name. Do not remove parts from shipping containers prior to being ready to clean them promptly—if you know that unpacking the parts increases the risk of new contaminants. define any particular cleaning or scrubbing actions required such as: brush all surfaces vigorously. Any required protective equipment. Wiping the part with a solution soaked brush. Any baskets for handling small parts. Use cleaning solution within 15 minutes before the temperature drops below 120 deg F. distributor/supplier. Dunking the part in the solution. actions taken in response to these levels and finally the conditions under which the bath is dumped should be defined. or b. For example: place parts in basket and run them under running tap water for 20 seconds while moving basket to assure all parts are exposed to running water. or ii. Presoak the parts in a defined detergent solution at a defined temperature and time prior to cleaning – for example presoak parts completely immersed in 1% Terga-zyme detergent (1. Any rinsing containers. Container of suitable size for the detergent solution— define container e. the trigger points and alert levels should be defined. but particularly be sure to use brush vigorously on the inside of the port for at least 30 seconds 6. absorbent cloth or sponge b. Wet part or surface with solution by i. 3. For example: Mix 1. manufacturer part number. Handle all parts with finger cots to avoid adding fingerprints to surfaces – if you do not want to add any new fingerprints to a surface where you are using a cleaning process that is only designed to remove particulates e. gloves. distilled water or water-for-injection as is appropriate c. or c. Any drying equipment. eye protection. or 98 The Aqueous Cleaning Handbook Standard Operating Procedures 99 . Parts to be cleaned within 4 hours of being processed to remove grime—if you knew that the grime had a tendency to dry onto the parts and become more difficult to clean. List of parts or surfaces being cleaned. Clean by scrubbing with the brush. absorbent cloth or sponge – i. List any requirements for handling prior to cleaning. Brush.person responsible for monitoring the baths should be defined. Define any level of training or certification required to perform this cleaning operation 2.5 gallon bucket. Directions for making up the detergent solution: Make up detergent solution diluted in water of suitable purity according to directions in a container of suitable size at a given temperature.25 ounces Terg-a-zyme in 1 gallon of water) at 120 deg F for 20 minutes prior to cleaning— if you know your parts have dried on protein soils that are difficult to clean without presoaking 4. The type of things you could optionally list as they apply would be: a. Tank to be cleaned within 3 days of last use—if you had validated that the tank could be successfully allowed to sit dirty for 3 days and still be cleaned by this manual procedure. manufacturer. Manual cleaning description: a. if used h. clothing etc. the maximum number of parts or surface area this process is designed to clean. List of Materials a. or d. Define the scope of the SOP.25 ounces of Alconox powdered detergent in 1 gallon of 120 deg F hot tap water in a 2. if used f. a. absorbent cloth or sponge—whatever is used d. Water of suitable purity—define tap water. the type of report or logbook entry should be defined.
is: 1. it will be necessary to close the gas tank valve and the lines leading from it to the unit. First all operating parameters (agitation. An example of a manual cleaning SOP written for manual cleaning of a bench top fermentation reactor adapted from “Fundamentals of Fermentation: Techniques For Benchtop Fermentors Part I .O. Dip part in bucket of rinse water for initial rinse. b. pH 7 buffer e. For cleaning bench top fermentation reactors b. Or. and then place under running water at the sink for 10 seconds as a final rinse. probe presents an easy removal as you simply unscrew the thread and gently pull it out. and should then be removed. probe the tip can be visually inspected for damage. coli” which was prepared by the R & D Lab. Materials a. such as: a. Additionally. and gas feed) must be set from their current control modes (such as “PID”. Record results in batch record.O. Remove the motor and place the protective cap over the agitation shaft. dip in second bucket of rinse water for second rinse. it is necessary to carefully shut the process down. glycerine 100 The Aqueous Cleaning Handbook g. always remembering to avoid touching the membrane at the tip. Water c. Define any inspection actions such as: take 10 parts from the batch and inspect for particulates and visible smudges with a 10X magnifying glass.O.b. Open all ports in tank and allow tank to air dry 8. dissolved oxygen (D. Dispose of used detergent solution down the drain. The D. Catalog Number 1201) b. It should be immediately rinsed off and then wiped dry gently. i. probes from the unit and replace their protective caps. Reject entire lot if there are any failures. Hose down all surfaces with running water assuring that all parts of surface are rinsed for at least 10 seconds. Liqui-nox Detergent (Alconox. date.”. close the ports to keep out dust. Removing the pH probe is usually not as difficult a process as inserting it because the Standard Operating Procedures 101 . Such as. Precleaning requirements and procedures: a. pH. place parts on rack and allow to air dry. New Brunswick Scientific Co. 7. Some runs will result in an accumulation of biomaterial on the probe and it may be necessary to wipe the probe down more vigorously but in no case should the tip be touched. Note that the manual air valve on the side of the unit should also be closed as well. The probe should then be stored in a clean area in such a way as to protect the sensitive tip. Or. If a recirculating chiller is in use. temperature. The air line must be disconnected from the sparger. non-abrassive pad 3.O. Any post cleaning handling procedures.E. The next day after the tank has dried. and operator who performed cleaning. Scope a. Place parts on tray and place in 210 deg F drying oven for 40 minutes.. “D. Always disconnect the water lines by disconnecting the incoming lines prior to the outgoing lines. Inc.O. or c. chemical resistant gloves f. Operator training a qualification required 2. The next step is to disconnect the vessel from the unit. After cleaning the D. Feed lines from any addition bottles which have been used should be clamped off prior to detaching them from the vessel. if a supplemental oxygen feed was used. it should be shut off when the temperature control is shut off. Disconnect the pH and D. Drying procedure a. The temperature probe needs to be removed from the thermowell. c. sponge h. or b.) level. or c. When the fermentation run is complete. Mark tank with “clean tags” recording time. Inc. Kimwipes® d. “Base”) to the “Off” mode.
It is often necessary to hand wipe surfaces with a paper towel in order to fully remove residual traces of small particulate debris. However the danger of probe breakage is still very real and extreme care must be taken when removing it. so extreme caution and the use of chemically-resistant gloves is recommended for this procedure. The headplate should be detached by loosening and then removing the clamps that hold it to the rest of the vessel. This electrolyte/buffer can be reused. Those clamps may require rinsing. To do this it will be necessary to remove any remaining cotton and foil covering the ports. in case of breakage. it is critical to remove the headplate very carefully. If at any point in this process the probe jams. the thermowell. The vessel can now be cleaned by washing with detergent. Note that some media may be incompatible with this procedure. Now that the vessel is detached from the unit. 4. all standard precautions must be taken. in which case the media can be placed into another container for sterilization prior to disposal. harvest and sparger tubes and the short beveled tips of the interior portion of the base-type addition ports will often require special attention. Note that there may be some residual base or acid left in those lines. We recommend the use of DI water. Note that for this purpose. It is still necessary to use two hands with one hand at the top of the port acting as a guide to ensure proper removal. there should be enough so that the headplate can be clamped to the lower portion of the vessel. Note that the sides of the vessel. and side ports (plugged or unplugged) may require special attention. The headplate should be washed thoroughly with warm water and then de-ionized (DI) water. The very tip of the probe should be handled with extreme care and a Kimwipe® should be used to gently dry it off after washing. it should be immediately washed off with warm water. but it should always be inspected prior to each use for precipitation or contamination. In extreme cases it may be necessary to remove the headplate with the probe still inside so that you can approach the problem from both ends. The agitation shaft. Unless you have already specifically wiped the residual grease off the top of the glass cylinder. Note that it is Standard Operating Procedures 103 . A pad that won't scratch the steel is required for this. If the vessel is to be sterilized. All tubes and shafts must be cleaned. the vessel does not need to be sealed except for those previously cited valves and tubing which run under the liquid level.) Once the pH probe has been removed. A gentle pace for this is required. it can be cleaned. It may be necessary to scrub accumulations of biomaterial off. The remaining culture broth should be sterilized or emptied into a bucket and disinfected by using bleach or other accepted disinfectant prior to disposal. The washing of the bottom portion of the vessel requires the same procedures as the headplate. In this case. using a sponge (or an equivalent that will not scratch glass) and gentle pressure to clean the surface. c. Manual cleaning. The valve on the sampling port and all clamps on all tubing connected to ports will need to be open for proper washing. rinsing and drying description a. If biomaterial has accumulated on the probe. The probe should be stored with the tip immersed in either electrolyte or pH 7 buffer. (Note that the media will need to be removed prior to unclamping any tubing that is below 102 The Aqueous Cleaning Handbook the liquid level. The sampling tube is detached and washed separately. (We recommend that you have a spare probe available at all times.shaft will be wet and thus should be relatively easy to remove. It will be necessary to use water in the vessel. it is essential to avoid trying to force it. The rubber bulb on the sampler should be removed and rinsed separately. as is the case with a side harvest line). It may be necessary to reinsert it part way and apply a lubricant such as glycerin to the shaft and port in order to effect the probes' removal. b. The glass wool can be removed at this point as well. particularly where the baffle was adjacent to it. and the fill should be at least as high as your standard level for a run. or by using a cleaning solution.
distributor/supplier. Instead. Directions for making up the detergent solution: Make up detergent solution diluted in water of suitable purity according to directions in a container of suitable size at a given temperature. and identifying specifications 104 The Aqueous Cleaning Handbook d. 3. the lightest possible pressure should be used. For example: Mix 1. Alternatively. Any required protective equipment. a rinsing of it with warm tap water and the DI water may suffice. The type of things you could optionally list as they apply would be: a. or e. Define the maximum number of parts to put into a batch to be cleaned. gloves. Handle all parts with finger cots to avoid adding fingerprints to surfaces – if you do not want to add any new fingerprints to a surface where you are using a cleaning process that is only designed to remove particulates f. d. Turn on heaters and preheat the tank to 120 deg F (50 deg C) c. or d. Presoak the parts in a defined detergent solution at a defined temperature and time prior to cleaning – for example presoak parts completely immersed in 1% Terga-zyme detergent (1. List of parts the process is intended to clean. This will help prevent biological materials from adhering. Inc. manufacturer. Any rinsing containers or equipment f. Ultrasonic cleaning tank—define size. Inspect visually prior rinsing and sterilization for next use. Do not remove parts from shipping containers prior to being ready to clean them promptly – if you know that unpacking the parts increases the risk of new contaminants. Post cleaning procedure a. as this could lead to vessel damage. add water so that the liquid level reaches the maximum working volume of the vessel. frequency. List any requirements for handling prior to cleaning. ITEMS FOR A ULTRASONIC CLEANING SOP 1. Note that if water will run over a vessel surface that has grease on it. Parts to be cleaned within 4 hours of being processed to remove grime – if you knew that the grime had a tendency to dry onto the parts and become more difficult to clean. deionized water. if you are using the vessel for consecutive runs with the same media. the grease should be removed by wiping it off with a wet paper towel. b. a. Allow vessel to air dry after thorough rinsing 5. manufacturer. e. In cases where the vessel must be decontaminated prior to cleaning. Baskets for handling small parts. The advantage to sterilization is that not only are residual viable organisms killed.neither necessary nor desirable to fasten these clamps with the same force used for attaching the headplate prior to a run. configuration. distilled water or water-for-injection as is appropriate c. If a cleaning solution is required. and internal part number as appropriate b. Degas solution for 10 minutes to remove dissolved gasses that will dissipate cavitation energy and decrease cleaning performance b. 2.25 ounces Terg-a-zyme in 1 gallon of water) at 120 deg F for 20 minutes prior to cleaning – if you know your parts have dried on protein soils that are difficult to clean without presoaking 4.25 ounces of Alconox powdered detergent in 1 gallon of 120 deg F (50 deg C) hot tap water which will fill to tank to within 1 inch of the top of the tank Standard Operating Procedures 105 . Define any level of training or certification required to perform this cleaning operation. List of Materials a. Store vessel in a clean area. use a 1% dilution of Liqui-nox cleaning solution (Alconox. if used e. Water of suitable purity—define tap water. catalog number 1201). Any drying equipment. eye protection. manufacturer part number. Detergent—define full name. if used g. clothing etc. but residual debris will loosen and become removable by washing after the vessel has cooled.
b. do a final rinse by immersing in a second ultrasonic tank filled with deionized water – change rinse water when it reaches 50 Kohms resistance. Degas solution for 10 minutes to remove dissolved gasses that will dissipate cavitation energy and decrease cleaning performance. If using a tray or basket to lower the parts into the solution. This is particularly important for freshly made up solutions. Keep solution within one inch of the top of the unit when a beaker or tray is in place. or 8. Place parts on tray and place in 210 deg F drying oven for 40 minutes. such as: a. List of Materials a. (see chart on pages 107-108) 106 The Aqueous Cleaning Handbook Standard Operating Procedures 107 . For the cleaning of small stainless steel and aluminum parts b. Ultrasonic rinsing tanks e.b. or b. It can cause the unit to fail because the parts will reflect the ultrasonic energy back into the transducer. This also permits free access of the sound waves to the parts. Turn on heaters and preheat the tank to 120 deg F (50 deg C) 5. Inc. Place parts on rack and allow to air dry. that is adequately perforated for drainage. Always allow at least one inch between the tank bottom and the beaker or receptacle for adequate cavitation. For another example: Fill the tank within 1 inch of top and turn on heaters. After 10 minutes lift basket and allow it to drip off for 1 minute to reduce dragout iii. Flow chart showing handling. To be carried out by trained and qualified operators 2. Define any inspection actions such as: take 10 parts from the batch and inspect for particulates and visible smudges with a 10X magnifying glass. Drying procedure a. Place beaker of Alconox solution in a beaker tray with the beaker immersed in the heated water. d. either an open mesh basket or an insert tray. c. Record results in batch record. Ultrasonic cleaning steps: a. rinsing. Any post cleaning handling procedures. Never place parts or receptacles directly on the bottom of the unit. Cover ultrasonic tank after removing and draining basket 6. alkaline resistant rubber gloves 3. Alcojet powdered detergent (Alconox. An example of an ultrasonic cleaning procedure adapted from a manufacturer of small stainless steel and aluminum parts is: 1. drying. Or. Clean the parts to be cleaned in the solution by i. c. filtered hot air dryers f. Deionized water g. Rinse Procedure: a. 7. Fill 3 other beakers with deionized water for rinsing and place them in the beaker tray. Drain rack with mounting pins to mount connectors on for cleaning operation c. For example: take basket and run them under running tap water for 20 seconds while moving basket to assure all parts are exposed to running water. 10X magnifying glass i. Ultrasonic cleaning tanks d. Air knife. b. Scope a. Reject entire lot for recleaning if there are any failures. Dispose of used detergent solution down the drain. Drying ovens h. Make up 1% Alconox solution in a beaker (20 g Alconox in 200 ml water in a 250 ml beaker). Placing them in basket and immersing them in the ultrasonic tank for 10 minutes ii. control and post cleaning handling a. catalog number 1450) b. it is better to use a holder that is of open construction. cleaning.
) BATH CHANGE NO PARTS.0 As required 500pcs/holder 1% R/ T R/ T 100k Concentration pH 1 min 5±1min 100k Pressure Concentration pH 1 min 1min 5min 2min Pressure Resistivity Resistivity Resistivity Temperature (Degree C) R/ T Check Frequency Once/Day Once/Day All By Technician Technician IQC tech Control Chart Trend Trend Insp report Check/ Equipment Cond meter pH meter 10 x Glass Trigger Points <5Megohms Out of spec 1% failure Alert Level 1 1 1 Trigger Actions Change DI column pH Incoming Inspect Visual Inform Customer Material input 1 Initial Presoak Rinse(water jet) 2 1st Ultrasonic Clean Alcojet Alcojet Water DI water Manually Manually Ultrasonic (40KHZ) Rinse(water jet) 3 2nd Ultrasonic Clean Alcojet DI Water DI water Manually Ultrasonic (40KHZ) Rinse(water jet) Rinse(DI water jet) 8 9 DI rinse (immersion) Final DI rinse (immersion) DI Water DI Water DI water DI water Manually Manually Air Ultrasonic 3 min 1min 5±1min 100K Qty/load Concentration 3% 10.5-8.4 2-4kg/c 3% 10.4 2-4kg/c >2 Megohms >2 Megohms > 2 Megohms 60-70 Once/Day R/ T 60-70 Once/Day R/ T R/ T R/ T Technician log bk Technician log bk Control Box pH meter 65±5 Out of spec 1 Concentration Increase/Dilute Control Box pH meter 64±5 Out of spec 1 Concentration Increase/Dilute (40KHZ) 11 12 Spin initial dry Dryer Machine Hot air 2 min 10min 55+5 Once/Day Technician Technician Control Box Spin Machine Control Box Control Box Insp report Insp report Microscope10 Visual 50-60 1 95±5 150±5 1 1 1 No Corrosion 1 Check temp probe Check temp probe Sorting 100 Rework 90±10_ Every Lot Technician Technician QC tech 13 Oven Dry Hot air 45min 150±10_ Visual Outgoing inspect 0.CLEANING PROCESS FLOW FOR PARTS STEP NUMBER STEP DESCRIPTION Incoming DI water CHEMICAL USED WATER USED AGITATION TIME (MIN.4-11.1% fail Corrosion 95+5_ 3pcs/lot Performance test Packing Storage Plastic tray/bag DI water 4h Every Lot Visual As Required As Required Technician ALERT LEVEL: 1. INFORM SUPERVISOR OR QC/ENGINEERING/PRODUCT MANAGER 108 The Aqueous Cleaning Handbook Standard Operating Procedures 109 . CONTROLS/ PARAMETERS Resistivity CLEANING PROCESS FLOW FOR PARTS Specified Limits >2 Megohms 5.4-11.
