02383

POLLUTION PREVENTlON
Waste Minimization for the Metal Finishing Industry

Developed by U.S. EPA/SEDESOL Pollution Prevention Workgroup May 1993
SECTION I
Introduction
INTRODUCTION
The production of economically competitive products is the driving force behind any successful business. Quite often the manufacturing process requires the use of various chemicals. The purchase and storage of these chemicals, their use in the process, and the ultimate disposal of the waste created by the manufacturing process can present many problems. These problems include financial concerns, as well as issues associated with environmental management and worker health and safety. Pollution prevention occurs when action is taken to reduce the waste created by manufacturing processes. It includes practices that reduce the use of hazardous and nonhazardous materials, energy, water, and other resources, as well as those practices that protect natural resources through conservation or more efficient use. Because of the enormous potential for pollution prevention along the United States and Mexican border, the U.S. Environmental Protection Agency and SEDESOL established a Pollution Prevention Workgroup in February 1990 to promote and coordinate the reduction of pollution through a broad range of approaches: technical assistance, training, public and private sector pollution prevention awareness programs, assessment of pollution prevention opportunities, policy development and institutional support, and technology development and investment activities. The purpose of this first manual is to provide pollution prevention information for the metal finishing industry. The manual will be expanded in the future to include other industries that are typical in the border area, such as the chemical manufacturing and wood finishing industries. The manual contains the following sections.
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Section I
The Goals and Benefits of Pollution Prevention
In this general introduction, the term pollution prevention is clarified. This section also includes an overview of the benefits of applying pollution prevention techniques.
Section II
Waste Minimization in the Metal Finishing Industry
This technical section contains descriptions of various processes associated with the metal finishing industry and pollution prevention options for that industry. This section may be of particular interest to process engineers.
Section III
Case Studies
This section includes specific examples of companies that have used pollution prevention techniques. These case studies describe the benefits, particularly cost savings, these companies have achieved.
INTRODUCTION
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Attachment A Information on Accessing Pollution Prevention Information Clearinghouses

This section describes how to access the International Cleaner Production Information Clearinghouse (ICPIC) database, which is an international clearinghouse for pollution prevention information.
Attachment B Survey
PLEASE COMPLETE THE SURVEY INCLUDED IN THIS SECTION. Your response provides valuable information for evaluating the usefulness of this manual. Additionally, by mailing in the survey, your name will be placed on a mailing list for updates to the manual and other documents as they become available.
Appendix A
Referencing Additional Information
This section lists additional technical documents pertaining to pollution prevention opportunities for the metal finishing industry, and other information. Currently these documents are available in English only.
SECTION 1: THE GOALS AND BENEFITS OF POLLUTION PREVENTION

The goal of a pollution prevention program is to minimize all waste produced. Pollution prevention includes any action a company takes to reduce the amount of waste created by a manufacturing process prior to recycling, treatment, or disposal of the waste. To effectively accomplish this, the program must be an ongoing, comprehensive assessment of the operations at a facility.
BENEFITS OF A POLLUTION PREVENTION PROGRAM

Both businesses and governments have strong incentives to reduce the toxicity and sheer volume of the waste they generate. The cost of producing each unit will decrease as pollution prevention measures lower operating costs. Therefore, companies with an effective, ongoing pollution prevention plan will have a significant competitive edge. The overall benefits of a pollution prevention program, discussed in more detail below, include the following: Protecting human health and environmental quality
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Reducing operating costs Improving employee morale and participation Enhancing your companys image in the community Reducing the potential for penalties and fines
WASTE MINIMlZATlON IN THE METAL FINISHING INDUSTRY
PROTECTING HUMAN HEALTH AND ENVIRONMENTAL QUALITY

Reducing the waste released to air, land, and water will help the environment and protect human health. Typical harmful pollutants that can be reduced significantly by pollution prevention techniques include the following:
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Air emissions - solvent fumes, fine particulates, and carbon monoxide Land disposal - heavy metal sludge, waste solvents, and debris Water disposal - wastewater contaminated with heavy metals, cyanide, and other toxic materials
The health and safety of employees can be affected by poor ventilation, mishandling of chemicals, and a lack of proper safety equipment. An informative employee training program is an important way to reduce accidents. Reducing the amount of chemical materials and wastes at a facility is also beneficial because it reduces the amount of space required for storage as well as the potential for accidental spills. Furthermore, there may be a reduction in hazardous waste transportation requirements if the volume of pollution is minimized.
REDUCING OPERATING COSTS

An effective pollution prevention program can yield cost savings that will more than offset program development and implementation costs. Cost reductions may be immediate savings that appear directly on the balance sheet or anticipated savings based on avoiding potential future costs. Cost savings are particularly noticeable when the costs resulting from the treatment, storage, or disposal of wastes are allocated to the production unit, product, or service that produces the waste. Materials costs, or the costs to purchase materials, can be reduced by adopting production and packaging procedures that consume fewer resources. This approach uses resources more efficiently and creates less waste. As wastes are reduced, the percentage of raw materials converted to finished products increases. This leads to a proportional decrease in materials costs. Waste management and disposal costs may be reduced when less waste is produced. Required procedures for proper handling of the waste at the facility, as well as specific treatment, disposal and transportation methods are typically labor intensive and very costly. These requirements and the associated costs are expected to increase. Production costs can be reduced through a pollution prevention assessment. When people examine production processes from a fresh perspective, they find opportunities for increasing efficiency that might not otherwise have been noticed. Production scheduling, material handling, inventory control, and equipment maintenance are all areas where facilities can work to reduce the production of waste of all types, and thus control the costs of production. Energy costs will decrease as the facility implements pollution prevention measures in various production lines. In addition, companies can reduce the energy used to operate the overall facility by doing a thorough assessment of how operations interact.
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IMPROVING EMPLOYEE MORALE AND PARTICIPATION

Employees are likely to feel better about their company when they believe that management is committed to providing a safe work environment and is acting as a responsible member of the community. By participating in pollution prevention activities, employees have an opportunity to be part of a team, and interact positively with co-workers and management. Helping to implement and maintain a pollution prevention program should increase each employees sense of commitment to company goals. This positive atmosphere helps to retain a competitive work force and to attract highquality new employees,
ENHANCING THE COMPANYS IMAGE IN THE COMMUNITY

The quality of the environment has become an issue of greater importance to society. Your companys policy and practices for controlling waste increasingly influence the attitudes of the community at large. Community attitudes are more positive toward companies that operate and publicize a thorough pollution prevention program. If a company creates environmentally compatible products and avoids excessive use of material and energy resources, the companys image will be enhanced in both the community and with potential customers and consumers.
REDUCING THE POTENTIAL FOR PENALTIES AND FINES

Mexicos environmental laws include administrative penalties that entitle government inspectors to require temporary or permanent closure of businesses that are out of environmental compliance. A clearly written pollution prevention plan that includes standard operating procedures that comply with environmental laws and regulations is very helpful. By following the plan, a company is less likely to incur any violations and associated penalties.
WHAT IS POLLUTION PREVENTION?

Pollution prevention (also known as source reduction and waste minimization) is any action that reduces the production of wastes (at their source) that may be otherwise released to the air, land, or water. There are two general methods to achieve pollution prevention: (1) process changes and (2) product changes. Various source reduction changes are summarized in Figure 1. Process changes allow resources to be more efficiently used during the manufacturing process. These changes include the following:
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Prudent purchasing, where the most appropriately sized container of new material is bought, rather than buying too much and having to dispose of the unused portion Operational changes, such as reuse of input materials during production and reduction of water consumption in the process lines
Technology changes, such as using a safer process material Increase in energy efficiency
WASTE MlNMlZATlON IN THE METAL FINISHING INDUSTRY
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Figure 2 - Process Change Methods The following process changes are pollution prevention measures because they reduce the amount of waste created during production. The following are examples of input material changes:
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Stop using heavy metal pigment. Use a less hazardous or toxic solvent for cleaning or as coating.
Purchase raw materials that are free of trace quantities of hazardous or toxic impurities.
The following are examples of technology changes: Redesign equipment and piping to reduce the volume of material contained, cutting losses during batch or color changes or when equipment is drained for maintenance or cleaning,
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Change to mechanical stripping/cleaning devices to avoid solvent use. Change to a powder-coating system. Install a hard-piped vapor recovery system to capture and return vaporous emissions.
Use more efficient motors. Install speed control on pump motors to reduce energy consumption.
The following are examples of improved operating practices:

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Train operators. Cover solvent tanks when not in use. Segregate waste streams to avoid cross-contaminating hazardous and nonhazardous materials. Improve control of operating conditions (e.g., flow rate, temperature, pressure, residence time, stoichiometry). Improve maintenance scheduling, record keeping, or procedures to increase efficiency. Optimize purchasing and inventory maintenance methods for input materials. Purchasing in quantity can reduce costs and packaging material if care is taken to ensure that materials do not exceed their shelf life. Reevaluate shelf life characteristics to avoid unnecessary disposal of stable items.
Stop leaks, drips, and spills. Turn off electrical equipment such as lights and copiers when not in use.
Place equipment so as to minimize spills and losses during transport of parts or materials. Use drip pans and splash guards.
WASTE MlNlMlZATION IN THE METAL FINISHING INDUSTRY
Figure 3 - Other Environmental Strategies The following are other environmental management strategies: Off-site recycling:
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Off-site recycling (for example, solvent recovery at a central distillation facility) is an excellent waste management option. However, it does create pollution during transport and during the recycling procedure.
Waste treatment:
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Waste treatment involves changing the form or composition of a waste stream through controlled reactions to reduce or eliminate the amount of pollutant. Examples include detoxification, incineration, decomposition, stabilization, and solidification or encapsulation.
Concentrating hazardous or toxic constituents to reduce volume: Volume reduction operations, such as dewatering, are useful treatment approaches, but they do not prevent the creation of pollutants. For example, pressure filtration and drying of a heavy metal waste sludge prior to disposal decreases the sludge water content and waste volume, but it does not decrease the number of heavy metal molecules in the sludge. Diluting constituents to reduce hazard or toxicity: Dilution is applied to a waste stream after generation and does not reduce the absolute amount of hazardous constituents entering the environment. Transferring hazardous or toxic constituents from one environmental medium to another: Many waste management, treatment, and control practices used to date have simply collected pollutants and moved them from one environmental medium (air. water, or land) to another. An example is scrubbing to remove sulfur compounds from combustion process off-gas.
carbon requires the use of another solvent or heating, transfering the waste to the air. In some cases, transfer is a valid treatment option. However, too often the purpose has been to shift a pollutant to a less-tightly regulated medium. In either case, media transfers are not pollution prevention. Off-site recycling is vastly preferable to other forms of waste handling because it helps preserve raw materials and reduce the amount of material that will require disposal. However, compared with closed-loop recycling (or reuse), performed at the production site, off-site recycling is likely to have more residual waste that requires disposal associated with it. Furthermore, waste transportation and the recycling process carry the risk of worker exposure and release to the environment. Waste treatment prior to disposal reduces the toxicity and/or disposal-site space requirements but does not eliminate all pollutant materials. This includes such processes as volume reduction, dilution, detoxification, incineration, stabilization, and other measures.
lNTRODUCTION
The pollution prevention hierarchy, represented on Figure 4, prioritizes waste management options from those that are most environmentally beneficial to those that are least environmentally beneficial. More specific technical information on pollution prevention options for the metal finishing industry is found in Section II of this manual.
WASTE MINIMIZATION THE METAL FINISHING INDUSTRY
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WASTE MINIMIZATION ASSESSMENT PROCEDURES MODULE III

WASTE MINIMIZATION IN THE METAL FINISHING INDUSTRY
A JOINT PROJECT OF
UNIVERSITY EXTENSION UNIVERSITY OF CALIFORNIA, RIVERSIDE ALTERNATIVE TECHNOLOGY DIVISION CALIFORNIA DEPARTMENT OF TOXIC SUBSTANCES CONTROL UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
AUTHORS:
JON W. KINDSCHY, M.B.A., CHWS

UNIVERSITY OF CALIFORNIA EXTENSION, UNIVERSITY OF CALIFORNIA, RIVERSIDE
DAVID RINGWALD, B.S. MOLLY CARPENTER, M.A.T.

PROJECT DIRECTOR:
M A Y
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ACKNOWLEDGMENTS
SPECIAL THANKS TO:
Review: Kathryn Barwick, California Environmental Protection Agency, Department of Toxic Substances Control, Office of External Affairs, Office of Pollution Prevention and Technology Development, Sacramento Dave Hartley, California Environmental Protection Agency, Department of Toxic Substances Control, Office of External Affairs, Office of Pollution Prevention and Technology Development, Sacramento Robert Ludwig, California Environmental Protection Agency Department of Toxic Substances Control, Office of External Affairs, Office of Pollution Prevention and Technology Development, Sacramento Andora Sprecher, Comtox Corp., Big Bear City, California Kim Wilhelm, California Environmental Protection Agency, Department of Toxic Substances Control, Office of External Affairs, Office of Pollution Prevention and Technology Development, Sacramento For Formatting and Graphics: Shelley Hall, Publications Department, UCR Extension Jack Van Hise, Publications Department, UCR Extension
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PROJECT ADVISORY COMMITTEE MEMBERS John Aubert, General Dynamics, Pomona Division Al Crane, General Dynamics, Pomona Division Cathy Godfrey, Bourns Incorporated, Riverside Jon Kindschy, University of California Extension, Riverside Marilyn Kraft, County of San Bernardino, Department of Environmental Health Services Robert Ludwig, California Environmental Protection Agency, Department of Toxic Substances Control, Office of External Affairs, Office of Pollution Prevention and Technology Development, Sacramento Michael Meltzer, Lawrence Livermore Lab, University of California, Berkeley Steve Mercer, formerly with Rohr Industries, Riverside Judy Orttung, County of San Bernardino, Department of Environmental Health Services Mike Shetler, Riverside County Health Department, Hazardous Materials Donna Toy-Chen, Board of Public Works, Hazardous and Toxic Materials Project, Los Angeles Linda Verhoeven, Rohr Industries, Riverside Janet M. Weder, Seven W Enterprises and Highland Supply Corp., Redlands
ACKNOWLEDGMENTS
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DISCLAIMER
The statements and conclusions of this report are those of the Regents of the University of California and not necessarily those of the State of California or the U.S. Environmental Protection Agency. The mention of commercial products, their sources, or their use in connection with material reported herein is not to be construed as either an actual or implied endorsement of such products.
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DISCLAIMER
CONTENTS
INTRODUCTION AND PURPOSE CHAPTER 1. SYSTEMS 1
DESCRIPTION OF METAL FINISHING
Metal Cleaning and Stripping ................................................................ 3 Organic Solvent Cleaning .................................................................... 5 Aqueous Based Cleaning .................................................................... 6 Abrasive and Thermal Methods ........................................................... 6 Surface Treatment and Plating ................................................................. 8 Chemical and Electrochemical Conversion ........................................... 9 Electroplating and Related Processes .................................................. 10 Metallic Coatings ................................................................................. 10 Case Hardening .................................................................................. 10 Printed Circuit Board Manufacturing ......................................................... 11
CHAPTER 2. WASTE MINIMIZATION OPTIONS FOR THE METAL FINISHING INDUSTRY

Source Reduction in Cleaning and Stripping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 Preventing the Need for Cleaning ......................................................... 13 Solvent Source Reduction ................................................................... 14 Aqueous-based Wastes ...................................................................... 14 Abrasives Source Reduction ................................................................ 15 Source Reduction in surface Plating and Related Processes.. .................... 15 Process Substitution ................................................................................ 16 Material Purchase, Storage and Handling ................................................. 16 Avoiding Material Degradation. ................................................................. 16 Managing Samples ............................................................................. 16 Spills .................................................................................................. 18 Residues and Empty Containers .......................................................... 18 Inspections ......................................................................................... 18 Process Baths.. ....................................................................................... 18 Material Substitution ............................................................................ 18 Extending Solution Life ........................................................................ 19 Drag-Out Reduction ............................................................................ 20 Rinse Systems ........................................................................................ 22 improved Housekeeping .......................................................................... 22
CONTENTS
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Source Reduction in Printed Circuit Board Manufacturing ......................... 22 Product Substitution ............................................................................ Cleaning and Surface Preparation ....................................................... Electroplating and Electroless Plating .................................................. Pattern Printing and Masking.. ............................................................. Etching .......................................................................................... Solvent Recycling ............................................................................... Aqueous-based Cleaner Recycling ...................................................... Material Recovery and Reuse .............................................................. Evaporation .................................................................................... Reverse Osmosis.. ......................................................................... Ion Exchange ................................................................................. Electrolytic Recovery.. .................................................................... Electrodialysis ................................................................................ Rinse Water Reuse ............................................................................. 24 24 24 24 24
Recycling and Resource Recovery in Cleaning and Stripping.. .................. 25 25 25
Recycling & Resource Recovery in Surface Plating & Related Processes .26 26 26 26 27 28 28 28
Recycling and Resource Recovery in Printed Circuit Board Manufacturing 28 Review Questions ................................................................................. 31 References ............................................................................................ 33 Glossary ................................................................................................ 35
WASTE MlNlMIZATlON IN THE METAL FINISHING INDUSTRY
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INTRODUCTION AND PURPOSE

This booklet is part of a project to develop training materials for hazardous waste generator inspectors. The three training modules address different aspects of waste minimization. This module outlines the processes involved in metal cleaning, metal finishing, and printed circuit board manufacturing and the potential for waste minimization within each of these activities. However, the applicability of waste minimization strategies to a particular shop will vary significantly depending on such variables as floor space for new equipment, utility service capacity, contractual specifications, or restrictions on wastewater discharge. Thus, a realistic evaluation of waste reduction potential must include qualitative information as well as a quantitative evaluation of the costs and benefits of proposed changes. This module is intended to provide the key concepts necessary to familiarize the inspector with the scope of the metal finishing industry and the search for viable waste minimization options. It will describe the two major categories of metal finishing operations, metal cleaning and stripping, and surface treatment and plating. An allied industry, printed circuit board manufacturing, will also be discussed. Strategies for reducing waste will include examples of source reduction, recycling and reuse. Economic factors which act as both a driving force for and a barrier against waste minimization will also be discussed. The glossary provides definitions of terms related to the subject beyond those used in this module. Accompanying this Module is a Department of Health Services publication entitled Hazardous Waste Reduction Checklist & Assessment Manual for the Metal Finishing Industry, It is available in quantity for distribution to metal finishers as inspections are completed. Section 1 of the booklet provides a checklist of waste minimization opportunities which parallels the discussion in this workbook. Section 2 of the booklet provides a series of tables for evaluating the potential applicability of the options discussed in this manual. The inspector should be thoroughly familiar with the Department of Health Services booklet as well as Modules I and II of this training series. Thus, the inspector will be prepared to assist the operators of the facilities inspected in their waste minimization opportunity assessments. Module III is intended to augment the information in the Department of Health Services booklet and to provide you, as an inspector, with the technical background to understand the related processes to maximize your effectiveness in enforcing regulations and in contributing to the goals of the State in reducing the volume and toxicity of our industrial waste stream.
Volume
Reduce Reduce Toxicity
INTRODUCTION AND PURPOSE
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WASTE MlNlMlZATlON IN THE METAL FINISHING INDUSTRY
Review the metal finishing processes of cleaning and stripping and the processes of treatment and plating Review the printed circuit manufacturing process
Chapter 1
DESCRIPTION OF METAL FINISHING SYSTEMS

There are approximately 13,000 metal finishing and printed circuit shops in the United States. The U.S. Environmental Protection Agency (EPA) estimates that in 1986 the metal finishing industry generated 129,000,000 gallons of metal-bearing waste. The industry includes a vast array of manufacturing facilities. The size of operations ranges from small mom and pop shops, which only use a few processes and typically do contract work for larger companies, to very large operations, which have many finishing lines using dozens of processes and have hundreds of employees. Almost all of these companies have installed wastewater treatment systems to comply with the Clean Water Act. As a result, these companies generate toxic metal sludges that are regulated pursuant to Resource Conservation and Recovery Act. Compliance with these two federal laws, in addition to other state, county and local regulations, can require industry to spend 10 to 15 percent of their sales dollar on compliance. Compliance with the landfill ban has caused disposal costs to increase by 25 to 150 percent. These facts of life for the metal finishing industry make waste minimization a high priority.
Large and small shops contribute to waste streams
METAL CLEANING AND STRIPPING