8. If heaters are supplied with the cleaner.htm) can be useful. Digital timers can be set directly. if both samples fail. or intensity. All safety regulations of your company should be followed in handling and transporting the items to be washed. 5. Turn the ultrasonic cleaner on for exactly 20 seconds. 5. Shake the foil sample dry of any water droplets. 2. 4. Also. The following aluminum foil test adapted from a Brooks Airforce Base procedure (http://www. Prepare a fresh solution of ultrasonic cleaning solution according to the manufacturer’s instructions and fill the ultrasonic tank to one inch of the brim. Allow foil to air dry. Temperatures in the GMP washer should be user programmable up to 95 degrees Centigrade. If future tests show marked changes over time you may need to service your unit.e. Conductivity measurement of final rinse water can be taken to validate rinsing efficiency. CLEAN-OUT-OF-PLACE IN RACK LOADED SPRAY-IN-AIR WASHER Standard Operating Procedures for the wash cycle in a machine washer. Prepare an aluminum foil sample. Do not tear. If areas greater than _ inch square show no pebbling. WFI. Hold the foil. The unit. Foil samples may be sent with units returned to the manufacturer for service. The foil should extend downward. Foil samples may be retained for future comparison. Precleaning is only required to remove bulk ingredients from the items to be washed and should be accomplished by a thorough rinsing. 2. USP) is performed to ensure removal of all cleaning chemicals at the end of the wash cycle. turn the ultrasonic cleaner on for five (5) minutes using the timer located on the cleaner. along with its latest foil record. Use scissors to cut the foil. it is sometimes useful to be able to test the performance of your ultrasonic washer. Exposure time of the cleaning chemistry at setpoint temperature will account for proper cleaning. if the unit is supplied with a HI/LO switch. For example: A tank with dimensions of 9 inches long by 5 inches wide by 4 inches deep would require a foil sample measuring 9 inches by 5 inches.mil/dis/ic guidelines/ attach2. turn them off for the remainder of the test. Before placing the foil in the tank. then back to the 5 minutes setting for maximum time accuracy if it is an analog timer. Be sure to turn the timer to 20 minutes. Place foil sample which was prepared in Step 1 into the tank in a vertical position. it should be set in the highest position. there may be a problem with the unit.ALUMINUM FOIL ULTRASONIC CLEANER TEST PROCEDURE In working with ultrasonics. 6. Purified Water rinsing (i. Properly functioning units will result in foil surfaces that are uniformly “peppered” (covered with a tiny pebbling 110 The Aqueous Cleaning Handbook effect). GMP Washers validate exposure time through continual monitoring of all parameters. Cleaning chemistry and concentrations of the cleaning chemicals is specific to the soiling on the items to be washed. Handling of the items to be washed must be done according to manufacturers recommendations. over the entire surface. but should not touch the tank bottom. approximately centered front to back. as steady as possible. Standard Operating Procedures 111 . which does not include the scope and list of materials is: 1. 4. should be returned to your service center for service. Retest with new foil to substantiate the failure.af. 3. Obtain a roll of standard lightweight household aluminum foil. 3. The dosing time will determine the amount of chemical delivered to the fixed volume of water in the wash chamber. Unroll a piece of foil measuring approximately one (1) inch greater than the depth of the tank by approximately the width (long dimension) of the tank. 1. The foil long dimension should be positioned with the long tank dimension.brooks. Turn the cleaner off and remove the foil sample. The GMP Washer should utilize precise dosing pumps to deliver chemicals to the wash chamber. 7. being careful not to wrinkle the foil.
I RINSE 1 ACID RINSE PERIOD ACID INTAKE W. 11 During the inspection and qualification of the GMP Washer.I RINSE 4 HOT W.F. 11 POSSIBLE SETTINGS FOR WASHER CYCLES Function Possibility PREWASH 1 PERIOD PREWASH 1 TEMPERATURE PREWASH 1 DETERGENT PREWASH 2 PERIOD PREWASH 2 TEMPERATURE PREWASH 2 DETERGENT PREWASH 3 PERIOD PREWASH 3 TEMPERATURE PREWASH 3 DETERGENT WASH PERIOD WASH TEMPERATURE WASH DETERGENT W. Postcleaning handling of the washed items must be performed in compliance with internal company procedures that assure cGMP compliance.F. After cycle.F. Testing protocols must be established. the wet parts are checked with an U.I RINSE 3 COLD W. An example is as follows: One test protocol for establishing cGMP washer operation that can be used can be done by the riboflavin U.6.I RINSE 2 0 to 30 min up to to 95° C 0 to 6 min 0 to 30 min up to to 95° C 0 to 6 min 0 to 30 min up to to 95° C 0 to 6 min 0 to 30 min up to to 95° C 0 to 6 min 0 to 9 0 to 30 min 0 to 6 min 0 to 9 Prog. All drying air is HEPA filtered.F. a drying step with temperatures up to 110 degrees Centigrade can be performed. Does Riboflavin remain? Test 1 Yes / No Test 2 Yes / No Glassware: Test 1: Test 2: Test 3: After all of the preparation of the cycle description.F.I TEMPERATURE Possibility 0 to 30 min 0 to 30 min 0 to 30 min 0 to 30 min 0 to 30 min up to to 95° C Prog. On Drying models.I RINSE HOT W.I RINSE 1 COLD W.V test: Soil the parts with a Riboflavin solution.F. Let them dry for 2 hours and then soil them again. Perform the cycle 11 as follows (this cycle must have no drying). 112 The Aqueous Cleaning Handbook Standard Operating Procedures 113 . the operators must be trained to load/unload the racks is an efficient manner. Let them dry overnight.I RINSE 2 COLD W. 7.V lamp.F. load patterns and testing of the spray coverage is completed.F. Function COLD W. verification of the effectiveness of the inventory system as described above must be demonstrated.
In the mix tank. White Plains NY USA cat no 1815) may need to be performed to reduce particulate and inorganic scale buildup. Rinse jar between uses. Continue until the return effluent is no longer badly discolored. Scope a.000 mg/l) b. f.5 gallons per minute (for 4 inch systems) at 345-518 Kpa pressure (for 4 inch systems) sending both brine and product side to drain. Circulate the cleaning solution through the filter block. Scope a.5 gallons/min at 345-1035 Kpa pressure for a 4 inch system. Operators must be trained and qualified 2. sampling ports and port connectors g. rinsing and drying description a. Continue flushing until no foam is observed in the shaken sample jar. SOAK AND AGITATE CLEANING 1. In large systems. Flush filter element block with water once through (10 gallons for a typical 4 inch diameter filter element unit – different sized units would take proportionally more or less water) c. Hot water hose 3. Flush residual cleaner with feed water at 4. Collect sample of effluent in a small jar. Brush c. CLEAN-IN-PLACE LARGE TANK FILL. b. Use the chiller to maintain the temperature below 35 deg C. When cleaning is completed. Cleaning. Pre cleaning conditions a. isolate the 1 block of filter elements to be cleaned. Filter system suffering from biofouling and/or inorganic particulate build-up 4. Bucket d. Post a. Turn on mixer to dissolve detergent e. Tank with waxy residue shall be cleaned within 24 hours. To clean a large ultrafiltration brine water filter system b. d. 316 stainless steel mix tank sized appropriately to the system (minimum of 3 minute retention time during circulation) with an exhaust fan. Suitable flexible piping. Detergent b. allowing the rest of the blocks to operate normally. 10 micron cartridge prefilter e. Circulate continuously or by alternately circulate/soak for 15 minute intervals. Send the first 20% of the solution to drain via the brine return valve. dissolve enough Terg-a-zyme to make a 0. and temperature indicator c. Observe pressure and performance to determine if further treatment with a citric cleaner such as Citranox (Alconox. shake and observe foam indicating the presence of detergent. Materials a.5% solution taking into account the volume of the tanks and filter element blocks (2. Good quality chlorine-free tap water (total dissolved solids less than 5. Precleaning conditions a. 316 stainless steel centrifuge pump sized for appropriate flow rates d. stop recirculation. To clean a large stainless steel tank to remove a blended material that contains a thick high melting wax. Circulate the rest of the cleaning solution 114 The Aqueous Cleaning Handbook at 4. The cleaning progress can be monitored by observing the color of the effluent. Terg-a-zyme (Alconox cat no 1350) enzyme cleaner 3. mixer. Recirculation pump e. cover. b. g. 5.5 gallons for a 4 inch system). drain mix tank to waste. cooling coil.CLEAN-IN-PLACE ULTRAFILTRATION BRINE WATER FILTER SYSTEM CLEANING 1. Operators must be trained and qualified 2. Materials a. Perform post treatment procedures and return block to normal operations. Flow meters f. Circulate for at least 2 hours for a 4 inch system. Standard Operating Procedures 115 .
af. R M Keeping Validation Current: Elements of an Effective Change Control Program. Use a hose with hot water to rinse the top part of the tank above the immersion line k. and a range of other industrial washers. n.com http://www. Add detergent recommended for the type of residue in the tank (see note) c. Postcleaning conditions a.b. You can add your own understanding of your situation to adapt this to a successful SOP. which melts around 200 deg F in mind. spray cabinet washers. Private communication regarding Lancer Washers May 2002 RESOURCES www. As long as the general topics outlined here are covered a successful SOP can be written. There are many types of cleaning machines.htm 116 The Aqueous Cleaning Handbook Standard Operating Procedures 117 . j. Tank ports should be kept closed while in holding 4. oscillating washers. Fill the tank with hot plant water that had been heated to 200 deg F with the agitation and any recirculation pump turned on for 10 minutes. presented at Cleaning Validation and Cleaning Processes Jan 14-15 Philadelphia. Cincinnati. Open top and manually scrub with a brush dipped in the hot solution the unexposed top sections of the tank that were not immersed by the cleaner h. f. Turn on mixer wipers to agitate d. Tag the tank as clean with a date to allow control for clean hold times b.alconox. Fill tank full with hot plant water b. JB. Rinse the tank thoroughly with hose of hot plant water or a spray ball apparatus with hot plant water. PA (2002) James Fry. each would have its own machine specific standard operating procedure. Turn on pumps and connect pipes to recirculate through any lines that need to be cleaned. Drain the tank i.lancer. rinsing and drying description: a. Record cleaning in equipment log. Drain the tank. Cleaning.com www. Allow tank to air dry with ports open 5. This cleaning regimen is designed for a wax. Many soils may not require heating to an excess of 200 deg F. Visually inspect the interior of the tank and clean any known problem areas with a hot bucket of detergent solution and a brush.mil/dis/icguidelines/attach2. The previous sections in this chapter give examples of standard operating procedures. The types of considerations and procedures could be adapted to many other kinds of cleaning. REFERENCES DuPont Company Bulletin 507 “Cleaning Procedures” p 1-4 (1982) Durkee. Turn on tank heaters to raise temperature above 200 deg F (see note) e. Depending on how well sealed the tank is. reel-to-reel washers. adjustment of the recommended 4 hour cleaning time may need to be done as experience is gained with specific soils and tanks. Many waxes are melted by 170 deg F and this procedure could be adapted to use a lower temperature for lower melting waxes of for residues that did not require such high temperatures.brooks. m. o. recording date. Run for 4 hours. Note pumps should be operated with sufficient head or at a slow enough speed to avoid cavitation due to foam formation. Philadelphia. The Parts Cleaning Handbook. time. Gardner Publications. you may need to top up the solution to compensate for evaporation g. The machine manufacturer should be able to help you understand the proper use of the machine. Drain the tank l. You could have procedures for a range of machines such as vibratory washers. 1994 Dollard. and operator Note.
The validation is specific to the detergent and method used for cleaning. bio-pharmaceutical. medical-device.CHAPTER EIGHT Cleaning Validation Cleaning validation is typically performed for pharmaceutical and other GMP manufacturing processes. and Performance Qualification (PQ) of manufacturing equipment and operations. Operational Qualification (OQ). The validation provides documentation and evidence of reproducible successful cleaning. cosmeceutical and clinical-diagnostic manufacturers. The validation is best done during Installation Qualification (IQ). To perform a cleaning validation one needs a validation master plan. 118 The Aqueous Cleaning Handbook Cleaning Validation 119 . The validation consists of a final report and a set of procedures to maintain a validated state. bulk-pharmaceutical. These include pharmaceutical. 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.
new cleaners In the course of the validation one can simplify things by assembling an equipment matrix that defines all shared and dedicated equipment. provide equipment data • R&D—recovery. and worst interactions with the next batch to be cleaned. Rinse water sampling involves taking a sample of an equilibrated post-final rinse that has been recirculated over all surfaces. For investigations of failures or action levels. 10 side by side strokes vertically.” The worst case is typically chosen based on product solubility in cleaner or detergent. The validation involves: • Residue identification. This procedure is used to document acceptable residues three or more times and then a rational monitoring program to maintain a validated state is put in place. and preservatives. The FDA prefers specific methods. The people or departments involved in carrying out the validation with defined responsibilities would include: • Validation Specialist—writes. In this way. This document is intended to help with the cleaner residue identification. transfer methods. a matrix of residues can be assembled to classify into residue groups of types that are cleaned by a given set of conditions and then determine which is hardest to clean. and conductivity. A matrix of cleaning procedures can then be assembled in order to standardize on as few procedures as is practical to improve execution and training for these procedures. 120 The Aqueous Cleaning Handbook • Sampling method selection. It is important to validate a worst case scenario and to justify the choice of “worst-case. It can also involve non-specific methods that detect the presence of a blend of ingredients such as: total organic carbon. or placebo sampling. but will accept non-specific methods with adequate rationales for their use. primary ingredients. Work can be done to justify which equipment represents worst case hardest to clean equipment that in turn must have a full validation done to represent the documented easier to clean equipment. flame photometry. coordinates validation • Manufacturing—write SOPs. the toxicity of the products or degredants being cleaned. collect data and then clean the old way before using any equipment while in the process of validating the new procedure. decomposition products. The cleaning validation for a specific cleaner involves testing for acceptable residues on pharmaceutical manufacturing or medical device surfaces. pH. first clean the new way.worker. 10 horizontally and 10 each with the Cleaning Validation 121 . ion selective electrodes. dose sizes and size normal therapeutic dose (smaller may be more critical to validate). and finally • Writing a procedure and training operators. Swabbing involves using wipe or swab that is moistened with high purity water (WFI) that is typically wiped over a defined area in a systematic multi-pass way always going from clean to dirty areas to avoid recontamination – i. do training • Quality Assure/Control—approve and do analytical methods • Engineering—inform of changes.e. • Setting residue acceptance criteria. a specific method is usually preferable. If changing any part of the procedure or cleaner. validate methods. (A later section of this chapter lists references to several methods for each cleaner brand. coupon sampling. and environmental safety while controlling the risk of cross contamination. swabbing surfaces. Residue detection method selection—for cleaners can involve specific methods for specific cleaner ingredients such as: high-performance liquid chromatography (HPLC). a worst-case residue or worst-case for a residue class can be confirmed.) Sampling method selection—for cleaners involves choosing between rinse water sampling. By the same token. hardest to clean equipment/residue. excipients. derivative UV spectroscopy. Rinse samples should be correlated to a direct measuring technique such as swabbing. • Methods validation and recovery studies. • Residue detection method selection. Residue identification—in a pharmaceutical manufacturing environment this involves: the cleaner. enzymatic detection and titration.
Coupon sampling involves the use of a coupons or an actual removable piece of pipe that is dipped into high purity water to extract residues for analysis. Placebo testing involves using placebo product and analyzing for residues from the previous batch. and the area of the mixer and filling equipment which is all used in the next batch is 100. toxicity. and you can have a lower internal action level. or concentration in equilabrated rinse water (ug/ml). chemical. excipients. Cleaning agent safety based limits are typically calculated from a safety factor of an acceptable daily intake (ADI). If the calculated limit is found to be higher than a less than 10 ppm carryover to the next batch. Limits are typically set for visual. degradation products. In this case. these are available in kits with clean sample containers. you might need to do separate residue studies on the filling needles or punches to be sure that there was not enough residue just on that equipment to contaminate the first few bottles or tablets of the next batch with a residue of 350 mg/daily dose. Note that in this example you are trying to avoid getting more than 350 mg of residue in a daily dose of the next product.005 kg). In the case of small final filling equipment such as filling needles for vials or tablet punches and dies. a (1/1000 or more) reduction of an LD50 preferably by the same route of administration.000 cm2 X 0.000 or 1/1000*) Comparison calculation of limit based on no more than 10 ppm carryover: Limit (mg/cm2) = 10 mg residue on just cleaned surface X Next Batch Size (kg or L) 1 kg of L of next product X Size (cm2 or L) shared equipment Note that for many residues one can validate a visual detection limit on the order of 1-4 ug/cm2. By comparison. the 10 ppm in next batch limit gives an acceptance criteria of 100 ug /cm2 (10 mg X 1000 kg/(1 kg X 100. Quartz glass fiber filter papers have been used successfully. You should have a calculated safety based acceptance limit. amount in a swab sample (ug or ug/ml). The calculated residual acceptance limit for a 2000 kg mixer and line where there might be a next smallest batch of 1000 kg. If the safety based limit in this example is set at 100 ug/cm2. The Texwipe large Alpha Swab 714A or 761 have been used. cleaning agents. bioburden and endotoxins. Example with a cleaner that has an rat oral LD50 of over 5 g/kg.000 cm2) X 1000ug/mg. Chemical limits can be expressed as a maximum concentration in the next product (ug/ml). These levels are determined based on potential pharmacological. safety. It is possible that the visually clean criteria will be the most stringent criteria. and contamination effects on the next product using that surface or equipment. The cleaning agent limits are generally covered under chemical criteria. and a lower process control level based on actual manufacturing and measuring experience. or reproductive hazard levels. For TOC analysis very clean low background swabs or wipes and sample vials such should be used. Then this limit can be expressed as a rinse water con- 122 The Aqueous Cleaning Handbook Cleaning Validation 123 . it is likely that you will be able to show that you can visually detect down to 4 ug/cm2 and since you need to have a visually clean surface. maximum carryover in a train (mg or g). stability. then the limit can be set to the more stringent 10 ppm carryover level for the safety based limit. Calculated safety based limit in mg/cm2 or mg/ml of cleaner residue on a just cleaned equipment: Limit (mg/cm2 or L) = ADI carryover – see below (mg) X Smallest Next Batch (kg) Size of Shared Equipment (cm2 or L) X Biggest Daily Dose or of Next Batch (kg) ADI carryover (mg) = LD50 by administration route (mg/kg) X body weight (kg) X (1/ 10. the ADI calculation using a 70 kg person and a safety factor of 1000 gives a result of 350mg (5 g/kg X 70 kg / 1000 ).000 m2 and the daily dose of the next product is 0. your most stringent acceptance criteria will be the visual limit. and microbiological residues. amount per surface area (ug/cm2). Setting residue acceptance criteria—in pharmaceutical and medical device manufacturing requires setting residue acceptance levels for potential residues such as the active drug.flip side of the swab in each diagonal direction.005 kg results in a calculated residual acceptance criteria of 700 mg/cm2 (350 mg X1000 kg/(100.
As and example. Residue detection methods can vary from non-specific methods such as total organic carbon (TOC) to selective methods that have been shown to be specific at a 95% confidence level in the conditions of use without significant bias or interference from impurities. Co nduct ivity H. storage conditions. protective clothing needs. and other ingredients. documentation needs. excipients. Dir LC ect U V/Vis ALCONOX® LIQUI-NOX® TERG-A-ZYME ALCOJET® ALCOTABS ® ® • • • • • • • • • • DET-O-JET® DETERGENT 8 CITRANOX® LUMINOX® CITRAJET® ® • • • There are some things that are unique to the cleaner being tested. No rate.000 cm2/100 L). and European Union (EU) have all defined validation requirements for analytical methods used in manufacturing pharmaceuticals. show a variety of residue detection methods for these cleaners (see the directory table). the following is excerpts from the Alconox Cleaning Validation References for cleaners made by Alconox. It is recommended that this process be done separately from the cleaning process so that the cleaning validation can be completed while the lengthier biobuden/endotoxin evaluation is done. Ph ospha te by Titrat ion E. The operators then need to be trained and certified in the procedures. nionic Kit Surfa ctant by HP C. and inspection required before next use. In some cases bioburden/endotoxin levels may need to be validated. As discussed under methods validation.centration of 100 mg/L in a post final rinse using 100 L of recirculated to equilibrium rinse water (0. Cit ric Ac id by HPLC . Ideally the expected values and limits should be multiples of the limits of quantitation. UV/ assium Vis by Fla me or IC J. The % recovery is used to correlate amount detected with amount assumed to be on the surface as an acceptable residue. typically spiked at 50%.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 cm2 swab area where 50% recovery has been established ((25 cm2 X 100 ug/cm2) X 50% recovery) X 10% TOC/20 ml. The methods validation and recovery study—is the use of the sampling and detection method on known spiked surfaces at representative levels. The FDA often prefers the use of 124 The Aqueous Cleaning Handbook Cleaning Validation D. This is a good time to consider wipe or rinse sample storage conditions and time limits to get the sample analyzed. post cleaning inspection procedures. Org anic C arbon by TO C G. the International Conference on Harmonization (ICH). Enz yme b y Ass ay F. Gly col Et her b y GC • • • • • • • • • • • • • • • • • • • • • • • • • • • 125 . Rinseability profiles showing the complete rinsing of the individual detergent ingredients should be undertaken if the solubility of any detergent ingredients or the rinseability after drying is in doubt. DIRECTORY OF CLEANER RESIDUE DETECTION METHODS FOR EACH ALCONOX DETERGENT A. The FDA. equipment disassembly needs. Inc. The United States Pharmocopeia (USP) gives method validation guidelines in Chapter 1225. Pot y. The written procedure and training of operators—involves writing out assigned responsibilities. The same safety limit can be expressed several different ways. Anio nic Su rfacta nt HP LC. different analytical methods will require different procedures for validation. Assa I.1 mg/cm2 X 100. labeling of in process and cleaned equipment with cleaning expiration date. Tit B. This same limit could be expressed as 6. monitoring procedures. degredants. 100% and 150% of the acceptable limit and at lower expected actual levels to show linearity with documented % recovery as analyzed and to determine the limit of detection and limit of quantitation.
Things one should look for from a cleaner supplier include: • Lot traceability of the cleaners • Certificates of Analysis for the cleaners • Consistent manufacturing • Ingredient disclosures under confidentiality • Cooperation with audits and quality questionnaires • Ingredient toxicity data • Ingredient reactivity information to help determine degredations and interactions • Cleaner shelf life information • Residue detection method information • Residue sampling information • Acceptance limits information • Recovery information • Residue detection methods validation information • Assistance with written cleaning procedures To discuss the specifics of these validations with the examples given with Alconox detergents. UV-vis – ultraviolet visible spectroscopy. journal articles. Typically changing a cleaner would require revalidation. There should be a list of assumptions made that would need to be reviewed whenever anything is changed. For some kinds of changes it is appropriate to continue operations the old way while simultaneously and sequentially doing 126 The Aqueous Cleaning Handbook the new process with monitoring to prove that the new process gives the same validated results as the old process. The final section of the final validation report would have the references to any standard methods.selective methods that have been shown to be specific. contact Malcolm McLaughlin at 914-948-4040. A defined procedure for changing validated processes is needed. hardest to clean. particularly for investigations. It also makes sense to include a review of validated 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.high performance liquid chromatography. This would be followed by a section of data analysis with statistical justification for the conclusions reached. IC ion chromatography. Wet methods. In selecting an aqueous cleaner for cGMP manufacturing where a cleaning validation is required. TOC. Non-specific methods such as TOC are commonly used where the limits of detection and quantitation are well below residue acceptance limits. or most toxic) that would require revalidation. or government documents. The following table reviews method validation requirements: TABLE: ANALYTICAL METHODS VALIDATION CONDITIONS Method HPLC GC X TLCX IC X Accuracy X X X X X X X Precision (Repeatability) Linearity Reproducibility Selectivity X X X X X X X X X X X X X X X X X X X Specificity LOD X X X X X X X X X X X X X LOQ X X X X X X X Ruggedness X X X X Wet Methods X UV-vis TOC X X X X X HPLC. GC – gas chromatography. 160. or write mmclaughlin@alconox. ext.com Cleaning Validation 127 . TOC also detects virtually all organic residues. consider both the efficacy of the cleaner and the ability of the cleaner manufacturer to support validation efforts. This should address the level of approval and review needed for specific changes.total organic carbon. Provisions for emergency changes should be considered. TLC – thin layer chromatography.titrations/assays In the final report the next section would deal with cleaning process design with references to standard operating procedures and how they were evaluated. in ways making it superior at showing overall cleanliness.
com www. Vol 8. PA (2001) Cooper. No 3.alconox. Most local governing authorities enforce acceptable criteria for pH.fdainfo. IVT. and metals.com TYPES OF CONTAMINANTS • Solids—Acid conditions are used to enhance breakup of the oil-water emulsion. Washington Group International . 128 The Aqueous Cleaning Handbook Wastewater Treatment and Cleaner Recycling 129 . Philadelphia.cleaningvalidation. 260-272 (May 2002) CHAPTER NINE Wastewater Treatment and Cleaner Recycling treatment is imperative for reducing the level of contamination present in the water from a cleaning system. p 74-89 (1996) FDA “Biotechnology Inspection Guide” (1991) FDA “Guide to Inspection of Bulk Pharmaceuticals Chemicals” (1991) FDA “Guide to Inspection of Cleaning Validation” (1993) ourman and Mullen. Nassani.ivthome. where a polymer flocculent is added. which may include insoluble oils. “Qualification of Quality Control in Laboratories. The water layer is pumped to a chamber. 5460 (1993) Leblanc.fda. including pretreatment. 17 (4). “Using Swabs for Cleaning Validation: A Review” Cleaning Validation. where they are dried in preparation for disposal. presented at Cleaning Validation and Cleaning Processes Feb 1-2 Philadelphia.gov.” Journal of Validation Technology. which is designed to reduce the volume of solids and wastewater. and dissolved inorganic solids such as chlorides. and chemical oxygen demand (COD). A typical wastewater treatment system involves a few common operations. and municipality to municipality. suspended solids. Rebecca Designing and Documenting Your Cleaning Validation Program to Meet FDA Requirements. Treatment requirements before discharge to the local sewer vary from state to state. Flocculation of the metals is achieved upon addition of a polymer. Specific discharge criteria will be noted on your discharge permit. other dissolved organics. PhD.REFERENCES 21 CFR 211 and Proposed Revisions Brewer. nitrates.com www. Wastewater RESOURCES www. emulsified oils. 136-148 (1998) Mowafak. which settles to the bottom of the chamber. Flocculated solids are transferred to a filter press. phosphates. “Establishing Scientifically Justified Acceptance Criteria for Cleaning Validation of Finished Drug Products.com www. The wastewater is then pumped to a clarifier. biological oxygen demand (BOD).” Pharm Technol 22 (10).com www. “Determining Cleaning Validation Acceptance Limits for Pharmaceutical Manufacturing” Pharm Technol. where much of the oil condenses into a floc. The supernatant liquid is pumped to a process tank where the pH is raised in order to promote precipitate metals.
Some alternatives to aqueous cleaning systems include “drop-in” semi-aqueous or solvent-based cleaning systems. these are not without their own problems. end-of-pipe wastewater treatment approaches tend to perform less efficiently in a continuous manufacturing operation and contribute to disposal problems. Metal contaminants and other inorganic materials will remain dissolved or suspended in the wastewater. and is able to be reused. in order to assure cleanliness. rather than destined for disposal. post-production. In the early transitional days. An inclined plate can be used to direct the flow of the oil layer away from the wastewater. which is separated by a baffle from the primary chamber and a reduced-pressure area below. • Design. A current method of oil-water separation applies Bernoulli’s principle. • Activated carbon—Suspended organic materials can be removed from the waste stream with the application of 130 The Aqueous Cleaning Handbook an activated carbon filter. A UV-oxidation system can be employed. maintenance. • Capital and operating costs may justify the recycling of wastewater in a closed-loop system. whereby the wastewater is split into two laminar flows. However. to reduce the BOD of the wastewater. EQUIPMENT OPTIONS • Evaporators—Evaporation is commonly used to reduce the volume of water for further treatment. and decanting methods. many process and manufacturing engineers were concerned that aqueous processes would reduce part quality and throughput while creating additional waste and wastewater treatment problems and costs. Such out-of-process. etc. • Separators—Gravity separation of nonemulsified oil in wastewater can occur in the clarification tank. SELECTION CONSIDERATIONS The following are basic guidelines for selection of a wastewater treatment system: • Treatment options should be studied by an engineer to assess process alternatives. a large number of companies chose aqueous cleaning solutions as replacement alternatives to solvent degreasing.• Oils—Capability to remove trace quantities of floating oil in a cleaning bath not only improves cleaner performance. away from the second chamber. oils collected may be evaluated for reuse. The oil is recovered from the top of the concentrated layer. Further. activated carbon is used for organic materials only. namely Wastewater Treatment and Cleaner Recycling 131 . when the layer reaches a designed thickness. filter capacities. The system should be optimized for proper flow rates. CLEANER RECYCLING As numerous ozone-depleting compounds became legislated out of use. However. The water is either discharged to drain (with the necessary permits and approvals in place). and operations should have contingencies for downtime. capable of absorbing material many times its own weight within its extensive pore network. Filters can be arranged in series or parallel. as necessary. tank overflow. upon filtering out any particulates or fines. Traditional mechanical separation of oil from wastewater involves the use of skimmers. Higherquality oil is recovered this way. The influent and effluent flow rates are optimized to allow efficient separation of the lighter oil layer from the water. The contaminants then become concentrated within the bottom sludge and the water is transferred to a holding tank. where it is allowed to cool to room temperature. The reduced pressure directs the flow of water down. • UV Systems—Ultraviolet (UV) light is an effective means to destroy biological organisms. Oil is continuously collected and concentrated in a second chamber. A parallel arrangement allows for change-out of one filter while the others remain operational. or undergoes further treatment. An activated carbon filter can be used as one of the last stages before discharge or recycling. throughputs. but extends bath life.
) In addition. • Physical separation—such as cooling and skimming.employee health concerns. • Solution recharge—is when a detergent solution life can be extended by using the detergent to exhaustion. light oils will generally rise to the surface and the overflow can be physically skimmed off with oleophilic wicks or cycling bands of oleophilic material. One public lab where solvent replacement work has been done is The University of Massachusetts at Lowell’s Toxics Use Reduction Institute. The concentration of useable detergent will then be sufficiently raised to a level where effective cleaning will occur. Modern closed-loop aqueous cleaning systems remove contaminants from both the cleaning bath and rinse water. users should ask the following questions: Wastewater Treatment and Cleaner Recycling 133 . (Because less water is used. leaving reusable cleaning solution. flash points (flammability). Aqueous cleaning has provided a sound alternative to vapor degreasing in as many as four out of five applications that the Institute reviews on a laboratory scale for industry clients. The soilfree permeate stream is then recycled back to the parts washer. many kinds of filters are available for ultrafiltration due to advances in membrane types and the continued evolution of systems with better temperature and chemical stability. Treating cleaning solutions can be accomplished through one or more of the following procedures: • Physical filtration—uses gravity or low-pressure pump cartridges at one to 100 micron levels of filtration to remove suspended particulates. it is easier to recycle the detergent solution separately from the rinse water because the equipment used is merely separating soils. In sequential tank cleaning this is accomplished by using a series of countercurrent cascading rinse tanks with each tank’s water being progressively reused. This type of system minimizes water usage while ensuring that the final rinse stages contain the cleanest water. recycling is also easier and less expensive to install. FILTER SELECTION Today. consisting of a thin “selective” layer over a thick. not trying to create high-purity water. extremely hydrophilic (water-absorbing and oilrepellent) polymeric membranes have been developed to resist fouling by free oils. and emulsion breakup. Recycling can help reduce or eliminate liquid waste by trading dilute liquid waste for more easily disposed solid waste in the form of spent filters or concentrated sludge. porous substructure. and possible worker discomfort due to odors. 50 percent of the original dose). may be relatively inexpensive to install. deionizing resins or reverse-osmosis. For example.0 micron levels of particulate filtration (used to break and remove 132 The Aqueous Cleaning Handbook very fine suspensions of particulates). The Institute has shown the viability of aqueous cleaning in industrial settings. emulsions. heavy sludge will generally settle to the bottom when a suspension breaks. • Ultrafiltration—is when multiplex membrane filters are packaged into a variety of cartridge configurations and integrated into the cleaning process. and other hydrophobic solutes in order to achieve efficient filtration rates over extended periods. The first place to install recycling equipment is in the rinse water portion of the cleaning system. A feed solution is pumped through the filters’ cartridge and split into a permeate or filtrate (material retained by the membrane) and retentate (fluid retained by the membrane).1 to 1. Filters can be either symmetric. Before deciding on a system. It may also save time and increase throughput while reducing system setup requirements. dead-end. with fairly uniform pore diameters throughout the membrane. or cross-flow filter membranes to realize 0. or asymmetric. • Microfiltration—uses low-pressure pumps. In emulsion breakup. for which you need activated carbon. settling. Cooling solutions allow emulsions and suspensions to break. and compared to solvent cleaning systems. and then adding some amount of additional detergent (for example. Membrane selection is critical to the effectiveness of any recycling system. Settling allows water-insoluble materials to separate by density. Recycling can also help reduce detergent consumption in order to get more parts clean per pound or gallon.
they must be shipped back to suppliers for regeneration. Contaminants with a diameter greater than the membrane’s MWCO are thus filtered out. content of both the recycled bath and the rinse water used. Particulates may be removed using settling tanks. These are selected for particular applications based on the size of the contaminants. Some very simple. rendering them inappropriate in procedures which depend on the removal of soil. mandating a fresh batch. yet effective. desirable for maintaining quality control in high-production applications. or canister filters. these recycling systems may also use reverse osmosis (RO) in conjunction with microfiltration in order to protect the filter membrane. and magnesium. In a separate system. MONITORING AND CONTROLLING CLEANING BATHS In order to extend bath life or recycle solutions. as well as Total Alkalinity. and vice versa. such as those based on salts Wastewater Treatment and Cleaner Recycling 135 CLOSING THE LOOP ON AQUEOUS CLEANING AND RINSING There are a number of methods for removing contaminants from aqueous-cleaner solutions. which measures total alkalinity as well as the alkalinity consumed in the cleaning process due to sludge formation or hydrolysis of animal or vegetable-based oils. Activated carbon may be used for the removal of the majority of organic contaminants. while ultrafiltration pore sizes range from 0. HPLC (high pressure liquid chromatography).1 microns. Ion exchange is another type of system that uses specially designed resins to capture cations and anions such as chlorine. Cleaners are recycled using physical filters. including: • Conductivity—The measurement of ionic content of the cleaning solution using electrodes connected to a conductivity meter. This is a useful technique for figuring out when to add more detergent to a cleaning solution with high ionic content. oil separators. which can adversely affect its performance and make disposal necessary. It is therefore important to monitor the salt 134 The Aqueous Cleaning Handbook . such as FTIR (Fourier Transform Infrared Spectroscopy). ultrafiltration. however. The rinsing recycle systems can be designed to deliver water to a level that leaves parts able to meet required cleanliness standards. There are numerous sophisticated analytical chemistry techniques. Since these types of cations and anions may be considered hazardous waste. Oils are collected using skimmers and coalescers. measure the level of surfactants. and microfiltration. rinse water must be purified.• Surface chemistry—Has the membrane been engineered for easy cleaning or to resist fouling by free-floating and emulsified oils? • Stability—Is it physically and chemically stable toward a broad range of pH and aggressive chemicals? • Pore size—Has it been designed to ensure complete passage of all cleaner components while sufficiently retaining the oils? • Temperature tolerance—What is the membrane’s temperature tolerance? While not all aqueous cleaning applications require the use of membrane-based filtration. Neither Free Alkalinity nor Total Alkalinity.1 to 1. In addition to particle. media filtration. heavy metals. their use can be especially helpful in achieving steady conditions. Detergents must be selected for their compatibility with the specific membrane employed. Usually you have separate rinse water recycling and cleaner solution recycling. calcium. Neither will reject salts.and ultrafiltration are pressure-driven processes. COD (chemical oxygen demand) and TOC (total organic carbon). techniques can be used to monitor bath life. Free Alkalinity.and ultrafiltration. micro. for analyzing recycled cleaner.and ultrafiltration.0 microns. chip baskets. Ultrafiltration membrane pore sizes are also specified by molecular weight cutoffs (MWCOs). Microfiltration uses a membrane with pore sizes from 0. a process which measures unreacted builder in the cleaner. the cleaning bath should be monitored to determine when the solution can be recharged with detergent and when it is spent. can also be used. It is important to keep in mind that both micro.0005 to 0. Most of the remaining contaminants can be removed using micro.