The objective of metal cleaning and stripping is simply to clean both metallic and non-metallic surfaces in preparation for subsequent processes. This generally involves removing contaminants such as rust, paint, old plating and a wide variety of soils. Removal of soils can be achieved by means of using detergents, solvents, chemical reactions, or mechanical action. In surface treatment and plating operations processes are used to impart particular characteristics to a material, such as reducing surface reactivity; increasing corrosion resistance, strength or conductance; or producing desired textures or colors. Both chemical and mechanical processes are used to accomplish these objectives and both produce waste materials containing metals and other chemicals, which must be disposed of properly Metal finishing often involves many steps, and there can be considerable periods of time between the steps. To protect the metal workpieces over these intervals, they are often coated with oils or paints to prevent oxidation from occurring while in storage or in transit. Prior to continuing with the next step, these protective coatings must be removed. Also, workpieces that must be handled pick up traces of body oils and other soils that can interfere
with subsequent processing steps. Traditionally, organic solvents have been used to remove these materials. These solvents do not add to the metalbearing waste load from metal finishing, but they are considered to have significant human health and environmental risks, This stems not only from their toxicity, but also from their flammability and resistance to biodegradation Industrial cleaning costs in the metal finishing industry are considerable. but the costs of improper or incomplete cleaning of surfaces prior to plating can be even higher. For example, early failure of moving engine parts has been traced to inadequate surface cleaning, which resulted in excessive wear. The primary cause of the failure of paint and plating to properly adhere is that they were applied to a soiled surface.
The cleaning process selected depends upon the form of contamination
The cleaning methods vary considerably depending on the type and quantity of the soil, the nature of the base metal and the coating material, as well as the shape of the workpiece and its end use. A cleaning process that proves adequate for subsequent anodizing of steel would be totally unsuitable if the same workpiece were to be nickel plated. In the cleaning process, four forms of contamination rnust be considered. They are grease soil, loosely adherent soil, adherent soil and moisture. A typical workpiece may have a combination of these soils.
Grease soil - Includes normal lubricating oils, oils used during machining, grease used for protection of components during storage and natural oils in fingerprint contamination. Loose soil - Includes dust and fine turning and grinding debris from
machining. These are often found in conjunction with machining oil This form of contamination can be compared to chalk on a chalkboard in that the particles adhere loosely to the surface.
Adherent soil - Commonly includes scale or rust, but might also include
burned-on oil or paint that has served its purpose and needs to be removed
Moisture - Normally present in the atmosphere, it may appear as condensation on workpieces or come from machining with water-soluble oils. This ubiquitous contaminant can also be blamed for some of the adherent soils described above.
Each of these types of contaminants and the methods for removing them will be discussed in subsequent sections. It should, however, be reemphasized that a single form of contamination will seldom be found in practice. A series of cleaning operations is generally required to fully prepare a metal surface for its final treatment. The order in which the workpieces move through the cleaning processes depends on the types of soils present. In these processes soils are removed using four different means: 1) solvent action, 2) detergent action, 3) chemical reaction, and 4) mechanical action. Some of these may be employed in combination to increase the effectiveness of others. For example, ultrasonic vibration, a mechanical action, is commonly used in conjunction with both solvent-based and aqueous-based baths to increase their cleaning efficiency.
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ORGANIC SOLVENT ACTION Describes the ability of one material (solvent) to easily make a mixture with another material (solute). For the purposes of this discussion the solvent and solute are both non-aqueousbased. DETERGENT ACTION Describes a substance or mixture of substances that removes a soil from a surface and maintains it in aqueous solution. Detergents are generally composed of surfactants or alkaline salts and caustics, individually or in combination. Surfactants are surface-active agents that promote the removal of contaminants from a surface. Emulsion cleaners combine surfactants and solvents. CHEMICAL REACTION Changes the target soil chemically (e.g., oxidation, reduction) by using chemical or electrochemical processes such that the soil is removed from the metal surface and retained in solution. MECHANICAL ACTION Direct contact with a solid material under force, or, in the case of ultrasonic vibration, high frequency sound waves through a liquid medium, to remove the target soil. This includes wiping, polishing and blasting. There are three primary cleaning processes used for metals: 1) organic solvent cleaning, 2) aqueous-based cleaning, and 3) abrasive and thermal methods.
ORGANIC SOLVENT CLEANING

Solvent cleaning describes the use of solvent to remove oil and grease from surfaces. This can be accomplished in a number of ways, including the simplest, wipe cleaning, where a cloth is moistened in a solvent and rubbed across a surface. Although still in practice for some heavily soiled workpieces, its effect can be to spread soils to areas that are not contaminated. The same can be said for immersion cleaning where a rack of workpieces is immersed in a bath of solvent. The bath quickly becomes contaminated with the soil so when the rack is withdrawn and the solvent evaporates, a film of soil evenly coats the surface. The classical method for the removal of oil and grease from a surface is vapor degreasing. It usually consists of boiling a solvent cleaner, generally one of the chlorinated hydrocarbons, resulting in the heated vapor phase, into which the contaminated workpieces are inserted. The vapor phase then condenses on the cold components to produce a clean hot solvent, which dissolves the oil and grease. As further solvent condenses, it removes the dissolved soils. Historically, the industry has used carbon tetrachloride and other solvents such as benzene for solvent cleaning. These have now been shown to constitute significant health risks and have been removed from the workplace. The most commonly used solvents now in use are 1,1,1trichloroethane (TCA), trichloroethylene (TCE), perchloroethylene (PERC), and methylene chloride (METH). The last three solvents named are rapidly disappearing from use for several reasons, including ozone depletion. In particular, trichloroethylene, a carcinogen, has been increasingly replaced with substitutes such as methanol and acetone.
Metal cleaning methods
AQUEOUS-BASED CLEANING
Aqueous cleaning comprises a wide range of water-based cleaning methods that use detergents, acids, and alkaline compounds to displace soil rather than dissolving it in an organic solvent. Aqueous cleaning has been found to be a viable substitute for many metal finishing operations currently using solvents. Alkaline and acidic cleaners are applied using soak cleaning, spraying, ultrasonic cleaning, electrocleaning, and steam cleaning. The principal advantages of aqueous-based cleaning are the ease of treating spent solutions by pH adjustment and generally good biodegradability of organic detergents used in alkaline baths. Its principal disadvantage is that the workpieces are wet after cleaning and ferrous parts easily rust under these conditions unless they are dried rapidly. A common technique to accomplish this is hot water rinsing, but this is a more costly alternative. Another disadvantage associated with aqueous-based cleaning is an increase in the chemical oxygen demand (COG) of the wastewater and wastewater treatment costs. Mild steels are difficult to clean effectively in an aqueous process. About half of the approximately 100 million tons of steel produced in the U. S. every year is treated in acid pickling baths. In this process sulfuric acid (H2S04) or hydrochloric acid (HCI) IS used to remove scale from the surface of the raw ingot, sheet, or rod. Acidic cleaning solutions may contain other mineral acids such as nitric or phosphoric: organic acids such as acetic. citric, oxalic, or sulfaamic; detergents; chelating agents; and possibly small amounts of solvents. This process removes up to 1.5 percent of the metal and dissolves it in a pickling liquor (the acid with the dissolved scale). As the iron content of the bath increases, the pickling efficiency of the bath decreases to the point where new acid must be added or the dissolved iron must be removed. When the steel is rinsed, residual acid and dissolved metal are dragged out into the rinse water, creating another waste stream. Three waste streams are created by the pickling process: spent pickling liquor, rinse water and metal sludge from acid recovery Alkaline cleaning solutions (usually run hot) are comprised of builders and surfactants. Builders usually consist of sodium salts of phosphate (PO4 ), carbonate (CO3 ), silicate (SiO4 ) and hydroxide (OH ). Their function is to promote chemical reactions which will remove the metal oxides from the surface of the workpiece. Surfactants are detergents and soaps that tie up the metal oxide, and cause it to remain in the solution and not recombine with the metal surface. Other additives are often used in conjunction with builders and surfactants to act as anti-oxidants and stabilizers. Some shops use an electrolytic cleaning method. All methods require a final rinse step after cleaning.
ABRASIVE AND THERMAL METHODS

Mechanical means of cleaning can be an effective alternative to aqueous cleaning. Abrasives can be used in tumbling barrels or applied to buffing wheels Abrasive blast cleaning methods use plastic, ceramic, or sand blast media to clean and strip parts. The blast media can be recycled, thereby reducing disposal costs. Acid or alkaline cleaners are sometimes added to form abrasive slurries in order to improve cleaning action. These slurries are discharged after a set period of use, but require controls for total dissolved solids (TDS) in the wastewater.
Heat or flame cleaning/stripping ovens offer another method of removing paint and other organic soils fro m workpieces by burning them off. The disadvantages of heat cleaning are high energy requirements, and the production of combustion emissions, which require control devices. Refer to Table 1 for a summary of primary cleaning processes. Table 1 - PRIMARY METAL CLEANING PROCESSES PROCESS MATERlALS HOW USED DISADVANTAGES
Solvent cleaning
1,1,1Trichloroethane methanol, & acetone
Vapor degreasing, immersion, wiping
High material costs; worker exposures & flammability
Aqueous-based cleaning
Detergents: caustic Heated tanks, & acidic spraying, steam compounds cleaning, & ultrasonic cleaning (NaOH, H2SO4)
High COD & TDS in wastewater; creates metal sludges
Abrasive
Grit, sand, ceramic and plastic media;
Grinding, tumbling, blast cabinets;
High capital costs, APC equipment required
Thermal cleaning
Heat
Burn-off ovens
High energy costs, APC equipment required
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SURFACE TREATMENT AND PLATING