It can be used to monitor the build up of soils and concentration of a solution due to water evaporation. The cost of installing recycling and reuse equipment and procedures must be weighed against the cost of disposal and solution use. for example. or saponifiable natural oils. • Refractometry—The indirect measure of the concentration of dissolved components which influence the refractive index of a sample of solution using a simple handheld refractometer. When cleaning with an alkaline detergent and the soil is either acidic or neutralizing in character (as most soils are). dragout. The value of the parts being cleaned. inorganic. probably cheaper and better to send to drain and make fresh solution. refractometry can be an effective means of measurement and control. Where regWastewater Treatment and Cleaner Recycling 137 . • Foam Height—Observation of the foam height of a volume sample of cleaning solution in a vigorously-agitated. because they commonly interfere with accurate readings. and loss of detergent. for example). stoppered test tube will show a decrease in foam height and foam stability with the build up of oils. Observations must be made at the same temperatures. As foam height decreases. When using a high-emulsi136 The Aqueous Cleaning Handbook fying or dispersing detergent to remove oils or particulate types of soils. This is not a useful technique for monitoring high emulsifying cleaners that rely on surfactants for a significant part of the cleaning mechanism. or even uncontrolled.(potassium hydroxide or sodium metasilicate. it is possible to be penny-wise and pound-foolish. Conductivity will drop as soils react with the salts. Empirical observations of cleaning solutions in use compared with recorded measurements can be used to derive appropriate times to recharge or discard solutions. With easily treated hazardous wastes. the increased risk of cleaning failure with each new part cleaned and the chance of cleaner exhaustion or soil redeposition must all be considered. which is measured using electrodes dipped in the solution connected to a pH meter. Each of the above methods has its application. pH can be used as a control measure. If the soils are acidic. expressed as the negative log of the hydrogen ion concentration. as pH drops 0. Note that pH paper should not be used with surfactant-containing cleaners. cleaning solution should be recharged or discarded. Foam height is most applicable to cleaners based on foaming surfactants that rely on emulsification of oily soils for their removal. conductivity can be used to monitor dilution. the detergent should be recharged. cleaning simply to get every last penny of performance from a detergent solution. Typically. TABLE 7A BASIC MONITORING AND CONTROL TECHNIQUE SELECTION BASED ON TYPE OF DETERGENT USED Conductivity Ionic cleaner removing nonionic soil such as a high alkaline cleaner used for degreasing Refractometry High emulsifying and dispersing cleaner used on mixed particulate and oily soil Foam height High-foaming cleaner used to clean oily soils pH decrease Alkaline cleaner used to clean acidic or hydrolyzable soils that react with the cleaner (most soils are acidic or hydrolyzable) pH increase Acidic cleaner used to clean an alkaline or neutral soil ECONOMIC FACTORS One must keep in mind that where detergent recycling is concerned. the pH will drop as the cleaning solution is used up. Then the solution can be used to exhaustion as it drops one full pH unit. perhaps not. One question that needs to be asked and answered is: Is it cheaper and better to send partially used cleaner to drain and make up a fresh batch of cleaner? With nonhazardous detergents and wastes. • pH—Measurement of the acidity or alkalinity of a solution on a scale of 0–14. When using an ionic cleaner to remove nonionic soils. based on the type of detergent used and the soils that need to be removed. A given brand of detergent will have a typical pH. It may not be worth risking inadequate.5 pH units.
The following additional parameters must also be fully reviewed: • Toxicity—by TCLP (Toxicity Characteristic Leaching Procedure) • Corrosivity—pH below 2 or higher than 12. Precision Cleaning. article “Aqueous Cleaning Technology: How long is a Cleaning Bath Really Effective?”.24. 50. 10. Fairfield. NJ 1994. recycling may be more economically beneficial than constantly playing catch-up with the evolving regulations surrounding industrial parts cleaning. 16–23. article “Filtration Systems. recycling the detergent may not be. an evaluation and determination must be undertaken as to whether the EPA needs to be involved.” p. The benefits of sophisticated closedloop systems must be weighed against the costs of maintaining those systems (for example. 36–42. But in low-volume.. p. high-performance cleaning applications with quality control inspection or low fault-tolerance parts such as electronic components and optical parts. pp. Ibid. article “Aqueous Cleaning System Design: Recycling.21-. recycling may well be worth it. 17–24. recycling can be as simple as making up a large soak tank for continuous use throughout the manufacturing process. Inc. Precision Cleaning. p. membrane systems need periodic cleaning or may need to be replaced). better to recycle. Toxics Use Reduction Institute. including the completion of a SARA report of discharge quantities of any listed chemical that is either in the soil or detergent discharge. REFERENCES Alkaline Cleaner Recycle Handbook. Membrex. MA. Fairfield. compressed gases and oxidizers as well as reactivity of the waste stream should be reviewed to determine if RCRA regulations apply as covered in 40 CFR 261. In the long run.” p. article “Sifting Through Filtration Options. 38. 5. in all probability. December 1997 issue. Lowell. then recharging with detergent at midweek intervals. soil-sensitive equipment. Inc.. Another factor to consider is the volume of your cleaning system. pp. saving time and money merely by recycling wash-tank water through a skimmer. Precision Cleaning. Membrex. This will allow you to avoid downtime during draining. 21–27. before considering recycling as an option.alconox. June 1997. University of Massachusetts. Toxics Use Reduction Institute. November 1996.ulatory compliance costs are prohibitive or no drain is available. Precision Cleaning. the answer is. refilling. Ibid. PROVEN TECHNOLOGIES There are numerous suppliers of closed-loop aqueous-cleaning systems designed to increase process efficiency by decreasing the generation of waste. medical devices and high-priced. October 1996. 3–5. p. Ibid. December 1997. Precision Cleaning. 4–5. 138 The Aqueous Cleaning Handbook RESOURCES www. NJ 1994. as well as any applicable state and local discharge regulations. but must also include a careful review of environmental and regulatory considerations. article “Closed-Loop Cleaner Recycling by Malcolm McLaughlin. Implementing such systems should not be based solely on short-term economic evaluation. p.. Personal interview. December 1997 issue. 1995. Also. p. University of Massachusetts at Lowell. 5. Alkaline Cleaner Recycle Handbook.com Wastewater Treatment and Cleaner Recycling 139 . 6. In high-volume. Precision Cleaning.” p. extreme-cleaning performance applications such as pharmaceutical process equipment. p.. In fact. Closed-Loop Aqueous Cleaning. It is important to note. that manufacturers already using aqueous-cleaning solutions don’t need a closedloop system to begin recycling today. recharging with detergent. p. however. article “Wastewater Treatment.5 • Ignitability—flash point below 60˚C (140˚F) ignitable In addition. and reheating the tank.
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 M .CHAPTER 10 Measuring Cleanliness easuring cleanliness can be done at different levels depending on the technique employed. electrical.01 grams per square centimeter include: • 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 . Processes which detect cleanliness at levels as low as 0. automotive and many surface preparation applications. cm level—a level of detection is suitable for aerospace.001 gram per sq.
and magnification of course improves detection. • Low-power microscope inspection—This is an excellent way to quickly and efficiently verify cleanliness of residual oils and greases. that the typical black light found in novelty or specialty gift stores may not be strong enough to cause much residue to fluoresce. flux residues. just as is done with the extraction method above. scanning electron microscopy (SEM) • Secondary ion mass spectroscopy (SIMS) The following are summaries of these various cleanliness measuring techniques as appropriate to each of the three levels of cleanliness required. cm. typically a yellow. Note. it may not always be suitable for precision cleaning applications.The highest level of cleanliness measurement—where levels below 1 microgram per sq. acetone and other solvents have been used for this purpose. any increase in weight is recorded as the nonvolatile residue. sometimes red.astm.) • Surface Ultraviolet Florescence (UV)—Many organic and some inorganic contaminants will fluoresce under UV light. CM • Visual inspection—is best used to detect residues of contrasting color or texture. • Wiping and visual inspecting—Wiping a surface with a white wipe will provide a contrasting surface with which to detect dark residues (the white glove test). and medical device applications. It will not readily detect non-hydrophobic residues. (Isopropyl alcohol. The solvent is then evaporated onto a coupon of known weight and after the solvent is evaporated off any residue is deposited on the coupon. can be detected—are suitable for use in semiconductor. The higher the intensity of the light used. particularly in a slightly darkened or dark room. The kinds of techniques that are used for this level of precise cleanliness measurement are: • Carbon coulometry • Electron spectroscopy for chemical analysis (ESCA) • Fourier transform infrared (FTIR) • Gas chromatography/mass spectrophotometry (GC/MS) • Ion chromatography (IC) • Optically stimulated electronic emissions (OSEE) • Particle counting.) The water break test is a fairly crude test which is suitable for detecting films of process oils and heavy finger142 The Aqueous Cleaning Handbook prints. color which glows Measuring Cleanliness 143 . • Atomizer test—A variation of the water-break test. fiber optic lights providing light across a surface improve detection.” ASTM Method F 22-65—found at www. disk drive. • Water-break test—Use running water and let it sheet across the surface. Good lighting can enhance visual inspection. Many solvents can be used for this purpose. The atomizer test is slightly more sensitive to hydrophobic soils than the water break test. the lower the level of contaminants which can be easily detected. • Nonvolatile Residue Inspection (NVR)—The NVR test involves extraction of soil from a dirty surface into a solvent. Observe if any breaks in the water occur due to hydrophobic (water-fearing) residues. It is important to use a solvent that can dissolve the soil being detected. however. When the coupon is reweighed. (See “The Hydrophobic Surface Film by the Water Break Test. Shining a UV light on the surface will cause the residues to easily be seen. CLEANLINESS DETECTION AT 0. This test is often used for parts washing. In the water break test the kinetic energy of the flowing water may overcome a hydrophobic residue where in the atomizer test you may be able to see the results of a little droplet of water being repelled by a hydrophobic contaminant. methalyne chloride. particles and surfaces. More powerful UV lights available from scientific supply houses or industrial suppliers will give far higher levels of detection. orange or green. this requires observing whether a gently sprayed water mist deposits uniformly or whether water repulsion occurs (usually due to a hydrophobic soil). The test is performed by shining the light on the surface and observing a fluorescent.org.01 GRAMS PER SQ.
flat material has a characteristic surface energy. Generally. easy way to visually monitor particulates and sometimes even film residues. is that an appropriate solvent must be used to extract any soils. The spray is collected. and liquid chromatography (LC). after soiling with an artificial soil. carefully removing it and then placing it on a sheet of clean white paper. If any filmy residues are present. When performing trace 144 The Aqueous Cleaning Handbook analysis for detergent residues it is advisable to use water as the solvent. CLEANLINESS DETECTION AT 0. Measuring droplet size will determine surface cleanliness. Gravimetric analysis is also very useful as a screening tool in lab cleaning situations where a coupon is weighed before soiling. cm. the amount of excess weight indicated the amount of soil present. a few drops of organic solvent can be deposited on the surface and then removed via pipette and placed on a watch glass. As a result. • Oil Soluble Fluorescence—Involves immersing a part in a fluorescent oil soluble penetrant dye and then observing under fluorescent light to see if any dye penetrates or adheres indicating the presence of oil. This procedure can be quantitative if one wipes a known area. CM • Millipore Filter Measurement—The Millipore Test— also known as the “patch” test—involves spraying samples of parts with filtered hexane. After cleaning if the part returns to it’s clean weight one can conclude that the part is clean. vacuum-filtered onto a clean filter membrane followed by microscope inspection for any particle-per-micron contaminants. (The sensitivity of an extraction test depends on the method of trace analysis.2-micron filter membrane inside a jet nozzle. isopropyl alcohol. low-power microscopes and generally require greater operator skill and training. or high purity swabs to wipe surfaces. total organic carbon (TOC) analysis. The limitations on this method. Comparing the sample with an adjacent piece of white paper provides a fast. firmly pressing it down.) The types of trace analyses most often used are UV visible spectrophotometry. one should observe a characteristic ring of organic-material deposits. however. • Tape Test—The Tape Test is a simple method for aiding visual inspection and is well suited to determining the cleanliness of smooth metal and plastic parts. this measurement technique employs a solvent-soaked glass filter paper. a deposit of a known volume of pure liquid (typically deionized water) will form a droplet of predictable size based on the amount of that energy. hydrophobic soils create smaller Measuring Cleanliness 145 . Extraction methods can be highly sensitive to a wide range of possible soils and residues. however.001 GRAMS PER SQ.” Of course cleaning procedures need to be established to remove the dye after testing. • Extraction—a particularly useful method for detecting detergent residues. • Surface energy—Any hard. and then weighed again after cleaning to derive percent of soil removed. (The membrane can also be weighed to determine total contaminants in milligrams. It involves attaching transparent adhesive tape to the surface being measured. • Gravimetric Analysis—With small parts of known weight. or trichlorethylene at pressures of 60 to 80 psi through a 1.) • Optical Microscopy—High-power compound microscopes can also be used (typically on circuit boards).under the light and is easily seen. This method is outlined in ASTM F601-98 “Standard Practice for Fluorescent Penetrant Inspection of Metallic Surgical Implants.01 TO . (These techniques are discussed separately in this chapter under “Detection below 1 microgram per sq.”) • Oil Evaporation—For filmy residues. atomic absorption (AA) or inorganic residues. high performance liquid chromatography (HPLC). The filter paper or swab is then extracted or digested and trace analysis performed on the extract. these are more delicate and more expensive than simple.
a known amount/type of particle contamination was deposited on glass slide test coupons. ISPM can be used to monitor bath performance. be sure to allow any bubble interference to reach baseline after addition of increased concentration of detergent prior to placing the soiled plate in the bath. thus providing the ability to quickly select.. during cleaning. and monitor filtration recycle performance. such as vacuum or diffusion pump oils. real-time particle counting could be used to determine when to take the parts out of the bath by observing when the particle counts had dropped back to baseline. adjust. For each concentration and each detergent. and electronic parts shrink in size and formerly inconsequential particles grow in comparison. Today’s precision industrial applications 146 The Aqueous Cleaning Handbook now employ ultrasonic cleaning baths as well. If you have a broad. The problem with the surface energy test is it only tests the surface directly underneath the droplet where you are measuring. By observing the shape of the particle counting curve. If you are trying to optimize detergent concentrations. the surfaces that are accessible for you to place a droplet of liquid to measure surface energy may not be representative of the types of soils that may be hidden in any cracks. If you have a part that has lots of cracks and crevices and holes. In-situ particle monitoring (ISPM) provides a tool to observe particle removal behavior in the ultrasonic cleaning bath process at work and in real time. Once the process is optimized.” which follows this section. a number of particles per ml per minute is determined by integrating the area under the particle size counting curves for a given length of time for each particle size monitored at each concentration of each detergent. and optimize the cleaning process. Typically after 10 or 15 minutes no more particles are observed. various particle sizes were observed in the bath at the addition of increased concentration of detergent. ISPM measures particle counts directly during the cleaning process in both ultrasonic rinse and wash baths.” which follows this section. such as ultrasonic bath cleaning are widely used.) • Contact angle measurement—A variation of surface energy testing is contact-angle. Contact-angle measurement is especially suited to manufacturing operations such as wire bonding on PCBs or the application of thin films on quartz glass which require a cleanliness test that is nondestructive. large surface where measuring one little area of it would be representative of the level of the cleaning that went on the entire surface. larger ones. optical. are all contaminants whose presence can be detected by changes in the contact angle. AN EXAMPLE OF HOW IN SITU PARTICLE MONITORING WORKS In work done by John Hunt (Pacific Scientific Instruments. various process chemicals. crevices. When the soiled plate is added. you will typically see an initial spike of particles coming off the plate when you add the soiled plate and then see particles continue to come off over time. High-technology cleaning techniques. or even human perspiration. this can be an excellent and highly sensitive method. This information can be used to optimize cleaning times in addition to cleaner concentrations. Several cleaning agents were tested for their effectiveness in removing the contamination by monitoring the rate of particle removal in the bath by recycling the bath through a filtration loop and detecting particles just before filtration.droplets. (For a fuller description of this measurement technique see “More on water-drop surface energy test. OR) to optimize a choice or concentration of cleaning agent. or blind holes.) • In-situ Particle Counting (ISPM)—Part cleanliness becomes critically important as mechanical. Vapors from the process itself. This method can be used to determine cleanliness since the properties of various contaminated surfaces are reflected by different contact angles. Grants Pass. defined simply as the relationship of certain forces when a liquid stabilizes on a part’s surface. Measuring Cleanliness 147 . By the same token. The surface-energy test is far more sensitive than the atomizer or waterbreak test and has the advantage of being able to detect both hydrophilic and hydrophobic soils. (For a fuller description of this measurement technique see “More on Contact Angle Measurement Methods. and then again when the soiled glass plate is added to the bath. hydrophilic soils.
a rise in this ratio indicated going from a dirty to a clean surface. Using a volumetric pipette a drop of typically 0. As with other cleanliness verification techniques. • Note the nature of the droplet after applying it to the surface. Several “real world” examples will help illustrate what can be learned from the use of the contact angle measuring techMeasuring Cleanliness 149 . cosmetics. Wait until the droplet has ceased its advancement and no more change in lateral movement has occurred. This will limit the number of measurement variables. If a volumentric pipette is not available. the ratio of droplet weight to area can be used to detect changes in surface energy. MORE ON CONTACT-ANGLE MEASURING METHODS Accepted methods of measuring contact angles to determine surface characteristics include the inverted bubble. A liquid droplet 3 to 4 mm in diameter is carefully deposited onto the substrate surface. Wilhelmy Plate. Gently move the sample to the liquid droplet formed at the end of the syringe/dispenser in order to minimize gravitational effects. Alternately. the specimen to be measured is loaded onto a specimen holder. Measure this time interval. It is useful to work with some known cleaned surface to observe droplet size behavior and known soiled surfaces to confirm that the residue will give the observed changes. The droplet size is measured with a micrometer. Retain consistent time intervals between the placement of the 148 The Aqueous Cleaning Handbook droplet and its measurement. if practiced.2 ml of water is placed carefully onto a surface being investigated. It is better at detecting films on smooth surfaces rather than particulates. • Accurately control liquid droplets so that they are repeatedly deposited onto the sample. will increase the repeatability and validity of the measurement results. • In case of very low contact angles. a line is drawn from the three-phase interface point through the apex. A tangent line is drawn at the three-phase interface point in order to determine the contact angle. Use a Teflon-coated needle of a higher gauge (smaller inner diameter). • Use medical-grade. The following tips from Precision Cleaning magazine. such as finger oils. The latter is the most widely practiced quality control technique. you may find it difficult to adhere the droplet from the needle to the solid sample. it may be easier to use a length times width method of estimating droplets – do not vary area calculations within a set of measurements.001 grams.MORE ON WATER DROP SURFACE ENERGY TEST Surface energy can be indirectly detected by measuring the size of a droplet of known volume sitting on a surface. and sessile drop techniques. then using an eyedropper to deposit drops and using a scale sensitive to 0. • Neutralize the effects of static charges on substrates. will skew the contact angle results. If the surface is scratched during cleaning. as it is relatively quick and requires minimal investment in time and financial resources. This angle turns out to be equal to 1/2 of the tangent angle and is reproducible by different operators. This method works well on glass and metal surfaces. Again. Substrates that are electrostatically charged can skew contact angle readings up to 5 degrees. Typically a surface with a hydrophobic oily residue film will repel the water and cause the droplets to be smaller than are observed on the clean surface. ultra-purified deionized water from a laboratory supply house in order to have a consistent measuring liquid. Organics. 23) were helpfully compiled: • Use gloves when handling the samples to be measured. and other contaminants. • Use test liquids of larger surface tension than the solid’s surface energy in order to obtain easy-to-read results. In the sessile drop technique. (Oct. If the droplet is circular the area is determined by the pi r squared method. • In the case of very high contact angles. special tips for contact angle measurement. making sure that you wait this period of time after every measurement. use the highest possible needle gauge (smallest inner diameter needle) for controlling very small droplet volumes onto the sample. 97 p. Note that any machining or scoring will distort droplets. the droplet size will become smaller causing false readings if the test is used as a before and after test.
• Optically Stimulated Electronic Emissions—When high-energy UV light hits a surface. This method is good for determining low levels of contamination (both ionic and nonionic). by MS. it cannot identify it. Very thin organic contaminants several monolayers in thickness (greater than 10 angstroms) can be evaluated using the contact angle technique. see the “In-Situ Particulate Monitoring” section of this chapter. 150 The Aqueous Cleaning Handbook • Fourier Transform Infrared Spectroscopy (FTIR)— FTIR spectroscopy is used for structural characterization of organic and inorganic molecules in solids. Organic compounds are then separated via GC and are then identified. However. followed by automatic CO2 coulometric detection. electrons are emitted.exchange resins are used to separate the atomic or molecular sample ions based on their partition ratios as they pass through the columns.nique to determine the existence of impurities on a surface. which employs the photoelectric effect. measuring the frequencies at which the sample absorbs the radiation and the intensities of the absorption. by comparing the unknown spectra to the standard frequency at which specific molecules are known to absorb light. • Gas Chromatography/Mass Spectrophotometry (GC/MS)—GC/MS is used to identify surface contamination by extracting contaminants into a solvent and analyzing them. The water contact angle correlates the “cleanliness” of the surface to the adhesion of the copper deposited onto the surface of the LCD. liquids. Spectrometers record the interaction of light energy in the form of infrared radiation with an experimental sample. LCD (Liquid Crystal Display) panel surfaces contaminated with organic matter will be less accepting of a variety of films. The measured kinetic energy of the electrons can therefore be converted to binding energies. while optically stimulated electronic emissions can detect contamination. • Ion Chromatography (IC)—Ion Chromotography is a form of liquid chromatography of aqueous samples used to determine ionic contamination on critical components. CM • Carbon Coulometry—The technique employs in-situ direct oxidation of surface carbon to carbon dioxide (CO2). The emitted photoelectrons have a kinetic energy equal to the x-ray less the binding energy of the electron. Whether you are checking the moisture effects on silicon wafers or LCD quartz panel glass metal adhesion. Sources of such contaminants include the vapor of process materials. Water contact angles can be used in various processes to determine contamination levels. resulting in poor manufacturing yields. Measuring Cleanliness 151 . After using an extraction method or by using a surface scanning machine. for the detection of elements and determination of elemental composition. (For a fuller description of additional in-situ monitoring techniques. enabling element identification. gases. chemicals. A clean surface will give the highest return current. it is generally agreed that the wetting behavior involves only the last layer or two atoms on either side of a solid’s interface. It is the only technique that can provide quantitative analysis of anions at the ppb level of an extract that has been swabbed or wiped from a surface and extracted into solution for analysis. such as metals and protective layers. all that is needed is an understanding of the basic theory involved and proper measurement techniques. so any drop in current represents contamination. and on surfaces. the sample’s chemical makeup as well as it’s concentration can be determined. Columns containing ion. predict cleanliness and adhesive bond strengths. and human perspiration. In fact. based on molecular weight. Electrons are ejected from a solid surface by irradiating the surface with an x-ray monobeam.) • Electron Spectroscopy for Chemical Analysis (ESCA)—ESCA is an extremely surface-sensitive technique. and monitor cleaning operations. DETECTION BELOW 1 MICROGRAM PER SQ. and the reflected current can be measured.
REFERENCES Alconox Cleaning Solutions newsletter. “Wetting of Thin Layers of SiO2 by Water. Mittal. “Investigation of Plasma Effects on Plastic Packages Delamination and Cracking.. edited by Les Hymes. . and Stromberg. Forward scattering primary electrons.Gypta. R. production of secondary electrons is attributable to the specimen being at high incident angles with the electron probe. George. The atomic electrons gain this lost energy. Cleaning Printed Wiring Assemblies in Today’s Environment.A. 122–132. the Netherlands. The material under investigation is bombarded with primary ions which. K. F-2265. S1-S12 (March 2001) Djennas.” 1996 Surface Mount International Conference. New York. Toshiaki Matsunaga. Kanegsberg. Ganesan. November 13–15. Laurent. p. 96. Clean Conference. Vol. The proportion of primary electrons collected as backscatter electrons (bse) increases as a function of the atomic number of the sample specimen. Kuman. 94 “Testing for cleanliness. J.2 Handbook for Critical Cleaning.” 1996 Surface Mount International Conference. Ed..” in Ch 3.” Journal of The Electrochemical Society. p. thereby impacting more electrons within the escape depth.” IEEE Trans. 2.. Carol LeBlanc. Hawkins.. 1535–39. those that are deflected at an angle of 90o or less. “Moisture Induced Stress Sensitivity Reduction of FSRAM 52 Lead PLCC’s. 431-448 Good. “An Inside Study of Aqueous HF Treatment of Silicon by Contact Angle Measurement and Ellipsometry. Armando.• Scanning Electron Microscopy (SEM)—By scanning high energy electrons across a specimen.. Frank.. 21–24. 1995. p. Carrasco. upon impact. Edward. which is determined by measuring their travel time from surface to analyzer. Yushi. 1. Number 1 article “How Clean is Clean?” ASTM. 135 (1988). October 1997 article “Contact Angles Measure Component Cleanliness. B. Those that are deflected at an angle greater than 90o can reenter the vacuum above the specimen and make up the backscatter signal. p. CHMT. Boca Raton.” ISHM Workshop on Flip Chip and Ball Grid Arrays. No. p. Trent Thompson. both elemental and molecular. 531–532. 4176. “Comparative Studies of the Contact Angle as a Measure of Adherence for Photoresist. The American Society of Testing Materials. Geosling. as well as ppb concentrations of impurities in semiconductors and metals. Wettability and Adhesion. Alvin M. 1995. cause secondary ions to be ejected from the sample’s surface. Volume 11. Richard and Goodman. 1993.” and p.R. Volume 25. Because an incline surface exposes a larger area to the electron beam.” Plenum. Toxics Use Reduction Program for The 22nd Mr. Gary and Berg. Ed. thereby portraying its chemistry. • Secondary Ion Mass Spectroscopy (SIMS)—SIMS is an extremely sensitive surface analytical technique used for chemical determination of surface constituents. p. Massachusetts.” Thin Solid Films. 607–611.” VSP. 71 (1967).” The ISHM Journal of Microcircuits & Electronic Packaging. 587–592. J “Contamination Control and Analytical Techniques. Gans.. 197 “Cleanliness Verification” Cleantech “Cleanliness Verification. Prack. Volume 1. allowing them to escape from their atoms. Oct. “Moisture Absorption and Autoclave Performance Optimization of Glob Top Ball Grid Array. No. Germany. “Contact Angle. p. “Colloid and Surface Science. These secondary ions can be identified by their mass. 18. Williams. Gould and E. Ed.L. “Relationship Between Surface Energy and Surface Contamination. 3. Herard. “The PBGA: A Systematic Study of Moisture Resistance. CRC Press Publishers. 1993. p. G. “Surface Treatment for Plastic Ball Grid Array Assembly and Its Effect on Package Reliability. 319–329. 75 (1981). Irene. Japan. Berlin.” p. Those that are very close to the surface (within the escape depth) may have sufficient energy to escape from the sample surface back into the vacuum as secondary electrons (SE).J. 1. November 1974. travel through the specimen while loosing energy. Precision Cleaning. Lewis. 1979.” Applied Physics Letters. 16. SEM allows the study of both morphology and composition of biological and physical materials. The resultant se image thus reflects the surface topography of the specimen. p. and Matsuda.” Physical Chemistry. Turi. 91–924. When high energy primary electrons impact the specimen they are deflected or scattered. 152 The Aqueous Cleaning Handbook Measuring Cleanliness 153 . R. Howard.” CleanTech Vol 3. 2001. C and Koran.
and clean. safe. Aqueous cleaning can. play a role all along this spectrum. Yet. It is. Water is a recyclable natural resource. clean. safe.photoemission.astp. as populations grow.com www.com www.alconox.pmeasuring. Water can also be a transport medium for various polluting or hazardous chemicals that may derive from the use of aqueous cleaning in specific instances. and sustainable processes. of course. Water is inherently environmentally sound and a substantially safe chemical to work with.com CHAPTER 11 Environmental Health and Safety Considerations he key environmental health and safety advantages and disadvantages of aqueous cleaners both derive from the fact that they use water for cleaning and rinsing. in fact. and reduced waste processes. possible to use aqueous cleaners with hazardous ingredients that are used to clean hazardous soils that 154 The Aqueous Cleaning Handbook Environmental Health and Safety Considerations 155 T .com www. 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 cleaning process? • How sustainable—in terms of energy and resources—is the process? All critical cleaning is a spectrum that ranges from polluting hazardous processes to clean and safe processes. clean surface water will become increasingly scarce.RESOURCES www.
all of these cycles involve far more chemical transformations and slower processes with longer residence times in various long-term forms. However. cleaning solution recycling. Then. after the water used in the cleaning and rinsing process has been recycled sufficiently to create sustainable energy consumption rates. Oxygen is also tied as geological carbonates. once again returning to surface water). and eutrophication potential. and finally. however. many of these cycles are relevant to aqueous-cleaning ingredients. Taking this a step further one can effect a reduced waste process by incorporating some degree of soil recycling. We are considering here natural processes that can contribute to sustainable processes achievable in the course of human lifetimes. limited volatile effluent and reduced solid waste by recycling cleaning and rinsing solutions with filters. Aquatic toxicity can come from very high or very low pH or the toxicity of the ingredients. Where extreme pH cleaning is required. in a purifying sense. Any water released could safely be incorporated into the natural water cycle (surface water to evaporated water to clouds to rain. It is possible to design a so-called “zero-discharge” system with no fluid effluent. one step in the carbon cycle involves extensive time spent as geological carbonates—in the same way nitrogen stays for extensive periods as nitrogen in the air. The use of biodegradable surfactants and the discharge of limited quantities of cleaning solutions generally results in no toxic concentration of surfactants in surface water. this is an oversimplification. Taking a larger view of the environmental issues concerning aqueous-cleaning processes it is reasonable to consider the energy and resources used in making the cleaner. safe. In order to move toward a clean. Improvement in safety can be achieved by eliminating the source of the hazardous soil in the process. viewed from the standpoint of a long enough time scale. sustainable processes. early detergent formulations contained poorly biodegradable surfactants that were capable of causing foaming in surface lakes and rivers when the spent solutions were discharged to drain.) One might argue that the carbon cycle. the now nonhazardous soil in the effluent would not create a hazard in the environment. industrial cleaning can also involve the use of an aqueous cleaner that has no hazardous ingredients used to clean the same hazardous soils whereby the cleaning solutions are treated prior to discharge—resulting in a clean and relatively safer process. polluting process. In fact.are then dumped in the environment—resulting in a hazardous. aquatic toxicity. but most do not have a basic natural process such as the water-cycle to purify and recycle key ingredients. For example. But by the same token. (Of course. as does water. or air pollutants. There are several important factors concerning discharge of spent cleaning solutions into the environment: biodegradability. ENVIRONMENTAL ISSUES IN AQUEOUS CLEANING The environmental issues involved in aqueous cleaning are mostly associated with the ingredients and their ultimate discharge into the environment. Phosphorus is an essential nutrient for algae. Certainly not all nonaqueous cleaners are hazardous and/or pollutants. When significant Environmental Health and Safety Considerations 157 156 The Aqueous Cleaning Handbook . Today. and the energy and resources consumed in using the cleaner. Eutrophication involves cleaners that contain phosphates. Older more highly toxic surfactants are no longer widely used in aqueous-cleaner formulations. safe and sustainable process. all modern detergent formulations use biodegradable surfactants that do no buildup and persist in the environment and cause surface water-foaming problems. almost anything can be considered to have a sustainable natural cycle of synthesis and decay. Historically. the oxygen cycle and many other elemental cycles also become involved in nonaqueous cleaning processes. Many nonaqueous cleaners are themselves health hazards. the nitrogen cycle. water pollutants. These elements simply do not cycle as rapidly. Most nonaqueous chemical cleaning methods generally have much greater difficulty in achieving clean. one would need to eliminate the use of whatever caused the hazardous soil and replace it with a nonhazardous biodegradable soil. The sur-factants in aqueous cleaners can have aquatic toxicity associated with them. and rinse water recycling. it is advisable to neutralize or discharge spent solutions in small enough quantities to avoid problems.