Surface treatment and plating operations are typically batch processes in which metal workpieces are dipped into and then removed from baths containing various reagents. The reagents are specially formulated to achieve the required surface condition. The workpieces can be carried on racks or in barrels that rotate in the plating bath.
Modifying the metals surface
Most surface treating and plating processes consist of three steps. The first is cleaning or preparation of the surface, which has already been described. The second step is the actual modification of surface itself, which involves some change in the properties of the surface. The final step is the rinsing of the workpiece. Metal-bearing waste is generated from all three of these processes. Four surface modification processes are listed below in Table 2
Table 2 - PRIMARY SURFACE TREATMENTS
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CHEMICAL AND ELECTROCHEMICAL CONVERSION
Chemical and electrochemical conversion treatments include phosphating, chromating, anodizing, passivation, and metal coloring. These treatments deposit a metal oxide coating on the metal surface, which is primarily intended to form an absorptive base for the adhesion of paints, lacquers, and oils applied in subsequent processes. The coatings also impart some corrosion resistance to the surface. See Figures 1 and 2 for illustrations of chromating of aluminum and steel passivation.
ELECTROPLATING AND RELATED PROCESSES
In electroplating, a workpiece is the equivalent of a cathode in a galvanic cell. It is placed in a solution of the dissolved metal to be plated. The electric potential applied across the cell is sufficient to attract the metal ions to the cathodic workpiece where they are reduced on the surface. Metals which are commonly electroplated onto workpieces are brass, bronze, cadmium, chromium, copper, iron, nickel, tin, zinc and precious metals such as gold, platinum and silver. In electropolishing, the workpiece acts as the anode. Surface metal is then oxidized and dissolved in the bath solution. High points on the metal surface dissolve faster than recessed areas. The result is a brightly polished surface.
METALLIC COATINGS
There are several nonelectrical techniques for applying a metal to a core of another metal. Frequently, aluminum, tin, or zinc is applied by dipping the core piece into a molten bath of the coating material. The high heat condition results in coating adherence through a lattice interdiffusion of the two metals. Cladding techniques bond the coated metal through high pressure, welding, or casting. Other techniques include vapor deposition and vacuum coating. See Figure 3 for a graphic showing vapor deposition of aluminum.
CASE HARDENING
This process produces a hard surface over a relatively soft metal core. The processes harden the surface through diffusion of carbon (carburizing), nitrogen (nitriding), or carbon and nitrogen (carbonitriding) into the steel surface. Nitriding involves the use of ammonia or a salt bath comprised largely of sodium cyanide and potassium cyanide. Alternatively, nonchemical processes achieve case hardening through very rapid heat application, which acts on the carbon already present within the workpiece.
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IIIIIIIIlIlIIIlIllIIIIIIII PRINTED CIRCUIT BOARD MANUFACTURING

Many aspects of printed circuit board manufacturing are very similar to processes used in electroplating. The circuit board consists of a nonconductive material laminated with copper foil. Holes are then drilled and deburred to allow for wiring and electrical component connection. The board is then plated with electroless copper to approximately seventy millionths (0.000070) of an inch thickness. This serves as the base for electrolytic copper which is plated to an approximate thickness of one thousandth (0.001) of an inch, or one mil. Then gold, lead, nickel or tin is electroplated, followed by the etching of the circuit pattern onto the board. Chemicals used in the manufacture of printed circuit boards include chromic acid, cupric chloride, and ferrous chloride for etching; stannous tin compounds and palladium chloride for catalysts; copper sulfate for electroless plating; copper pyrophosphate, acid-copper sulfate, acid copper fluoroborate, tin-lead, gold and nickel solutions for electroplating; and sulfuric dichromate for resist stripping. Refer to Table 3 for a list of materials and their components. Table 3 - CHEMICALS USED IN THE MANUFACTURE OF PRINTED CIRCUIT BOARDS Product/Process Raw Material
Board materials C l e a n e r s glass-epoxy, ceramics, plastic, phenolic paper, copper foil sulfuric acid, fluoroacetic acid, hydrofluoric acid, sodium hydroxide, potassium hydroxide, trichloroethylene. 1.1.1-trichloroethane. perchloroethylene, methylene chloride sulfuric and chromic acid, ammonium persulfate, hydrogen peroxide, cupric chloride. ferric chloride, alkaline ammonia stannous chloride, palladium chloride copper sulfate, sodium carbonate, sodium gluconate, Rochelle salts, sodium hydroxide, formaldehyde silk polyester, stainless steel composed of oil, cellulose, asphalt, vinyl or other resins -polyvinyl cinnamate, allyl ester, resins, isoprenoid resins, methacrylate derivatives, polyolefin sulfones thiazoline compounds, azido compounds, nitro compounds, nitro aniline derivatives, anthones. quinones, diphenyls, azides, xanthone, benzil ortho-xylene, meta-xylene, para-xylene, toluene. benzene, chlorobenzene. cellosolve and cellosolve acetate, butyl acetate, 1,1.1trichloroethane, acetone, methyl ethyl ketone, methyl isobutyl ketone copper pyrophosophate solution, acid-copper sulfate solution, acid-co per fluorobate solution, tin-lead, gold, and nickel plating solutions sulfuric-dichromate, ammoniacal hydrogen peroxide, solutions methachloroperbenzoic acid, methylene chloride, methyl alcohol, furfural. phenol, ketones, chlorinated hydrocarbons, nonchlorinated organic solvents, sodium hydroxide
Etchants
Catalysts Electroless copper bath
Screen
Screen ink
Resists
Sensitizers
Resist solvents
Electroplating
Resist stripping
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Outline source reduction techniques used in: metal cleaning and stripping surface plating and related processes printed circuit board manufacturing Outline recycling and recovery processes used in: metal cleaning and stripping surface plating and related processes printed circuit board manufacturing
Chapter 2
WASTE MINIMIZATION OPTIONS FOR THE METAL FINISHING INDUSTRY

SOURCE REDUCTION IN CLEANING AND STRIPPING
If workpieces must be cleaned, the least hazardous material should be considered first. Ideally, the cleaning method of choice would involve the fewest number of steps, employ the the least toxic medium, and generate the least waste. The most desirable cleaning media are air and water. If these are not effective, abrasive media with air or water as carriers are the next most desirable. These may be applied by either hand wiping or with a blast-type device that uses pressure. If chemicals are required to achieve the necessary finish, they should be tried in the following order: aqueous detergent solutions, alkaline solutions, acids, and solvents. This hierarchy is based on the hazardous properties of the options and treatment costs. Many aqueous detergents can be discharged directly to a POTW without treatment. Effluent containing aqueous detergents will often meet POTW discharge requirements without additional treatment unless metalcontamination is excessive. When treatment is required, it is usually for total dissolved solids (TDS) or chemical oxygen demand (COD). Alkaline solutions typically require only pH adjustment before discharge. Acid solutions can have considerable metal content and must therefore be treated more extensively. Solvents present a number of problems, including their flammability hazard and health risks to workers. Before a shop changes from one cleaning process to another it should fully evaluate the effects of the new cleaner, such as the effect of a substitute cleaners surface residue or drag-out, on downstream processes. The shop should also check with its local air district to make sure that this use of the solvent is permissible.
PREVENTING THE NEED FOR CLEANING

The first step in implementing this very desirable option is to identify the type of surface soil. A wide variety of materials is used in order to facilitate the cutting, grinding, and drawing of metal parts. These include mineral oils,
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talc, graphite, chlorinated synthetic oils, and metallic soaps. Workpieces may also be coated with water scale, heavy metal salts, or simply covered with rust. Metal finishers should be encouraged to explore other less hazardous materials to facilitate these operations. Metal finishers should be encouraged to establish a just in time approach to manufacturing, where parts are cleaned in batches no larger than can be immediately fed into subsequent processes. This eliminates the need to warehouse parts between operations, during which they may contact new contaminants and need to be cleaned again. If cleaned parts must be stored, dry nitrogen bagging is a proven way to keep parts clean and free of oxidation as they are stored for subsequent coating.
Substitute non-hazardous coatings
Some coatings are applied by vendors supplying the workpieces to the metal finisher. These coatings are intended to protect the material, but they simply add another waste stream when they have to be removed. The metal finisher should work with the vendor to replace the coating with a nonhazardous peel coating or shrink wrapping with polymeric sheeting. It should be emphasized, however, that although the avoidance option should be examined first, unwarranted relaxation of cleaning requirements may have an opposite effect of increasing waste generated due to rework of rejects caused by poor coating.
SOLVENT SOURCE REDUCTION

Halogenated compounds are the solvents typically used in cleaning operations These compounds are known to pose significant environmental health hazards and should be used only when an alternative aqueous-based emulsion, or mechanical cleaning method is not feasible. If non-solvent cleaning is not possible, the use of alternative, less hazardous solvents such as terpenes, N-methyl-2-pyrrolidone, or dibasic acid esters should be considered.
Substitute alkaline cleaners
The use of hot alkaline cleaners can prove a viable substitute for solvent degreasing. The purchase price for alkaline cleaners can be as little as half that of solvents. Treatment and disposal costs are also generally lower for alkaline cleaners. Some need only pH adjustment before discharging to a publically-owned treatment works (POTW). Others may require treatment for excessive TDS or COD. Other alternatlves to solvent cleaning are discussed below, with the emphasis on minimizing their waste output.
AQUEOUS-BASED WASTES
While aqueous-based cleaning methods are superior to solvents, consideration should first be given to the use of water, steam, or abrasives as substitutes for acid or alkaline cleaners. If their use is not feasible, then work with the shop operator to evaluate each aqueous-based cleaner with an eye toward selecting the cleaner that is least hazardous to workers and the environment.
Extending the useful life of the cleaning solution bath
Regardless of the aqueous-based cleaning method selected, a key to achieving waste minimization goals is to extend the useful lifetime of the cleaning solution bath. It is critical to ensure that workpieces entering the cleaning solution are as free of oils, solvents, or other cleaners as possible. A hot water bath for precleaning may be desirable. The bath should be supplied
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with demineralized water, possibly from the last rinse bath of the cleaning operation. The accumulation of metal fines and paint chips is detrimental to aqueousbased cleaning solutions. Continuous filtering or regular sludge removal should be used to prolong the useful life of the solution. Tanks should have plastic liners or be coated with protective finishing to eliminate the entrance of impurities from the tank itself into the cleaning solution. The racks and barrels used to hold the workpieces should be corrosion-free so that rust is not added to the cleaning solution and excess drag-out from solution adherence to roughened surfaces can be avoided. Float valves, while important to maintaining the proper level in the tank, should be closely monitored to ensure that leaks are not diluting the bath. The effectiveness of alkaline cleaner baths is reduced by introduction of materials that reduce the alkalinity, including the target soil. Bath life can be enhanced by avoiding unnecessary loading with hard water or carbon dioxide in the air used for agitating the tank. Mechanical agitation and the use of softened or deionized water are solutions to these problems. The operator should also consider keeping the tank heated continuously to minimize the absorption of carbon dioxide, with occasional cooling to allow for oil removal.
ABRASIVES SOURCE REDUCTION