When cleaning by hand. NPDES (National Pollutant Discharge Elimination System) discharge permits. clean. inhalation hazards can exist with some aqueous cleaners. it is important to consider OSHA (Occupational Safety and Health Administration) regulations. however many states and municipalities have enacted legislation that restricts the use of phosphates in household cleaners. In addition. A review of this information should disclose important environmental and health hazards and regulatory issues. Eye tissue is particularly prone to attack by chemically active aqueous solutions. natural process. Gloves also afford a degree of comfort when working manually with hot solutions. However. When performing an initial review of regulatory issues for an aqueous cleaner. the acceleration of this process by phosphates is undesirable. At the very least. a review of the cleaner’s material safety data sheet should disclose any long-term chronic exposure concerns relating to carcinogenicity. it is also considered good industrial practice to wear safety glasses or other eye protection when working with aqueous-cleaning solutions. The main source of phosphorous to surface waters is agricultural run-off from farming. most completely aqueous cleaners are usually not flammable. processes that comply with current environmental and health safety regulations should be used. Good industrial practice usually involves storing acid and alkaline chemicals separately to avoid any reactions between them and aqueous cleaners in the event of accidental spills. In fact. SAFETY ISSUES IN AQUEOUS CLEANING Worker safety issues with aqueous cleaners can involve skin exposure. and to assemble as much information as you can about the soils you will be removing. There are no national regulations restricting the use of phosphates in cleaners. The first step in evaluating the environmental health and safety of an aqueous cleaner is to secure the material safety data sheet and technical bulletins for the cleaners you plan to test or use. Physical safety issues with aqueous cleaners are generally concern storage and handling to avoid any hazardous reactions with other industrial chemicals. and chronic systemic exposure. many highly acidic or alkaline cleaners require the use of chemical-resistant gloves for worker safety. As previously mentioned. Accordingly. eye exposure. some aqueous cleaners can contain ingredients that can create hazardous chemicals when burned. it can result in vigorously growing algae blooms. There are currently no restrictions on the use of phosphate containing cleaners in industrial cleaning applications. and reduced waste cleaning processes— and to continually strive toward achieving ultimately sustainable processes. Even the mildest cleaners can sometimes cause “dishpan-hand” skin irritation. Particularly hazardous aqueous cleaners should have warnings and recommended eye protection on the label.) PRACTICAL REGULATORY REVIEW In today’s manufacturing environments. The algae die and settle to the bottom of the water causing more rapid than normal filling in of lakes and ponds with silt and organic matter. DEP (Department of Environmental Environmental Health and Safety Considerations 159 . Some aqueous cleaners contain bleaches or other oxidizing agents that should be stored away from reactive chemicals that might undergo hazardous oxidation reactions. Eye exposure is also a concern with many aqueous cleaners. Because aqueous cleaners generally do not have volatile solvent ingredients. ingestion. Some semiaqueous 158 The Aqueous Cleaning Handbook cleaners may contain volatile solvents that require special ventilation and possibly even flammability controls. (It is considered good practice to wear respiratory protection when fighting any fire involving industrial chemicals. Although eutrophication is a normal.amounts of phosphorus are discharged into surface water. inhalation. While it is relatively unusual for an aqueous cleaner to contain any carcinogenic ingredients. it is always good practice to wear protective gloves. Consult the label and material safety data sheet on the cleaner for warnings and safety precautions. However. it is considered good industrial practice to have some respiratory protection when working with sprays and mists in openspray cleaning. it is realistic to try to achieve safe. it is somewhat unusual to find the need for respiratory protection with such cleaners. Any special ventilation required should be noted on the material safety data sheet.
By choosing the safest. In the long run. environmentally sound cleaning.gov 160 The Aqueous Cleaning Handbook Appendix 161 . Such an audit may result in changes in the way you currently manufacture and clean. article “Surfactants and the Environment. December 1995. Inc. Vol. 1.gov www.Protection) sewer connection/extension permits. the majority of cleaning problems can be solved with more than acceptable levels of worker safety and environmental impact. it may be wise to conduct a full scale environmental audit no matter what type of cleaning system you are using.osha. State and local environmental regulations should also be considered. and any RCRA (Resource Conservation and Reclamation Act) hazardous waste class or Clean Water Act regulations. p. In fact. 13–18.) When compared with many of the hazards of nonaqueous and semiaqueous cleaners—such as those containing ozonedepleting fluorocarbon solvents. No.” by Larry N.alconox. (A program of regular re-auditing can assure continued regulatory compliance.com www. most environmentally sound aqueous cleaner that will perform to your cleaning requirements. Appendix I II III IV V VI List of Abbreviations Cleaner Types from Alconox. and flammable components—aqueous cleaners are a sound choice for safe. Britton. Detergent Selection Guide Glossary of Essential Terms Application Case Histories Index ADDITIONAL READING Precision Cleaning. article “Environmental Auditing: Learning from Common Pitfalls and Issues”. January 1998. RESOURCES www. Journal of Surfactants and Detergents. 1. carcinogenic organic solvents.epa. after conducting a full-scale environmental audit many companies turn to aqueous cleaning as a means to more easily and safely achieve regulatory compliance.
pressure spray. spray CIP. circulate CIP siphon tube and pipete washer machine washer.APPENDIX I LIST OF ABBREVIATIONS BOD Biological Oxygen Demand CFC Choloro Fluoro Carbon CIP Clean in Place COD Chemical Oxygen Demand DEP Department of Environmental Protection EH&S Environmental Health & Safety EPA Environmental Protection Agency FT-IR Fourrier Transform Infra Red GWP Global Warming Potential LAS Linear Alkylbenzene Sulfonate LCD Liquid Crystal Display MSDS Material Safety Data Sheet NPDES National Pollution Discharge Elimination Systems ODP Ozone Depleting Potential ODS Ozone Depleting Substance OSHA Occupational Safety and Health Administration RCRA Resource Conversation and Reclamation Act SARA Superfund Authorization and Reauthorization Act SNAP Significant New Alternatives Policy TCVLP Toxic Chemical Leaching Properties UV Ultra Violet VOC Volatile Organic Compound APPENDIX II CLEANER TYPES FROM ALCONOX.alconox. low-foaming Mild alkaline tablet Neutral. ph 877-877-2526. circulate CIP manual.. ultrasonic. high alkaline Ion-free. pressure spray. INC. alkaline Low-foaming. www. low-foaming Enzyme cleaner Low-foaming. spray Brand ALCONOX® powder LIQUI-NOX® liquid CITRANOX® liquid ALCOJET® powder DET-O-JET® liquid DETERGENT 8® liquid ALCOTABS® tablet LUMINOX® liquid TERG-A-ZYME® powder CITRAJET® liquid 162 The Aqueous Cleaning Handbook Appendix 163 . ultrasonic. pressure spray. email cleaning@alconox. soak. soak.com. 30 Glenn St. spray CIP machine washer. acidic Cleaning Methods Used manual. mild alkaline Acid cleaner Low-foaming.com Cleaner Type High emulsifying. ultrasonic. soak. spray CIP. circulate CIP machine washer. circulate CIP machine washer. spray CIP machine washer. ultrasonic. soak. soak. pressure spray. circulate CIP manual. ultrasonic. pressure spray. manual. White Plains. manual. NY 10603.
tissue on instruments. Ultrasonic. food-contact equipment.5. CITRAJET ALCONOX. Proteinaceous soils. brass. Manual. The charge on the surfactant determines the charge of the cleaner or detergent. C-I-P* Machine washer. CITRAJET CITRANOX CITRAJET TERG-A-ZYME ALCONOX. Acid cleaners are able to clean using the cleaning mechanism of acid solubalization (see other definitions) where an acid reacts with a soil molecule to create a water soluble molecule. Inorganic residues.APPENDIX III DETERGENT SELECTION GUIDE Application Key Concerns Healthcare Effective preparation for sterilization. Reduce waste. sani-sterilizer Manual. Laboratory safety. ALCONOX Pharmaceutical Passing cleaning validation for FDA good manufacturing practices. samplers. Aqueous cleaner—a blend of water soluble chemicals designed to remove soils into a water based solution with a water continuous phase during cleaning. solubilizing (see other definitions) alkaline soluble soils. LIQUI-NOX ALCOJET. DET-O-JET ALCONOX. Soak Machine washer. benches. conductive residues. Soak. Ultrasonic. Soak. Ultrasonic. ware washer Manual. plastic. pressure spray Manual. fluxes. Ultrasonic. C-I-P* Machine washer. assemblies. LUMINOX. Glossary of Essential Terms 483—the warning letter threaten close from FDA. power spray board and screen washers Manual. Oxides. salts. Filter membranes. Ultrasonic. Soak. DET-O-JET. ARP—annual product review. Soak. Glass. Soak. Spray *Clean-in-Place by circulating. Ultrasonic. Bailers. CITRAJET ALCONOX. bioreactors. Soak. buffing compounds. no interfering residues. Ultrasonic. trace metals. pressure spray Manual. Soak. DET-O-JET. clean rooms. LUMINOX ALCONOX. tissue culture. labware washer. animal cages. C-I-P* Machine washer. API—active pharmaceutical ingredient. DETERGENT 8 DETERGENT 8. pigments Protein/ferment residues. anaesthetic. Soak. Ultrasonic. pipes. C-I-P* Manual. porcelain. Soak. LUMINOX ALCONOX. Ultrasonic. C-I-P* Parts washers. Circuit boards. Glass. Metal brightening. DET-O-JET. power wash Manual. CITRANOX DETERGENT 8. Typical anionic surfactants include organic sulfates. milkstone. and hydrolysis (see other definitions). Alkaline cleaner—a water based cleaner that contains alkaline ingredients that cause the cleaner to have a significantly high pH. Food and Dairy Avoid interfering residues on food-contact equipment. Ceramic insulators and components. metal. protective equipment. C-I-P* Parts washer. Stainless steel. longer instrument life. avoid CFCs.5 would be a high alkaline and corrosive cleaner. Ultrasonic. labware washer Manual. pressure washers Manual. Inorganics. Acid cleaner—an aqueous cleaner that has a pH significantly below 7. Ultrasonic. scale. LIQUI-NOX CITRANOX. power wash Manual. Manual. machine washers Nuclear Avoid waste interference. LUMINOX. warewasher Manual. LIQUI-NOX ALCOJET. Environmental No interfering residues. CITRAJET ALCOTABS LIQUI-NOX. bio-wastes. blood and other body fluids. LIQUI-NOX ALCOJET. sequestration or Laboratory Reproducible results. buffing compounds. C-I-P* Manual. DET-O-JET. Cleaning Method Manual. Trace metals. salts. LIQUI-NOX ALCOJET. ceramics. Soak. LUMINOX CITRANOX ALCOJET. Tubes. resins. and other soft metal parts. Water and environmental sampling. Soak. for spray clean-in-place see machine washer detergents. U/F membranes. Phosphatesensitive labware. salts. Soak. cage-washers Siphon-type washer-rinsers Manual. Lenses. Manual. Metal oxides. fibers. washer-sterilizer. Proteinaceous soils. blood and other body fluids. LUMINOX DETERGENT 8. reflectors. power spray. A cleaner with a pH above 12. Soak. LUMINOX DET-O-JET. Minimize crosscontamination. C-I-P* Machine washer. Oils. salts. Difficult proteinaceous soils. stainless steel. teflon. power wash Manual. Anionic surfactant—a cleaner ingredient that is a surface active agent(see other definitions) that has a negative charge on the organic portion of the molecule. Metalworking and Precision Manufacturing Clean parts. and other hazardous chemicals. Product-contact surfaces. CITRAJET ALCONOX ALCOJET. screens. LUMINOX DETERGENT 8. C-I-P* Machine wash. DET-O-JET ALCONOX. reusable pipets. R/O. sulfonates and carboxylates. DET-O-JET LUMINOX. mirrors. chemicals. pressure spray Manual. Ultrasonic. particulates.5–11 can be considered to be a mild alkaline cleaner. metallics. rubber. power spray Cosmetics Avoid crosscontamination. LUMINOX DETERGENT 8. LIQUI-NOX ALCOJET. Radioactive equipment/contaminants. LIQUI-NOX ALCOJET. copper. Ultrasonic. Bioburden—microbes on the surface. pressure washers Manual. augers. salts. metallic complexes. Ultrasonic. DET-O-JET.5 is at least an unqualified alkaline cleaner. plastic labware. Catheters and tubes. porcelain. Soak. EPA procedures. Phosphate free. tissue. Electronics Avoid conductive residues. C-I-P* Machine wash. parts. Ultrasonic. Optics Avoid optical interference. Alkalinity helps promote saponifying(see other definitions). C-I-P* Parts washer. Soak. tools. LUMINOX. A cleaner with a pH of 8. rubber. A cleaner with a pH of 11–12. The most common anionic surfactant is sodium dodecylbenzene sulfonate. An anionic detergent contains anionic surfactants. power wash Manual. C-I-P* Machine wash. Ultrasonic. Stopcock grease. particulates. CITRAJET ALCONOX ALCOJET CITRANOX CITRAJET TERG-A-ZYME ALCOJET. and acid hydrolysis (see other definitions) where an acid reacts with a soil molecule and breaks it into a smaller water soluble soil. typically below a pH of 5. Soak. strong acids. avoid volatile solvents. Aluminum. pass cleaning criteria. Silicone oils. and examining instruments and equipment. C-I-P* Parts washer.. containers. CITRAJET TERG-A-ZYME ALCOJET. Anionic surfactants can be and usually are emulsifiers (see other definitions) and dispersants(see other definitions). Soak. trace metals and oxides. Reactor cavities. Soak Parts washers. Builder—a cleaner ingredient that enhances the cleaning ability of the surfactants in at least one. C-I-P* Machine washer. Ultrasonic. scale. power wash Manual. stainless steel. rosins. Ultrasonic. Product contact surfaces. scale. Soak. glass. Acid cleaners contain acids and often other cleaning ingredients such as surfactants. metal oxides. Soak Machine washer. substrates. Ultrasonic. tubing. particulates. APPENDIX IV Articles Cleaned/Soil Removed Surgical. LIQUI-NOX ALCOJET. ceramic. CITRAJET CITRANOX CITRAJET TERG-A-ZYME ALCONOX. LIQUI-NOX CITRANOX. safety equipment. Ultrasonic. Soak. C-I-P* Machine washer. mold-release agents. C-I-P* Glassware washer Manual. Ultrasonic. and usually a combination of the following ways: softens water to prevent water hardness ions from reacting with the surfactants or soils by chelation. Ultrasonic. fermentation residues. C-I-P* Parts washer. LUMINOX ALCOJET. LUMINOX ALCOJET. extending equipment life. Soak Machine washer. tubing. Ultrasonic. 164 The Aqueous Cleaning Handbook Appendix 165 . sani-sterilizer Manual. chemicals. DET-O-JET CITRANOX CITRAJET LIQUI-NOX. Soak Parts washers Recommended Detergent ALCONOX. Keep laboratory accreditation. C-I-P* Machine. scale. Oils.
An nonionic detergent contains nonionic surfactants. Typically an ion-free cleaner will contain nonionic surfactants and other ingredients that are not metallic salts. Degreaser—a cleaner that is designed to remove oils and greases. 166 The Aqueous Cleaning Handbook Appendix 167 . IQ—installation qualification. CFR—code of Federal regulations. non-active pharmaceutical ingredients. Nonionic cleaner—a cleaner that contains nonionic surfactants. Cleaner—a chemical or blend of chemicals designed to clean. Dissolve—a cleaning mechanism that relies on a cleaning fluid to be able to form a stable mixture with individual soil molecules. inhibits redeposition of soils. below 7 is acidic and above 7 is basic or alkaline. These are typically heavy duty cleaners that are designed to remove gross amounts of oil and grease leaving a visually clean surface rather than light duty fine cleaners that are designed to remove lower or trace levels of oils that leave a measurably or analytically clean surface. A typical builder is sodium polyphosphate. Dispersant—a cleaner ingredient that reacts with water insoluble particulates to overcome electrostatic attraction by the particulate to a hard surface to create a liquid solid mixture in the form of a suspension. and improve the handling. These cleaners tend to rely more on emulsifying and dissolving rather than aggressive chemical attack on soils that are possible with acid or alkaline cleaners. provides corrosion inhibition. CIP—clean in place. saponifies soils. adds alkalinity. ppm—parts per million (mg/liter. ICH—International Conference on Harmonization. This occurs when a fat or oil is hydrolyzed to make soap as in saponification (see other definitions) or when an enzyme breaks down a protein. Typical examples of chelating agents include sodium polyphosphates and ethylene diamine tetra acetic acid (EDTA). flowing. detergents. which in the case of oil and water involves a small droplet of oil surrounded by emulsifier such that the emulsifier is in contact with the water and the entire surrounded droplet or micelle is dissolved in the water. Excipients—fillers.binding. the word detergent is used when the word surfactant is meant. emulsifies oils. Typical nonionic surfactants include organic ethoxylates. In the context of cleaners these molecules are surfactants usually arranged in sphere or rod shapes with the hydrophilic end of the surfactants facing outwards into the water solution with the hydrophobic ends of the molecules facing toward the inside of the aggregate. In some industry usage.5 to 8. OQ—operational qualification. The charge on the surfactant determines the charge of the cleaner or detergent. IC—ion chromatography. and/or water based blends. cGMP—current good manufacturing practice. and storage characteristics of the cleaner. typically in the range of 5. In aqueous cleaners. Emulsifier—a cleaner ingredient that lowers the interfacial tension between immiscible liquids such as oil and water thereby allowing them to mix. A typical dispersant is sodium polyphosphate. (see ion-free cleaner). In practical terms. one of the cleaning mechanisms is for the water to dissolve water soluble soils. Nonionic surfactant—a cleaner ingredient that is a surface active agent(see other definitions) that has a no charge on the organic portion of the molecule. acids. These may be solvents. buffers a cleaner to maintain alkalinity. Micelles are able to hold hydrophobic oil molecules inside them and create stable emulsions. A nonionic cleaner may easily contain nonionic surfactants blended with many ionic builders that are sodium salts or other metal ion salts. Hydrolyze—to break a molecule apart using acid (H+) and hydroxyl ions (OH -) from water (H 2O). pH 7 is neutral. disperses particulates. A nonionic detergent may contain many ionic salts. bases. Neutral cleaner—a cleaner that has a pH near 7.5. Many chelating agents are also sequestering agents (see other definitions). microgram/liter). Ion-free cleaner—a cleaner that has no metal ion ingredients. Most degreasers are either high alkaline aqueous cleaners or solvent based cleaners. enhances surface tension lowering of surfactants. pH—a measure of how acidic or basic a solution is defined as the inverse log of the hydrogen ion concentration in water. Chelating Agent—a cleaner ingredient that is an chemical with at least 2 available sites on the molecule to bind with metal ions in a water based solution to form a ring compound with metal. just the surfactant is not ionic and does not have an electrical charge. The most common anionic surfactants are alcohol ethoxylates and alkylphenol ethoxylates. The term does not mean an ion-free cleaner. breaks up clumps of particles by deflocculation. ppb—parts per billion (ug/liter. Detergent—a blend of ingredients intended for cleaning that include at least a surfactant (see other definitions) to give at least emulsifying or dispersing and a builder (see other definitions) to inhibit water hardness precipitation from calcium and magnesium salts. Emulsifiers are surfactants (see other definitions). An ion-free cleaner does not contain sodium or other metal salts. A nonionic detergent is not necessarily ion free (see other definitions). Nonionic surfactants can be and usually are emulsifiers (see other definitions) and dispersants (see other definitions). GC—gas chromatography HPLC—high performance liquid chromatography. LOD—limit of detection (signal to noise S/N = 3) LOQ—limit of quantitation (signal to noise S/N = 10) Micelle—is a sub-microscopic aggregate of molecules. milligram/liter). A typical mechanism for emulsifying is for the emulsifier to form a micelle.