Oil-based binders can burn due to the heat of friction generated during buffing. This results in the need for additional cleaning to remove the burned-on oil. As an alternative, greaseless compounds, if used properly, will result in parts which are clean and dry after buffing. These greaseless buffing compounds also prolong wheel life by adhering to the surface of the wheel. The technique used for applying liquid spray abrasives to the buffing wheel can make a significant difference in waste generation. Too little will result in excessive wheel wear, while over-application will produce waste compound and create the need for further cleaning of the workpiece. The use of a spray gun for applying liquid abrasive spray has proven to be the most effective technique in controlling the application rate. Maintaining the proper water level in mass cleaning operations is critical to source reduction. If not enough water is used, parts will leave the solution dirty. Excessive water flow will increase the attrition rate of the abrasive and increase replacement frequency.
Using greaseless buffing compounds
SOURCE REDUCTION IN SURFACE PLATING AND RELATED PROCESSES

There are significant opportunities for waste reduction by metal finishers. When changes are first suggested the inspector may encounter resistance to change by some metal finishers. If its not broken, why fix it, can be a common response from them when alternative chemistries or operating procedures are suggested. With waste disposal costs skyrocketing it may
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be just such an attitude that results in going broke. The primary goal is to challenge the metal finisher to Initiate a review of his operation. Success stories of others can be extremely helpful. The bibliography contains references for numerous case studies.
PROCESS SUBSTITUTION
Plating operations are inherently more dangerous to the environment than many other metal coating techniques. It is not likely that the inspector will get Involved in rethinking the entire process used by a finishing shop, but one should generally be aware of potential process substitutions such as buffing. cladding, and electroless coating, some of which were introduced in the previous section titled metallic coatings. Also, some accepted material substitutions to reduce or eliminate the toxicity of the waste are referred to in Table 4.
MATERIAL PURCHASE, STORAGE, AND HANDLING

Proper control over the chemicals used in the finishing process is an important way to reduce waste generation. This can be accomplished by establishing material purchase and control procedures. As one of the first steps in an Inspection. the inspector should determine the extent to which the metal finisher has established procedures relating to the purchase of chemicals. For instance, it is important that all material purchases be reviewed by a key individual or group within the operation prior to purchase The approval process should determine it the materials being evaluated contain hazardous constituents. If so. the cost of treating and disposing of the waste generated should be determined and added to the cost of purchase This will help the facility to evaluate the total costs of purchasing a chemicalm before the purchase is made Many substitute materials may have a higher purchase price than presently used materials, but disposal and treatment costs may be lower. The inspector should encourage the metal finishing facility to use a cradle to grave philosophy when evaluating the purchase of all materials
Avoiding Material Degradation

Hazardous materials that have deteriorated due to prolonged storage or materials held beyond their shelf life must be managed as hazardous wastes. You should encourage metal finishers to review their inventory and material usage policies of the finisher. Suggestions may Include strict tracking of inventories. minimizing the volume of materials inventory, and adopting a firstin first-out material usage policy Limiting employee access to raw materials is likely to reduce careless waste. The assignment of responsibility for mixing chemicals for process baths to a limited number of employees will ensure batch consistency. thereby reducing waste
Managing Samples
The metal finisher should ask chemical suppliers for small samples of less hazardous replacement chemicals. The metal finisher should also arrange in advance with the chemical supplier to return the unused portion of the sample, since it must be managed as a hazardous waste. A bench scale test of the sample may be run to determine the quality of the final finish before any large scale tests are run. Many alternative products may need to be tested before an adequate replacement is found. Bench scale tests make the screening process
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Table 4 - CHEMICAL SUBSTITUTES
POLLUTING SUBSTITUTE COMMENTS
Fire Dip (NaCN)
Muriatic Acid with additives Copper Sulfate
Slower acting than +H202 traditional fire dip. Excellent throwing power with a bright, smooth, rapid finish. A copper cyanide strike may still be necessary for steel, zinc, or tin-lead base metals. Requires good pre-plate cleaning. Noncyanide process eliminates carbonate build-up in tanks. Nonchrome substitute. Nonfuming.
Heavy Copper Cyanide Plating Bath
Chromic Acid Pickles, Deoxidizers, & Bright Dips Chrome-Based Anti-Tarnish
Sulfuric Acid and Hydrogen Peroxide
Nonchrome substitute. Benzotriazole (0.1-1.0% Extremely reactive, solution in methanol) or water-based proprietaries requires ventilation. Trisodium-Phosphate or Ammonia Noncyanide cleaner. Good degreasing when hot and in an ultrasonic bath. Highly basic. May complex with soluble metals if used as an intermediate rinse between plating baths where metal ion may be dragged into the cleaner and cause waste water treatment problems. Works faster and better that the polluting chemical. Reduces worker exposures to more hazardous hexavalent chromium. Reduces worker hazards.
Cyanide Cleaner
Tin Cyanide
Acid Tin Chloride
Plating with Chromic Acid
Plating with trivalent chromium, or bright nickel
Hydrofluoric Acid in Pickling and Stripping
Proprietary Fluoride Salts
WASTE MINIMIZATION OPTIONS FOR THE METAL FlNlSHING INDUSTRY
17
much easier and less expensive. Plus, valuable production time is not lost and large numbers of workpieces can be reworked if the candidate chemistry does not produce acceptable results.
Spills
The best way to reduce spilt-generated wastes IS for the shop to have a training program for personnel in proper handling of materials and appropriate procedures for handling spills. Simple techniques such as the use of spouts, funnels, and drip pans during material transfer can have a significant cumulative impact. Shops can place collars or drainboards that direct drainage back into the process bath to eliminate spills to the floor Providing adequate freeboard, the distance between the top of the tank and the liquid level in the tank, can reduce overflows in process tanks. Liquid spills may be best cleaned up through use of a mop and wringer rather than being soaked up with an absorbent, which must then be transferred offsite for treatment or disposal. However, spills must be compatible with the mop, and mop and other clean-up tools must be kept segregated. Spill containment berms should also be suggested for areas of high spilt probability Spills resulting from equipment failure can be prevented through strict adherence to preventive maintenance programs.
Residues and Empty Containers

Controlling access to raw materials and Instituting a check-in procedure for empty containers will result in the complete use of one container of a chemical prior to the opening of another. In this manner residues will be minimized and container rinsing. if appropriate, will be ensured. Otherwise, empty containers can be readily gathered for return to the manufacturer, avoiding their accidental, and possibly illegal, deposit into the solid waste receptacle. Unfortunately, many suppliers will not take containers back. Try to get a commitment from suppliers to take empty containers back before purchasing
Inspections
Successful Implementation of the suggestlons in this section depends upon close monitoring by the shop manager A key element in this monitoring is a regularly scheduled Inspection program The inspection should include examination of all equipment, piping. chemical storage areas, chemical containers and labels, training records, and chemical inventory records
PROCESS BATHS Material Substitution

Chemical chelators are used in many processes to increase the solubility of metals in the bath. Included in this class of compounds are organic acids such as citric acid, maleic acid and oxalic acids and amines, such as EDTA In alkaline solutions these chemicals have a strong affinity for metal ions and they are able to support higher concentrations of metals in solution. The problem with these chemistries is the large volume of sludge produced when they are treated The first step in the treatment of chelated process chemistries IS to adjust the pH to between 3 and 5 This Inactivates the chelators so the metal ions may be precipitated This is generally done by adding ferric sulfate in a
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ratio of up to eight to one by weight to the contaminating metal. The volume of sludge generated is thus increased eight-fold over that of the contaminant alone. Non-chelated chemistries are an alternative you might suggest to the metal finisher. The cost of these non-chelated materials is slightly higher than the chelated alternative, but the sludge volume generated is significantly lower. The non-chelated chemistry usually requires continuous filtration, which will cost between $400 to $1000 per tank, plus filter replacements and maintenance costs. For this modest investment the metal finisher will reduce waste and lower treatment costs, and the treated effluent is more likely to meet POTW discharge requirements. The health risks of hexavalent chromium are well documented. Its treatment as a waste requires the addition of sodium metabisulfite to reduce it to the trivalent state. Cost savings have been demonstrated through the direct plating of trivalent chromium. This process has proven especially viable for decorative chrome plating. The most significant drawback to this system is that the plated pieces tend to have a darker and less shiny appearance than hexavalent plated pieces. On balance, though, the disadvantages of this substitution are outweighed by the advantages which include decreased liability, lower disposal costs and increased worker safety. One of the most hazardous materials used by the metal finishing industry is cyanide. Inspectors finding this material in general use should suggest that alternative chemistries be sought by the facility. When disposal of the cyanide-bearing baths is necessary, they are usually treated by alkaline chlorination using hypochlorite salts or chlorine gas. If complex cyanides are being treated, ferric sulfide must be used for precipitation with the previousiy mentioned large volume of sludge being generated. Refer to Table 4 for alternatives to hexavalent chromium and cyanides. Successful non-cyanide plating of zinc and copper has been demonstrated. Research is focusing on the development of a practical non-cyanide cadmium plating process. Economic incentives can make the change to non-cyanide chemistries extremely attractive to a metal finisher. A two gallon per minute rinse water flow containing cyanide can require as much as $12,000 in treatment equipment and $3.00 per pound in treatment chemicals.
Extending Solution Life

Metal finishers should also consider methods of extending the life of process baths as a waste reduction strategy. The longer a bath can be used, the lower annual treatment and disposal costs will be. Deionized make-up water should always be used in process tanks and rinse systems. The carbonate and phosphate present in tap water reduce the efficiency of rinsing operations and reduce the life of process baths. The solids in tap water also increase the amount of hazardous sludge created. Deionization systems consist of a series of steel tanks containing a mixed bed of resins. These resins have active sites on their surfaces, which have affinities for either negatively charged anions or positively charged cations. As the tap water is passed through the resins, ionic compounds are adsorbed by the resins, thereby purifying the supply water. The cost for installation and rent of a
Using de-ionized
make-up
water
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deionization system will generally be offset by reduced costs resulting from longer rinse bath lives. One problem commonly found in alkaline baths is the build-up of carbonate salts. These come from the dissolution of atmospheric carbon dioxide in the baths. Accumulated salts. as well as other cleaning and etchant compounds. can interfere with the efficiency of the process bath and reduce its useful life. Removal of these precipitates using continuous filtration can extend the useful life of the bath and thereby reduce the waste produced annually from that process. Process baths are depleted in a number of ways. Chemicals essential to the process are removed as drag-Gut coating workpieces; water evaporates from the bath, and contaminating chemicals are introduced when workpieces are not completely rinsed. Replenishing the bath is one option the metal finisher should consider before dumping the bath. This requires some simple monitoring practices such as routine measurement of pH and metals concentration. When the effectiveness of the bath falls off, part of the bath can be dumped and fresh water and chemicals can be added to replace what has been lost. The introduction of contaminants cannot be controlled by simply adding more water and chemicals. Eventually, the levels of contaminants will increase to the point where process efficiency will begin to be affected. It is at this point that the finisher should be encouraged to seek out a treatment process that can extend the life of the bath. For example, copper can contaminate zinc and nickel plating baths. When this happens some platers will use a treatment process called electrolytic dummying. This process relies on the fact that the contaminant, copper, has a lower electrolytic potential than the zinc or nickel in the process bath. An electrolytic plate IS placed in the bath and a very low current is applied to it. Since the copper requires less electric potential to be reduced, it plates Gut preferentially on the panel. It can take several days to reduce the copper contaminant to acceptable levels, but the trade-off is the extension of the baths life and reduction in waste generation. In another example, the plater may take advantage of the extreme insolubility of lead and cadmium sulfide salts. By simply adding ferric sulfide to the process bath and filtering the resultant precipitate from the bath, the bath life can be extended. In all cases, the inspector should encourage metal finishers to use their special knowledge of their own processes to find new ways to extend the useful life of their process baths Periodic laboratory analysis of process tank contents will enhance understanding of the unique chemistries involved and how to increase process solution life.
Replenish baths rather
than
dumpirng them
Remove contaminants from baths
Drag-Out Reduction
Reduction of drag-out from process baths is a key to reducing waste in the metal finishing industry Drag-out occurs when process solutions adhere to workpieces and are carried into subsequent rinse tanks. The drag-out creates a waste stream that must then be treated. Reducing drag-out can save in both reduced process chemical costs and waste disposal costs. The volume of drag-out is influenced by the size and shape of workpieces, the viscosity of the process bath, and the concentration of the bath. Some workpieces have concave surfaces, which can trap considerable volumes
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of solution when they are withdrawn from a bath. The inspector should observe the procedures the operators are using when the racks containing the workpieces are removed from baths. Try to determine if by simply turning, twisting or shaking the racks, additional drainage of process solution can be achieved. Also make certain that the time the racks are allowed to drain over the tank is sufficient. Some metal finishers have installed a rail over their process baths where operators can hang racks to increase the drainage time. Also, observe the rate at which the racks are withdrawn. The slower the rate of withdrawal, the thinner the film of drag-out on the workpieces. The higher the viscosity of the bath, the thicker the film coating the workpieces will be. There are several ways the metal finisher can reduce the viscosity and resultant dragout. Reducing the chemical concentration in the bath will not only reduce viscosity, but also will reduce the costs of chemicals and of treatment when the bath is dumped. The inspector should encourage the finisher to test lower chemical concentrations when process baths are formulated to determine if this option is viable. If product quality is reduced, the chemicals can be added in increments until the desired quality is achieved. This may not be an option if contractual specifications require a minimum bath concentration. Another way to reduce the viscosity of process solutions is to increase the temperature. While temperatures can increase the effectiveness of some cleaning, it can also pose a greater risk to workers through higher emissions of toxic air contaminants, such as chromium and cyanide, and it will increase energy costs. When high temperature baths are used in conjunction with drag-out tanks, the benefits can be doubled. A drag-out tank is a tank placed next to a process bath and filled with deionized water. When the workpieces are withdrawn from the process bath and drained, they are placed in the dragout tank. The contents of the drag-out tank can eventually be used as make up for the process tank either after an evaporation step is used to concentrate the drag out tank solution, or directly. Drag-out tanks can reduce rinse water volumes and chemical costs by as much as 50%. Fog sprays and air knives are very useful in reducing drag-out. A spray of deionized water or air can return as much as 75% of the drag-out back to the process tank. Fog sprays are typically located just above the surface of the bath and work best where the rate of spray matches the rate of evaporation from the tank. Air knives, also located just above the tank, reduce the dragout by mechanically scouring the liquid adhering to the workpiece. However, when using compressor-supplied air, it is important to properly filter the air to prevent the contamination of the bath or the part with oil. Further, in some cases it may not be desirable for the workpiece to dry between process steps. Both of these very effective drag-out reduction techniques can be installed for about $500 per tank. The use of wetting agents can reduce drag-out by up to 50%. The metal finisher should ask his chemical supplier if wetting agents are used in the chemistries being supplied and, if not, whether wetting agents can be added.
Allow longer drainage Use less viscous baths
Other methods
for reducing
drag-out
WASTE MlNlMIZATION
OPTIONS FOR THE METAL FINISHING INDUSTRY
21
In some plating baths wetting agents have been found to improve the quality of the finish as well as reduce drag-out. The manufacturers of the process chemicals may recommend concentrations greater than are necessary to do a quality job. Maintaining baths at the lowest acceptable concentrations will reduce the amount of drag-out. Fresh baths will function at lower concentrations which can then be Increased during replenishment. The inspector should try to impress upon the metal finisher that these drag-out reduction measures, alone or in combination, are essential to an effective waste minimization program and may in fact result in sirgnifcant reductions in water usage and treatment costs.
RINSE SYSTEMS
The focus of rinse system design and review IS on the conservation of wastewater. If the shop has sufficient floor space, the installation of a multi-stage counter-current rinse system can reduce water consumption up to 99%. This system utilizes multiple rinse tanks, through which the workpiece is dipped in succession. Fresh rinse water flows into the last of the tanks. Overflow from each rinse tank flows into the tank up the line, in the opposite direction of the movement of the workpiece. Effluent from the uppermost rinse tank is used as make-up water for the process tank or captured for recycling, resource recovery, or treatment
Use countercurrent rinse systems
Whether or not multi-stage rinsing is used, spray rinsing prior to drip rinsing will significantly reduce drag-out, thereby allowing a reduction in the rinse tank(s) flow fate. Agitation of rinse tank water or of the racks holding the workpieces also Increases the efficiency of the rinsing process. Pre-set block valves or valves with restrictive orifices can be used to control water flow.
IMPROVED HOUSEKEEPING
Elimination of space between tanks or installation of drainboards to direct dragout back into the tanks when moving workpieces from one tank to another will prevent drainage onto the floor, which would otherwise enter the floor drains during hose down operations.
SOURCE REDUCTION IN PRINTED CIRCUIT BOARD MANUFACTURING

Due to the similarities of many of the processes used in surface plating and those used in printed circuit (PC) board manufacturing, this section focuses on those aspects of source reduction unique to PC board manufacturing. For additional information on source reduction in cleaning and surface preparation, electroplating and electroless plating, and rinse systems, refer to these sections in the prior discussion of surface plating and related processes. Table 5 lists chemicals and subsequent wastestreams generated in the manufacture of PC boards.
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Table 5
WASTE SOURCE WASTE STREAM DESCRIPTION WASTE STREAM COMPOSITION
Cleaning/Surface preparation
1. Airborne particulates 2. Acid fumes/organic vapors 3. Spent acid/alkaline solution 4. Spent halogenated solvents 5. Waste rinse water
Board materials, sanding materials, metals, fluoride, acids, halogenated solvents, alkali.
Catalyst application / Electroless plating
1. Spent electroless copper bath 2. Spent catalyst solution 3. Spent acid solution 4. Waste rinse water
Acids, stannic oxide, palladium, complexed metals, chelating agents.
Pattern printing/masking
1. Spent developing solution 2. Spent resist removal solution 3. Spent acid solution 4. Waste rinse water
Vinyl polymers, chlorinated hydrocarbons, organic solvents, alkali.
Electroplating
1. Spent plating bath 2. Waste rinse water
Copper, nickel, tin, tin/lead, gold, fluoride, cyanide, sulfate.
Etching
1. Spent etchant 2. Waste rinse water
Ammonia, chromium, copper, iron, acids.
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PRODUCT SUBSTITUTION
New products being developed
The conventional method for attaching components to a circuit board requires that there be holes in the board. New developments in surface mount technology allow for closer contact area of connected leads, thereby allowing a reduction in board size to as little as thirty-five percent of the conventional design. As board sizes are decreased, waste generation is decreased commensurately, with the exception of degreasing agents such as CFC-113 which are required in significantly greater quantities to adequately clean the boards for surface mounting. When an appropriate substitute for the ozonedepleting CFC-113 is identified, the relative environmental impacts of this technology should be less than those of the traditional technology. Battelle has developed a technique which couples injection molding of the board with a fast-rate electrodeposition technique that is used to produce a complex circuit board without the need for etchants, thereby reducing waste generation.
CLEANING AND SURFACE PREPARATION