nonionic. liquidliquid. and liquid-solid interfaces. Soap is a surfactant (see other definitions) that usually has good emulsifying properties for the oils or fats from which it is derived. or they may be blended with water during use. Titrate—wet chemistry test to detect an amount of something. Surface active agents are either anionic. 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). This means that a surface active agent can act as a wetting agent to allow a cleaner to wet a surface or penetrate into small cracks and crevices to perform cleaning. UV-vis—ultraviolet or visible spectroscopy. Typical saponifiers are potassium hydroxide and sodium hydroxide. The hydrophilic end of the molecule is stable in water and the hydrophobic end of the molecule is more stable out of the water next to the air. Saponifier—a cleaner ingredient that reacts with a natural oil ester. Surfactant—see surface active agent. RAL—residue acceptance limits. This tension acts to minimize surface areas of a solution. In an aqueous cleaner the water acts as a polar solvent to help solubilize polar soils. A surface active agent can act as an emulsifier with oil. One issue with soap is that it can react with calcium or magnesium hardness ions in tap water to form water insoluble calcium or magnesium salts that precipitate out as a soap scum film. The main cleaning mechanism of solvent based cleaners is solubilizing or dissolving. or resin ester such as rosin to split the poorly water soluble ester into a more water soluble salt (or soap) of an acid. In the context of cleaners this means chemicals that lower the surface tension or interfacial tension at liquid-gas. Fluorocarbon based freon cleaners are solvent cleaners. cationic. Solvent cleaner—a cleaner that is made up of one or more organic chemicals that have some ability to dissolve soils. or amphoteric (see other definitions). 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. SOP—standard operating procedure. oil or surface away from the water solution. in fact there is usually no water present in their formulations. A typical sequestering agent is sodium polyphosphate. Surface active agent—or surfactants are an ingredient in most aqueous cleaners that are chemicals that are active at solution surface 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 end of the molecule that is hydrophilic (“water loving”). In the case of many compounds this converts a water insoluble oil or resin into a water soluble soap that in turn acts as an emulsifier to emulsify any unreacted oil or resin and assist with cleaning. Soap—the salt of an acid. Solubilizing—a cleaning mechanism that involves dissolving a soil into a single aqueous phase that relies on a “like dissolves like” principle. Typically solvent cleaners contain volatile organic compounds. These are usually either a solvent or blend of water soluble solvents that are used straight without water as a cleaner followed by a water rinse. 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. Semiaqueous cleaner—a chemical or blend of chemicals or solvents that are used to clean that rely on a water rinse. TOC—total organic carbon analysis. particulate.PQ—performance qualification. 168 The Aqueous Cleaning Handbook Appendix 169 . A surface active agent react with a particle to act as a dispersant. Solvent cleaners do not have a water continuous phase present during cleaning.
OPTICAL WAX MORE HEAT FOR FASTER CLEANING An optical lens manufacturer had been using ALCONOX powdered detergent in a heated ultrasonic bath for years to remove a wax from the lens during manufacturing. Time Temp Agitation Chemistry Rinse Dry Problem Initial Problem 10 min 60 deg C ultrasonic 1% ALCONOX deionized water air cleans to slow Solution 5 min 70 deg C ultrasonic 1% ALCONOX deionized water air 170 The Aqueous Cleaning Handbook Appendix 171 .APPENDIX V Application Case Histories 1. By increasing the temperature. this system was not able to clean fast enough. As production grew. adequate cleaning performance and speed were achieved.
a metal valve manufacturer had been using LIQUINOX liquid detergent in an immersion tank that was made up and depleted in one shift to remove process oils from metal valves. they observed that their standard cleaner could not even get their coating equipment visually clean. The valve manufacturer observed that toward the end of the day the tank did not clean as well as at the beginning of the day. PRECISION MANUFACTURING PROCESS OILS HIGHER CONCENTRATION INCREASES BATH LIFE For years. When the company started to make tablets with enteric coatings. PHARMACEUTICAL TABLET COATING EQUIPMENT SOIL CHANGE CAN REQUIRE CLEANER CHANGE A pharmaceutical company had been using a typical high alkaline cleaner for manual cleaning of tablet coating equipment. By changing to an acid cleaner that was effective on the water insoluble inorganic salts used in the enteric coating they were able to get their equipment clean. As production grew. This worked fine with their standard tablet coatings. the manufacturer was able to increase the soil capacity of the solution and thereby extend the bath life to meet his needs.2. 3. Time Temp Agitation Chemistry Rinse Dry Problem Initial Problem Solution 20 min 20 min 50 deg C 50 deg C soak soak 1% LIQUI-NOX 1. the number valves and quantity of oils to be removed increased.5% LIQUI-NOX deionized water deionized water air air tank did not last long enough Time Temp Agitation Chemistry Rinse Dry Problem Initial Problem Solution 10 min 10 min 50 deg C 50 deg C manual manual 1% High Alkaline 2% CITRANOX deionized water deionized water air air system could not clean enteric coating on tablet coating equipment 172 The Aqueous Cleaning Handbook Appendix 173 . By increasing the concentration of detergent.
spot free drying was achieved. The filter flow rates and pressures would not recover after cleaning. Finally bio-fouling began to occur in the filter and the resulting proteinaceous soils would crosslink and become tenacious when exposed to the hot alkaline cleaning solution.4. Time Temp Agitation Chemistry Rinse Dry Problem Initial Problem 10 s/ft 55 deg C spray 1/2% DET-O-JET hard tap water air knife water spots Solution 10 s/ft 55 deg C spray 1/2% DET-O-JET deionized water air Time Temp Agitation Chemistry Rinse Dry Problem Initial Problem Solution 1 hour 1 hour 55 deg C 55 deg C circulate circulate high alkaline 1/2% TERG-A-ZYME tap water tap water none needed none needed fouled filter membranes 174 The Aqueous Cleaning Handbook Appendix 175 . 5. In their existing plant the tap water was soft without much dissolved calcium or magnesium in it. When they set up another plant in another part of the country they kept getting water spots because the local water at the new plant site was hard water with a lot of dissolved calcium and magnesium in the water. WASTE TREATMENT FILTERS ENZYME CLEANER CURES BIOFOULED FILTERS A small scale in-house waste treatment filtration plant was being used to remove oils from a waste stream at a manufacturing plant. The filter membranes were typically cleaned with a high alkaline cleaner at high heat. By switching to a deionized water rinse at the new plant and by beefing up the air knives. The manufacturer was able to clean and rinse sheets of glass in a conveyor spray system using tap water to rinse prior to air knife drying. ARCHITECTURAL GLASS MANUFACTURER SEES SPOTS WHEN SETTING UP MANUFACTURING IN A SITE WITH HARD WATER DEIONIZED WATER STOPS WATER SPOTS An architectural glass manufacturer had one plant where they used DET-O-JET cleaner to clean glass prior to coating. The solution was to treat with TERG-A-ZYME enzyme cleaner at moderate temperatures to restore the filters to their normal flow rates and pressures.
The old cleaning process involved soaking the pipets in a static soak bath and then rinsing them in a siphon pipet rinser before air drying. “I can’t begin to tell you how many dinner parties I have attended where the wonderful.or 20-year-old Pauillac was flawed by the smell of dishwater detergents. 7. rinse water continues to flow and rinsing is completed. Time Temp Agitation Chemistry Rinse Dry Problem Initial Problem Solution 30 sec 30 sec 50 deg C 50 deg C manual manual dish detergent 1% LIQUI-NOX tap water tap water air air Fragrance residues on wineglasses interfered with wine bouquet Time Temp Agitation Chemistry Rinse Dry Problem Initial Problem Solution 8 hours 8 hours ambient ambient soak soak followed by circulate lab detergent lab detergent plus ALCOTABS DI water DI water air air soaking alone could not remove all reagent residues in pipets 176 The Aqueous Cleaning Handbook Appendix 177 .. a concentration of detergent became available for cleaning during the higher agitation rinse process to complete the removal of residues that had been loosened during soaking.” In fact the human palate is very sensitive to fragrances found in many detergents. LABORATORY PIPETS FAIL TO DELIVER INCREASED AGITATION IMPROVES CLEANING An analytical laboratory had been using volumetric pipets to precisely measure volumes of analytical reagents. A major supplier of wine tasting glasses found that he was able to satisfy the needs of his discerning clientele by suggesting they use free-rinsing. When they calibrated their pipets they found that their old pipets were not as reliable as brand new ones.. After the ALCOTAB had completely dissolved in the siphon rinser. By adding ALCOTABS tablets to the siphon pipet rinser. cedary. WINE TASTING GLASSES ELIMINATING DETERGENT FRAGRANCE RESIDUES The world renowned wine critic Robert Parker observed in his book BORDEAUX. blackcurrant bouquet of 15.6. The problem was traced to incomplete cleaning. fragrancefree LIQUI-NOX cleaner instead of the depositing fragrance containing household dishwashing detergents they had been using.
153 Atomic absorption (AA). 137. 17. 139. 88. 27. 27. 65. 123 Aggressive. 44-46. 57-60 Bioburden. 60. 59. 80. 81 B Batch cleaning. 42. 86. 26 BOD. 68. 9. 95. 46. 43. 52. 90. 66. 121. 91 Activated carbon. vii. 80 Alkaline. 71 Blood. 97. 135. 44. 78. 15. 57-60. 63 Bench-scale testing. 6769. 168 Aqueous cleaner. 173. 163. 41. 80. iii. 107. 134-135. 3-4. 135. 11-13. 54. 66. 1. 77. iii. 14. 68-69. 14. 37. 141. 1-2. 93. 65-66. 155160. 46. 89. 88 Anti-redeposition. 24. 13. 9. 80. 62. 44. 157 Aqueous. 166. 4144. 27. 83. 61-62. 61-62. 143. 165 Alkaline salt builders. 45. 11 Aluminum. 174 Carbon. 31. 26. 34. 171-177 Air knife. 175 Alkaline cleaner. 165. 20. 11-12. 22. 124. 110 Amphoteric surfactant. 168 ASTM. 65-66. 39. 108. 55. 86. 23-25. 14. 51. 39. 138-139. 15. 146 Automatic syphon washing. 167 Anodized part. 66 Blow-drying. 46 Bath life. 48-49. 125. 122. 25. 28. 6. 124-126. vii. 162 Body fluids. 35.APPENDIX VI Index A Absorption. 78. 56. ix-x. 151 Anionic surfactant. 107. 54. 9-10. 4-9. 172 Bench-scale. 119-120. 38. 155-160. 84. 78. 38-39. 82-85. 56. 127. 17. 131-132. 110. 151. 164 Blood-born pathogens. 9. 1316. vii. 91. 56. 165 Biodegradable. 135. 23. 48. 90-94. 15-16. 13-16. 165-166. 6-9. 159. 1-2. 92. 127. 135 Additives. 12. 11-13. 18-20. 125126 Anion. 145. 34. vii-x. 10 Analytical method. 116. 107. 42. 19-20. 174 Air pollution. 80. 134. 48-49 51. 151. 78. 129. 20 Aquatic toxicity. 57. 164 Aluminum foil. 145 Atomizer. 52 Air/solution interface. 165-167. 153. 32. 130-132. 16-18. 158. 95. 168. 142. 46. 19-20. 28. 178 The Aqueous Cleaning Handbook Appendix 179 . 34. 165-167 C Calcium. 167 Agitation. 39. 128 Blender. 14. 135. 87-91. 131. 4. 103. 156157 Biotechnology. 153 Acid cleaners. 130. 165-166. 37. 164 Builder. 78 Bath dumping. 22-23. 165 Acrylic. 87-93. 67-68. 145. 4647. 75 ADI carryover. 101. 46. 30-31.
165-167. 131. 166. 172. 149. 98. 73 Change control/maintenance. 164 Certificates of Analysis. 42. 60. 9. 3. 8182. 79. 32. 37-38. 122 Cross-contamination. 160 Flash point. 125. 8. 82 Cationic surfactants. 78. 167. 117. 85. 162 Computer parts. 105. 84. 164-165 Ferrous. 97. 128. 24 Circulation system. 78-80. 26. 19. 45. 105-106. 88-89. 23 Coupling agent. vi. 124-125. 34. 102. 94. 124. 166 Corrosion inhibiting agents. 148. 132-133. 44. 147. 45. 157. 42 Filler. 52. 6. 68. 15 Controlled foaming. 15. 13. 58. 57. 62. 63. 156. 17. 131. 27. 38. 80. 138. 37-39. 139 COD. 135. 138. 134. 141. 67. 164. 175 Flammable. 129. 129 Dissolved organics. 125 Eutrophication. 104. 166. 39. 121. 111. 9-10. 177 Concentration gradient dissolving. 13-14. 33. 85. 105. 116. 163 Cleaning performance. 60. 19. 47. 58. 164 Counterflow-cascade. 81-82. 109. 135. 134. 52. 33-34. 22. 44. 16 Concentration. 85. 54. 10 Cavitation. 9. 93-94 Foam height. 132. 71. 166 Filter. 23-24. 163 Cleaning efficiency. 45. 28. 128. 36. 24. 138 Flocculent. 88-89. 119 Chelating. 15. 38. 129. 83 EU. 151 F FDA. 144. 56 Corrosion. 11-12. 145 Evaporators. 52. 106-107. 93. 16. 125. 37. 6. 61-62. 108109. 17. iv. 88 Closed-loop. 12. 1. 48 Equipment "blanks". 35. 177 Cleaning process design. 129. 67. 117. 47. 68. 137 Dipole moment. 122. 24-29. 42. 147 Detergent solution. 120. 24. 55. 135-137 Contact-angle. 88. 59 Electronics. 166 Corrosion inhibitor. 12-14. 26 Ceramic. 27. 33. 147 Cleaning validation. 161. 54 Evaporation. 43. 22. 58 Disposable. 90. 142. 56. 38. 48. 112-114. 121 Enzymatic hydrolyzing. 34. 45 EDTA. 15. 150 Carcinogens. 166 Defluxing. ix. 30. 87. 84. 157. 41. 167-168 Distilled water. 142. 73. 44. 11-12. 21. 34. 84-85. 103. 33. 55. 52. 151 Contaminant dispersants. 71. 59. 24. 164 Electrostatic repulsion. 39. 20 180 The Aqueous Cleaning Handbook Appendix 181 . 44. 104 Drying. 1. 44. 71. 171 Cleaning process. 45. 21. 58. 45. 6. 84. 67-68. 98-100. 58 Counterflow-cascade rinse. 117. ix. 93. 88. 100. vii. 137 Dissolved inorganic solids. 21. iv. 149 Contaminant. 156. 150. 129. 164 Cleanroom. 105. 88. 138 Electronic solder flux cleaning. 15-17. 75. 51-52. 132. 39. 162 Chamber flexibility. 31. 131. 105. 41. 93. 84 Conductivity. 24. 71 Emulsification. 73 D Deflocculation. iv. 136. 11. 66 Endotoxin. 47. ix-x. 33. 130. 9. 116. 23. iv. 32. 142. 103 Dispersant. 88 Concentrated cleaner. 54. 85 Disinfectant. 94. 159. 157.130-132. 78. 143-145. 78. 24. 16. 79. 121. 139 Cleaner type. 46. 95. 169 Dispersing. 19. 52. 121. 122. 82 Environmental considerations. v. 131-135. 126. 123 Detergency. 15. 72. 3 Chlorofluorocarbon. 67. 147 Cleaner recycling. 70-71. 15 Corrosion inhibition. 82-83. 54. 33. 119. 52. 61. 90. 9. 19. 31. 159. 61. 44. 130 Extenders. 65-67. ix. 24. 10. 163. 43. 23. 86. 20 E Economic factors. 168 Chelating agent. 62. 94. 98. 36. 94. 22-23. 67. 55 Enzyme. 132. 54. 12. 114-115. 16 Coupon sampling. 22-23. 13. 82. 94. 146. 143. 84-85. ix. 57. 83. 22 Fluid processing. 80-81. 17. 107. 56-57. 15. 51. 23-24. 33. 165-169 Endoscopes. 20. 25 Chlorocarbon. 68. 84. 68. 6-7. 67-68. 136. 80. 97-98. 124. 137 Emulsified oils. 122. 13-14. iv. 88 Corrosivity. 25. 85. 119. 79 Disposal. 23. 99. v. 31-35. v. 127 CFC(s). 126 Cleaning time. 48 Cleaner concentration. 137 Economy. 158 Evaluation method. 39. 116. 3-4 Circuit board cleaning. 42. vii. 21 Foaming agents. iii. 95 Cycle time. 133. 15. 175 EPA Priority Pollutants. 125. 15. 84. 141. 71. 135. 111. 9. 35. 166 Displacement. 25. 107. 147. 65-66. 167. 17. 114. 129 Flow-through clean-in-place. 145. 150 Carbon coulometry. 92. 90-91. 13-14. 15. 92. 42. 24. 99. 39. 144. 146. 2. 16 Extraction. 32. 156. 80. 171-174 Detection limit. 87. 130. 36 Clean Air Act Amendment. 2-5. vi. 31. 114. 43. 69 Cleaning method. 24. 44. 116 Centrifugal drying. 54. 148. 174. 61. 137. 46. 54. 129 Dissolving. 150 Electronic component. 129. 151-152. 58 Conductive residue. 133. 97. 93. 58-59. 45. 134 Emulsifier. 51. 15. 91-92. 21. 105-106. 37-38. 15. 141. 168 Chemical drying. 28-29. 8. 86. 177 Drying method. 166 Electron spectroscopy. 90. 34. 79. 65. 127128 Clean-in-place. 54. 138 Cosmetic. 38. 75. 48 Enzymatic detection. 129130. 119. 56. 155. 63. 85. 18. 87 Deionized water. 15. 80. 136-137 Foam suppressing capabilities. 51. 24. 135. 69 Detergent concentration. 95. 124 Environmental and water testing. 8.