While it is possible to use chelators in printed circuit board manufacturing process solutions to increase the solubility of metal ions, this practice has been curtailed due to tighter controls on wastewater. When used, this practice results in the need for additional reducing agents, such as ferrous sulfate, which cause the generation of significantly more sludge The use of non-chelate process solutions or a mild chelator such as ethylenediaminetetraacetic acid (EDTA) may be feasible. For etching, non-chelate etchants such as sodium permanganate and hydrogen peroxide/sulfuric acid may be feasible, but their use requires rigid controls. However, non-chelate process baths require continuous filtration to control buildup of solids. a cost item the operator must evaluate in comparison to waste management costs.
PATTERN PRINTING AND MASKING Use aqueous

resist and screen printer
The desired pattern on a circuit board is created by the application of a material which resists plating. Such a material is called resist. Conventionally used resist must be processed and developed with organic solvents. Aqueous processable resist is available which results in decreased waste generation. Screen-printing of circuit patterns instead of photolithography is recommended to eliminate the need for developers. New high-resolution screen-printing techniques have increased the potential applicability of this alternative approach.
Etching
The potential for using thinner copper foil should be explored. This alternative reduces the copper load produced during the etching process. Explore the use of non-chelated etchants. Sodium persulfate and hydrogen peroxide/sulfuric acid are non-chelate mild etchants which can be used to replace the chelate etchant, ammonium persulfate. The use of non-chromium etchants such as ferric chloride or ammonium persulfate will result in a less toxic waste.
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WASTE MINIMIZATION IN THE METAI. FINISIHING INDUSTRY
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Many manufacturers have switched to pattern instead of panel plating. This change reduces the amount of copper which must be etched away, thereby reducing waste volume and toxicity. This change is not possible in all instances, but should be encouraged wherever possible. Additive plating of boards, instead of the conventional subtractive method, eliminates the need for etchants. However, current additive techniques necessitate the use of solvent processable resists and the spent baths contain heavily complexed copper which may complicate wastewater treatment.
RECYCLING AND RESOURCE RECOVERY IN CLEANING AND STRIPPING

Notwithstanding a significant effort in source reduction, most metal finishers will continue to generate waste. Many options exist for recovering valuable metals from these wastes. Any type of treatment process beyond simple neutralization or pH adjustment requires a treatment, storage or disposal (TSD) permit either under RCRA or California law. Treatment activities not requiring a RCRA permit may be eligible for inclusion in Californias permit by rule program which might be exempt from permitting requirements. However, a permit by rule still involves agency and public notifications and financial assurance. The generator must check the recycling laws to ensure compliance before considering onsite or offsite recycling. The requirements for such an exemption are very specific and the determination is made on a case by case basis.
Check the regulation
SOLVENT RECYCLING
If solvent use is unavoidable, the best waste management strategy to suggest is recycling with onsite distillation equipment. This equipment can handle volumes as low as five gallons. If the plant operator does not want to purchase or lease onsite equipment, then offsite recycling should be the option of the last resort. Care must be taken to avoid cross contamination of solvents. Mixed solvents are difficult and, at times, impossible to recycle, and must be incinerated.
AOUEOUS-BASED CLEANER RECYCLING

The prospect of recycling aqueous-based cleaners is enhanced through the use of non-emulsifying cleaners, which limit the separation of oil. Closed-loop systems have been demonstrated for acid pickle wastes. Spent pickle liquor has recently been processed through a bipolar membrane, which results in a regenerated pickle liquor and a filtrate containing the precipitated metals
WASTE MlNlMlZATlON OPTIONS FOR THE METAL FINISHING INDUSTRY
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lIIlIIIlIIIIIIllIIIIIIIII RECYCLING AND RESOURCE RECOVERY IN SURFACE PLATING AND RELATED PROCESSES
MATERIAL RECOVERY AND REUSE
As regulatory requirements for plating wastes have increased, previously uneconomical recovery methods have become feasible, particularly for larger facilities. While smaller facilities may not be able to implement these technologies onsite, they should be informed of their relative merits so that they may make appropriate decisions regarding offsite treatment. The technologies available are: 1) evaporation, 2) reverse osmosis, 3) ion exchange, 4) electrolytic recovery, and 5) electrodialysis.
Evaporation
Evaporation is used to reduce the volume of a wastestream for subsequent treatment or to concentrate a contaminant sufficiently for use as a feedstock. Atmospheric evaporation systems cannot recover the vaporized water like vacuum evaporation systems do, but are considerably less expensive. The energy demand of evaporation systems is their biggest drawback. See Figure 4.
Reverse Osmosis
Reverse osmosis (RO) technology has long been used to recover plating chemicals from rinsewater as well as to purify mixed wastewater for reuse. It is used most commonly to purify rinse water from acid nickel process baths. The water is returned to the rinse tank while the nickel salts are used to replenish the plating tank. The method involves forcing metal laden water through a semipermeable membrane under pressures of 200 to 1200 psi. The membrane
EVAPORATION SYSTEM
Figure 4
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REVERSE OSMOSIS SYSTEM

Figure 5
is impermeable to most dissolved solids. The operator must carefully evaluate the type of membrane and module design to ensure that the unit will perform adequately and will fit into the allotted space. This method is not suitable for compounds having a high oxidation potential (e.g., chromic acid) and must be augmented with activated carbon treatment if non-ionized organics are present. The energy costs can be high because of the high pressures required. See Figure-5.
Ion exchange
Ion exchange is also effective for recovery of dragout from rinse waters. The process exchanges ions of harmless substances contained within the exchange resin for the ionized metals in the rinse water. The solid ion exchange particles in the resins are either naturally occurring Inorganic zeolites or the more commonly used synthetically produced organic resins. This system is suitable for chromic acid rinses and is being used to recover several metals (e.g. Ni, Cu, Ag) as concentrated solutions to be returned to the process. However, rinse waters must be segregated to do this. This method is generally less delicate than reverse osmosis. It can also be effective in removing/recovering aluminum, arsenic, cadmium, copper, and cyanide. On the other hand, ion exchange units require close monitoring and may add to the wastewater treatment load due to large volumes of regenerant and wash solutions. See Figure 6.
lnfluent Water, B+ Ions
Ion Exchange Active Zone
Treated Water. A+ Ions Legend: B = B+ Ions = Resin Containing B+ Ions = Resin Contaming A+ Ions A = A+ ions
Figure 6
WASTE MINIMIZATlON OPTIONS FOR THE METAL FlNISHlNG INDUSTRY
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Electrolytic Recovery
Electrolytic recovery captures metals in solution by plating them out on a thin starter sheet made of the metal to be recovered or a stainless steel blank, which serves as a cathode in the tank. The product of this process is a solid metallic slab, which can be reclaimed or used as an anode in an electroplating tank The technology, also called electrowinning, is applicable to rinse water and spent process baths. This technique requires rinse water segregation to prevent contamination of the anode with mixed metals.
Electrodialysis
Electrodialysis uses selective membranes to separate anions and cations from rinse waters. Each component can then be cycled back into the appropriate tank. See Figure 7.
RINSE WATER REUSE

Consider the potential of using rinse water following acid cleaning as makeup water for rinse tanks following alkaline cleaning. The method should prolong the life of the rinse water and will enhance rinsing of the alkaline-cleaned workpiece by reducing the viscosity of the drag-out film. Workpiece quality specifications will determine whether this method of recycling will work since it results in salt deposition (ie. spotting) on the part. Final or critical rinse water may be clean enough for use as makeup water in rinses requiring lesser efficiency. (See discussion of rinse systems in source reduction section.)
RECYCLING AND RESOURCE RECOVERY IN PRINTED CIRCUIT BOARD MANUFACTURING

There are several opportunities for recovering metals from solutions involved with printed circuit board manufacturing in addition to the methods previously described for electroplating. Copper from etching baths may be recovered and purified and used as makeup for the electroplating baths. Cupric chloride etchant, reduced to cuprous chloride by the etched copper, may be regenerated through direct chlorination. This is a new idea and the equipment and technology are not currently available. Recovery of metallic forms of copper, lead, and tin has been demonstrated by passing wastes through an exchange reactor containing aluminum, which displaces the metals due to the higher oxidation potential of aluminum.
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ELECTRODIALYSIS
Figure 7
WASTE MINIMIZATION OPTIONS FOR THE METAL FINISHING INDUSTRY
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Review Questions
The Metal Finishing Industry
1. 2. is there such a thing as a typical metal-finishing shop? Briefly discuss the range of metal-finishing shops. Why is it important for the metal-finishing industry to reduce its waste streams?
Physical and Chemical Processes

3. What are the primary metal cleaning processes? What are the advantages and disadvantages for each process? 4. Describe the following chemical and electrochemical processes: Phosphating, chromating, anodizing, passivation and metal coloring.
5. What occurs during electroplating and electropolishing? How do they differ? 6. How are metallic coatings placed on workpieces? 7. Describe case hardening. 8. List the steps in printed circuit board manufacturing.
Source Reduction
9. What is the hierarchy in cleaning and stripping? What is the basis for this hierarchy? 10. What alternatives can be implemented to reduce the need for cleaning? 11. Discuss substitutes for the following: Solvent cleaners Alkaline/acid cleaners Detergents 12. 13. 14. 15. Name the substitutes for both chromic acid brightener and cyanide cleaner. How can material purchasing, handling and storage contribute to source reduction? What are some of the best ways to avoid or reduce spills? Discuss how frequent and regular inspections by facility personnel can minimize waste.
REVIEW QUESTIONS
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16. Review the following techniques for process bath source reduction: material substitution extending solution life drag-out reduction modified rinse systems improved housekeeping 17. Name three source reduction techniques for the printed circuit board manufacturer.
Recycling and Resource Recovery