81 Magnesium. 142 Master validation plan. 42. 79. 4. 44. 141. 143. 15. 58 Mass spectrophotometry. 84. 55-67. 68. 72 Gravimetric. 149. 82 OSEE. 130. 123 Montreal Protocol on Substances that Deplete the Ozone Layer. 84 Overkill system. 5 Lipophilic. 42. 158. 82. 100. 59. 85. 6. 166 Glass. 167. 114. 71. 34. 65. 47. 174 Glassware washer. 82. 119. 60. 9. 133 Operating cost. 132. 1. 9. 167. 14. 145 Oil viscosities. 134-135 Millipore filter measurement. 151 143. 21. 151. 11. 144 Optically stimulated electronic emission. 91-92. 87. 99100. 145. 143. 150. 28. 65. 44. 173. 14-16. 16. 55-57. 129 Insoluble particles. 67-69. 37. 82-84. 56. 85-86. 6. 45. 30. 32. 159-160. 87. 8. 44. vii. 142- P Parenteral medical device. 164. 16. v. 30. 142. 42-44 56. 84. 66 PC board. 44 Ion chromatography (IC). 162 Outgas. 86. 10. 30 Global warming. 164 Hazardous chemicals. 162. 90. 129. 135. 32. 151. 164 HEPA filter. 85 PC board washer. 98 Mass displacement. 167 Ignitability. 6. 70-71. 45. 45. 92. 125. 126. 9. 114-115. 1. 79-80. 150. 45-47. 133. 79. 20. 168 Low-foaming detergent. 174 Manual. 47 HCFC.81. 39. 12-14. iv. 1. 88 Micelle. 107. 85. 145-146. L Laboratory cleaning. 2-5. 48. 15. 176 FTIR. 135. 9192. 22. 142. 37. 146. 88. 20. 44. 13. 85. 165. 17. 57. 79 Particulate. 47 M Machine cleaning. 142 I ICH. 45 G Gas chromatography. 85. 90-91. 11-12. 131. 42. 10. 159 Hazardous substance list. 11. 11. vi. 78. 79. 135 Free-rinsing. 46. 84. 66. 135-137. 94. 155-159. 8. 3. 9. 59 Forced-air drying. 136 High volume/low pressure. 91. 167 Hydrophilic. 165-167 Inhibitor. 20 Medical device manufacturing. 137. 136. 93. 47. v. 46. 47. 92. 42. 9. 36. 30. 14 Liquids. 22-23. 21 Low volume/high pressure. 44-45. 8 Healthcare. 111. 167 Nonferrous. 164 Pathogens. 138 Immersion. 45. 29-30. 56-57 High-agitation spraying. 44. 136. vi. vii. 9. 46. 3. 5. 151 Optics. 158-160. 135. 5 167 Nonpolar. 137. 133. 119 Permeate. 167 Hydrochlorofluorocarbon. 168. ix. 37. 11. 151. 47. 150. 75. 162 Measuring cleanliness. 32. 167. 42 Nonionic. 5. 11. 132. 166. 164 Organic. 80. 121. 141. 151. 122 Metal finishing. 166 Lot number tracking. 37. 11. 146 Insoluble oils. 17. 11. 122-123 Limonene. 141 Mechanical action. 155-156. 34-36. 67. 39. 85 Nonvolatile Residue Inspection (NVR). 87. 122. 75 High emulsifying. 90. 176 Manual cleaning. 111. 47. 90-91. 103. 90. 923. 24. 14 Installation Qualification (IQ). 12. 151. v. 133 pH. 20. 131. 14. 58. 91. 34-36. 141. 16 Hydroxide. 30. 162 GMP. 158-159. 35. 167 Optical microscopy. 144-148. 45. 24. 97. 7. 20. 172 Immersion cleaning. 90. 173 Inorganic soil. 144 Minimal system. 17. 86 Nonionic surfactant. 74. 169 Organic-free. 126. 135. 168.Food and beverage processing. 16-17. 163-164. 5. 63. 71. 133. 3-5. 135. 135. 10. 82-83. 148. 11. 164. 44. 5. 11. 13 Mechanical agitation. 116. 79-81 LD50. 141. 42. 155. 63 Ozone depletion. 44. 61. 114. 102-103. 91-94. vi. 167-169 Hydrotropes. v. 15. 60. 115. 7. 56 HPLC. 75. 145. 30-31. 67. 142. 9-10. 173 Manual surface cleaning. 102. 65-66. 42. 98-102. 69-71. 32. 60. 166. 84. 14. 54. 55. 69. 34. 23. 119 Interfering detergent residue. 137. 131 Operational Qualification (OQ). 41. 151. 124-125. 126. 20. 151 Ionic. vi. 136. 26. 125. 55 High-foaming cleaners. 54. 85. 61. 142. 164 O Oil evaporation. 125. 14. 79. 57. 129. 163. 121. 13. 119 Material Safety Data Sheet. 91. 10 Hydrolysis. 90 In-situ particle counting (ISPM). 145. 142 OSHA. 14. 2. 84. 83 Forced-air. 39. 167 Irritants. 31 Performance Qualification (PQ). 169 Nonionic contaminant. 10. 39 Free alkalinity. 28. 81 Low-power microscope inspection. 29. 163 N Neutral. 141. 71. 166-167 Microfiltration. 20. 13-14. 30-32. 137. 121. 169 Parts washer. 143 Nuclear. 72-78. 86. 14-17. 81 Machine washing. 88 Inorganic. 63. 119 GMP washing machines. 113. 63. 160. 3. 83. ix. 169 Hydrophobic. 65. 71. 14. 182 The Aqueous Cleaning Handbook Appendix 183 . ix. 165 Hydrolyzed. 56. 28. iv. 61 Oleophilic. 20. 92. 17. 69. 15. 56-57 Low-foaming. 92 Ingredients. 76. 145 H Hazardous. 36. 93. 63 Mixer. 54. 9. 42. 80. 74. 55-57. 164. 116. 3-5 Hydrogen bonding. 20. 41. 124. 83. 13. 8.
165 Sessile drop technique. 138. 151. 87-88. 30. 176-177 Residue acceptance criteria. 28. 57-61. 27. 97 Presoaking. 25. 17. 22-23. 21-22. 19. 132 Physical separation. 1920. 175 129. 177 Soap. 164 Stainless steel cleaning. 165. 47. 71. 168. 115. 97. 32. 65. 31. 23-25. 133 Pilot scale. 93. 9.15. 69. 114-117. 14 Skimmer. 54-55. 54-55. 71 Placebo sampling. 102-107. 21. 9. 104-107. 28. 80-82. 99. 6-7. 66-68. 85. 59. 78-79. 98. 133. 144 Temperature. 77. 158 Spray clean-in-place. 44. 93. 46-48. 167 Saponifier. 11-17. 136. 10. 81. 115. 81-82. 15-16. 45 Retentate. 97. 59. 36. 67. 157. 55. 111. 67. 121-124. 82-90. 17.84. 114. 9. 122. 168 Steel. 105. 164. 20. 164-166. 141. 65. 90. 71-72. 159 Residue. 97. 58-59. 99. 97-98. 87. 17. 167. 166. 137-139. 44. 121 Plastic. 65-66. 77. 106-108. 136. 105. 144. 17. 78. 82-83. 68. 142. 80-83. 61. 75. 109. 44. 41. 47. 33-34. 159. 28-36. 58-59. 80. 167168 Soil. 85-87. 72. 80-81. 21. 132-133. 63. 82-84. 138. 90-91. 111. 30. 22-23. 28. 135. 39. 69 Standard operating procedure. 158. 19-23. 124. 83. 75. 34. 23-26. 164. 52. 45 Reactivity. 166. 168 Polar solvent. 147. 166 Swabbing surface. 134. 93. 168 Polymerized rosin. 141. 114. 41. 42. 103. 24. 116117. 80-83. 35. 59. 23. 69. 7880. 28. 164 Stabilizers. 73. 175 184 The Aqueous Cleaning Handbook Appendix 185 . 17. 1-2. 91-94. 164 Sterilization. 173 Sampling method. 115-117. 12-16. 94 pKa. 11. 138 Recycling. 52. 106. 133 Solvent. 55 Spray cleaning. 153 Plastics compatibility. 13-14. 89 Polar. 73. 20. 134-135. 26. 89. 43. 58. 168 Polar soil. 22. 71-72. 156. 5. 13. 162 RCRA Hazard Classification. 137. Scanning Electron Microscopy (SEM). 168 Surfactant. 33. 120-121 Sampling procedures and recovery. ix. 51. 105. 14. 164 S Safety based limit. 39. 47. 164 Surface active agent. 88. 88-89. 89-90. 13. 86. 65. 28. 113. 52. 24. 110. 11-12. 99. 138. 30 Saponification. 85. 125. 143-145. 21. 134. 32-34. 44-45. 36. 67. 23. 91. 111-117. 105. 164. 105. 93-95. 135-138. 69. iv. 77. 165-169 Surfactant-free cleaner. 30 Protein. 39. 55. 104. 119 Sanitizer. 114. 68. 71. 157. 37. 120-121 Residue identification. 97. 160. 15. 85. 152 Secondary Ion Mass Spectroscopy (SIMS). 155-156. 5152. 37. 121. 71. 13. 149 Silicates. 15. 74. 158-160. vi. 1. 94. 160. 145-146. vii. 51-52. 17. 12-15. 71 Soaking. 107. iv. 168. 59. 54-56. 115-116. 92. 44. 149 R RCRA. 156 Refractometry. 42-43. 44. 2. 44-45. 27. 65-66. 25. 44. 9. 141. 82. 21. 136-137 Regulatory review. 5. 52. 9-14. ix. 160. 12-15. 29 Precleaning handling. 25. 11. 133-134. 3. 168 Sequestration. 67-68. 55. 129 Suspension. 34. 98. 116. 164 Scale-up. 23-26. iv. 30. 119122. 92. 81. 35-36. 32. 139. 91-93-94. 125. 5859. 92. 149. 74. 168 Scale. 69. 113. 44. 134. 166. 129-130. 13. 123 Salt. 135. 43. 172 Tap water. 147. 42. 36. 175. 70. 173 Phosphate. 166-168. 105. 1-8. 78. 39. 163 Power spray wand. 83. 84. 117. 71. 20. 46. 83. 149. 152 Semiaqueous cleaner. 28-29. 91. 168. 4. 158. 34-36. 20 Suspended solid. 60 Postcleaning handling. 111-113. 136. 15. 13. 84. 165. ix. 82. 131-132. 35-36. 19-23. 29 Power washer. 19-20. 2. 167-169 Surface contact-angle. 13. 155-156. 29-31. 44-45 Rinse procedure. 1-3. 97. 131-135. 99. 24. 148-149. 20. 46. 5-7. 164. 87 Porous surface. 90. 164 Physical drying. 1. 10. 67. 163-164. 92. 92. 117. 75. 127. 163-164. 132. 37. 143-146. 80. 175 Solder paste. 65-66. 91. 13. 24-26 Physical filtration. 11. 46. 47. 130. 126. 94. 72. 142. 57-59. 172-173. 103-104 Sterilizing. 2-3 T Tank. 63. 44. 1. 144. vi. 99-100. 61-63. 94-95. 42. 14. 5-6. 60. 89. 176 Tape test. 68. 54. 12-13. 6771. 174. 111. 139 Soak. 45. 134 Sequestering agent. 168 Separator. 59-61. 44. 62. 44. 139. 79. 121 Synthetic solvent. 141-145. 79. 102. 19. 41. 92. v. 121 Rinsing. 15 Stainless steel. 44. 31-32. 128. 168 Spray. 177 Soak cleaning. 80. 28-31. 99. 32. 134. 6. 71. 87 Solubilization. 48. 78. 121122 Residue detection method selection. 54 Surface energy. 95. 42 Solution recharge. 82-84. 1. 171. 100-102. 90-91. 171-177 Rinse aid. 6. 128. 99. 28-33. 68. 93. 16-17. 106 Rinse water sampling. 39. 44. 14. 130. 164. 172. 39. 134. 55-57. 66-69. 132. 80-83. 82-83. 112 Powder. 38-39. 45. 83. 78 Substrate. 88. 22-24. 65. 32. 85. 107. 39. 71. 90-91. 57-60 Q Quality control. 99. 68. 115. 69. 67-71. 78 Piping system. 22. 100-101. 21. 23-24. 130. 55-57. 32-34. 61. 114-115. 80. 11. 174 Spray agitation. 136-138. 167 Pharmaceutical. 85. 129. 168. 101. 92. 48. 107. 88-89. 166. 29. 21. 34. iv. 12. 6-7. 168 Rubber. 18. 42. 91. 22-24. 133 Rinse. 89-90. 43. 74. 19. 120-121 Residue-free. 16. 105 Pressurized spray. 74. vii. 41-46. 91. 44-45. 134-135. 15. 42. 65-66. 148. 167 Proteinaceous soil. 15. 91-94. 176-177 Rosin. 99. 71. 6. 120-127. 153 Surface tension.
91. 141. 81. 169 WFI. 3. 34-35. 17. 141. v. 82 Wax melting points. 35. 20. 156 186 The Aqueous Cleaning Handbook . 153. vi. 113. x. 120. 90-92. 86-87 Wiping and visual inspecting. 152. 88. 77. 97. 61-63. 119. 12. 85. 78. 113. 104. 82. 148 Water testing. 106-107. 54-57. 52. 86 Visual inspection. 8. 20. 3-4. 61. 54. 34-36. 119 Test cleaning. 110. 114. 130. 8. 168 W Wash cycle. 147-149. 51. 1. 57. 19. 66-68. 82. 133-135 Ultrasonic. 111. 169 Wetting agent. 9. 144. 122. 156-157. 158-159. 120. 111 Waste treatment. 163-164. 41 Volatile. 4. 106-108. 22-23. 27. 114. 88. 80. 94 Wastewater treatment. 131 Water break. 20. 132. 139. 121. 48. iii. v. 5 Vesication. 11. 121 White residue. 127. 94. 164. 8283. 124. 104. ix. 51. 138. 135 Toxicity. 13-14. 162. 145-146 Testing. 78. 162 VOCs. 116-117. 39 Vapor degreasers. 52. 12-13. 23 USP. 29. 5 Test. 33. 99-100. 141142. 61 Test soil. 43. 31. 97. 38-39. 44. 91. 9. 67. 80-83. 18. 28. 105. 59-61. 125 UV. 169 UV spectroscopy. 145. 146-147. 11. 156. 25. 75. 121 Z Zero-discharge. 45. 162. 47. 97. 68. 25. 59. 2-4. 71. 37. 54. 157 Trace analysis.175 Waste-treatment filtration. 143. 22 Wetting. 22. 150. 19. 29-32. 51. 110. 72. 146 Water drop surface energy test. 126. 171-177 Titration. 57-62. 131. 52. 153 Time. 122. 22. 147 Ultrasonically agitated rinsing. 54. 129. 44-45. 59 Testing. 82. 141. 41. 110111. 52. 160 U Ultrafiltration. vii. 52. 125-126 Total alkalinity. 74. 148 Test acceptance limit. 142 Worker safety. 29. 61. 158. 90. 43. 56. 60 Test substrate. 57. 121. 86. 1. v. 111. 151. 73.Terpene. 81. iv. 141-143. 68. 51. 41. 61 Waxy or oily soils. 89. 164 V Vacuum drying. 144-145 Trace metals. 79. 54-55. 51. 171 Ultrasonic cleaning. 80. 144 VOC. 46-47.
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