18. 19. Discuss solvent and aqueous-based cleaner recycling. Describe how the following technologies are utilized for material recovery and reuse: evaporation reverse osmosis ion exchange electrolytic recovery electrodialysis rinse water reuse
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WASTE MINIMIZATION IN THE METAL FINSHING INDUSTRY
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REFERENCES
REFERENCES
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GLOSSARY
Abrasive Blasting
A method used to remove brittle material such as millscale oxide, remains of paint, etc. More generally referred to as grit blasting.
Acid Descaling
An alternative name for pickling, a process using acid to dissolve oxide and scale.
Activation
Process of removing last trace of oxide on a metal surface and a thin layer of the metal itself to ensure that the metal surface to be plated is electrochemically active. (see etching)
Alkaline Descaling
A chemical process for removing scale. A typical descaling solution uses caustic soda with additives such as detergents and chelating agents.
Alloying
The addition of one metal to another metal or non-metal or combinations of metals. For instance, steel is an alloy of iron and carbon. Other metals are added to steels to impart specific characteristics like strength or corrosion resistance.
Alochrom
A proprietary process applied to aluminum and its alloys to improve corrosion resistance or to prepare surfaces for painting. Treatment produces an adherent aluminum oxide with some absorbed chromate.
Amalgamating
Process in which alloys are formed with mercury such as gold, silver, iron, copper and aluminum. Due to the toxicity of mercury, use of the technique IS declining.
Annealing
A heat treatment process which may be applied to all metals to soften them.
Anodic Etching
A form of electrolytic etching where the workpiece being etched is anodic in the electrolytic circuit (in electroplating, the workpiece is the cathode).
Anodizing
A process generally applied to aluminum and its alloys to produce an adherent oxide film to impart corrosion resistance or surface hardness
GLOSSARY
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Aquablast
A surface cleaning process which can be applied to any material where an abrasive material is suspended in water. The resulting slurry is pressurized and ejected through a nozzle. Since higher pressures can be used in this process than in other types of blasting, surface metal can be quickly removed and leaving a good surface finish.
Blasting
See listing by specific medium (e.g. Abrasive, Dry, Grit, Shot, Aqua).
Borax Treatment
A method of coating steel with a thin film of dry lubricant. After surface cleaning or acid pickling, the material is placed in a hot borax solution, allowed to come to solution temperature and removed and dried. The resulting alkaline coating imparts lubrication for subsequent drawing operations and provides minor corrosion protection.
Boriding
A high temperature process used for surface hardening of mild low carbon steels.
Bright Chrome Plating

l
Decorative chromium plate deposited directly on a nickel plate substrate
Bronzing
A chemical process generally applied to steel to impart the appearance of bronze (antimony chloride in hydrochloric acid followed by ammonium chloride in dilute acetic acid). The resulting bronze film does not have the corrosion resistance of a true bronze.
Buffing
A specific type of mechanical polishing using a high speed disc made from layers of cloth, leather or plastic impregnated with an abrasive. The workpiece to buffed is pressed against the disc.
Burnishing
A form of metal finishing where the surface is treated mechanically so that no appreciable metal is removed but the surface is smoothed.
Carbonitriding
A surface hardening technique for steel in which a hydrocarbon (e.g. propane, butane) and ammonia are are injected into a furnace (750o-800o C) containing the workpiece. The resulting atomic carbon and nitrogen react with the surface iron to form iron carbides and iron nitrides.
Carburizing
A process used for certain types of ductile steel which increases surface hardness from two to six times. It generally is conducted in a heat resistant box containing an atmosphere of carbon monoxide, carbon dioxide, water vapor, methane, hydrogen, and butane in correct ratios and heated to 900o C.
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Case Hardening
A family of surface hardening processes generally applied only to steels. (See specific listings for carbonitriding, carburizing, chromium plating, cyanide hardening, electroless nickel plating, nitriding.)
Casting
A general term covering a production technique where any metal is heated until it is molten and then poured into a mold, allowed to cool and solidify.
Cathodic Etching
A technique applied to steel workpieces where the workpiece is made the cathode in an electrolytic cell with sulfuric acid as the electrolyte. The anode will generally be lead or stainless steel. When a current is applied, hydrogen will be evolved at the cathode and the surface metal oxide will be reduced. The technique is usually applied immediately prior to electroplating.
Cathodic Protection
A technique applied to steel where metals anodic to iron (e.g. zinc, aluminum, magnesium) are applied to the surface on the steel workpiece to provide a corrosion resistant surface. The process relies on the fact that where a cell exists between two metals with an electrolyte, one of the metals will corrode and in the process of corroding protect the other metal.
Chemical Polishing
A process carried out on mild- and low-alloy steel, stainless steel, aluminum. Special solutions are used to attack the surfaces of these metals in such a manner that the peaks or corners are affected in preference to the concave surfaces. The result is a general smoothing of the surface.
Chromate Coating (Chromating)

A corrosion protection technique which has many variations and can be applied to steel, aluminum, magnesium, and zinc. It results in the formation of metal oxides on the surface of the workpiece which reacts to form metallic chromates. Chromating of aluminum and magnesium improves corrosion resistance considerably. With steel it is much less permanent.
Chromium Plating
This electrodeposition of chromium is generally applied to steel in all its forms. It is usually done for decorative purposes (bright chromium) or to provide a hard surface for engineering purposes (hard chromium). Chromium plate is nearly always deposited on top of a nickel deposit. The nickel deposit supplies the necessary corrosion resistance. Chromium plating solutions contain chromic acid (500 gm/l) and sulfuric acid (5 gm/l). Proprietary additives are sometimes used to improve throwing power, regulate the solution and to help the distribution of current.
GLOSSARY
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Chromizing
A treatment applied to mild- and low-alloy steel only. It is a surface diffusion process in which chromium is alloyed with iron to give a chromium-rich surface layer. Thoroughly cleaned workpieces are placed in a heat resistant box with a proprietary powder of an unstable chromium compound When the box is heated to over 1000o C, the chromium decomposes into an active state which reacts with the iron to produce an alloy. The longer the workpiece IS retained in the heated box the deeper the penetration the chromium alloy
Cold Galvanizing
A term sometimes used to differentiate between electroplating zinc on steel from the hot dipping of steel in molten zinc. It can also refer to a form of painting with specialized paints which result in a film of up to 90% powdered zinc, The purpose of all these processes is to provide corrosion resistance.
Color Anodizing
A process used only on aluminum and its alloys using dyes to color the anodic film. The anodic process produces a porous film which when fresh will absorb dyes The anodizing is carried out using the sulfuric acid process After completion of the anodizing the workpieces are rinsed in cold water and placed in a dye solution. After dyeing, the workpieces are again rinsed in cold water followed by immersion in nearly boiling water. The heat seals the anodic film and the surface remains permanently colored.
Contact Tin Plating

A form of electroless plating commonly used in the printed circuit board and general electronics industries to improve solderability of workpieces. The workpieces are immersed in a hot chemical solution containing unstable tin compounds. The tin reduces on the surface of the workpieces.
Copper Plating
Copper is electrodeposited for conductivity in the printed circuit and electrical industries, and for decorative purposes. There are four basic types of copper plating solutions; copper sulfate, copper cyanide, copper pyrophosphate, and copper fluoborate. The oldest technique uses copper sulfate (200 gm/l), sulfuric acid (30 gm/l) and potassium (12 gm/l). Modern solutions use proprietary additives which make it possible to plate at higher temperatures and with a high leveling action. Copper cyanide solutions are often used when steel is to be plated. It produces a thick, dense, non-porous film. A typical copper cyanide solution consists of copper (8 gm/l), and free sodium cyanide (5 gm/l). Like cyanide, copper pyrophosphate solutions can be used for plating on steel provided an initial strike is made before plating. The strike solution will usually contain copper (5 gm/l), pyrophosphate (60 gm/l), oxalate (5 gm/I) and chloride (10 gm/l). It may be heated up to 50o C. After the strike the workpieces are placed in the standard pyrophosphate plating solution which contains copper (20 gm/l), pyrophosphate (160 gm/l), oxalate (17 gm/l) and ammonia (6 gm/l). The pH of the bath must be maintained at 8.4. Additives are generally present to give good leveling. Pyrophosphate solutions
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WASTE MlNIMIZATION IN THE METAL FINISIHING INDUSTRY
require careful control and are more expensive than some alternatives, but give a bright, dense deposit with good throwing power. Copper fluoborate solutions are used when a rapid build up of thick deposits is necessary. Tight laboratory control is generally required for optimum plating efficiency. A typical solution contains copper (120 gm/l), fluoric acid (30 gm/l), and is operated at 45o C.
Corrosion
Corrosion occurs in all metals at some time and can be divided into four basic forms. Room temperature oxidation, by far the most common form, is most obvious in mild and low-alloy steels. The process is accelerated dramatically by comparatively small amounts of contaminants like chloride, sulfate, and fluoride. When exposed to high temperatures, metals will almost invariably result in oxidation of metal surfaces. Chemical corrosion is the result of attack by acids or alkaline compounds which dissolve the metal surface. Electrolytic corrosion occurs when two metals in contact with each other have different electrode potentials. It is a major contributor to most of the corrosion found in steels.
Cromodizing
A name given to the chromating of steel where a film of iron chromate is formed on the surface. The corrosion protection provided by this treatment is of a very low order. Phosphating and oiling will probably provide superior corrosion resistance without the use of chromium.
Cyanide Hardening
A surface hardening technique which uses molten cyanide salts to give workpieces a case containing carbon and nitrogen. Temperatures of 650o C to 80o C must be maintained for 20-30 minutes to be effective. The high toxicity of the cyanide used makes it expensive because of treatment requirements.
Degreasing
A form of cleaning which generally uses chlorinated solvents. In the most common form, a liquid solvent is heated in an open topped container. As it boils a hot vapor rises above the liquid. The vapor is held within the container by means of a cooling coil which runs around the inside of the container a short distance below the rim. This cold zone causes the vapor to condense and be returned to the sump for reboiling. It is therefore a form of continuous distillation. When any cold component is placed in the container, the vapor immediately condenses on the surface. The solvent dissolves any grease on the surface and as further solvent condenses it runs off the workpiece carrying the soluble soils into the sump.
Descaling
This term describes a process that can be applied to all materials to remove scale. Scale is generally produced during manufacture or storage
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and it may be obvious such as rust or millscale or it may be very unobtrusive The various methods of descaling include blasting, pickling, acid or alkaline sodium hydride treatment, and polishing.
Die-casting
A method of casting in which molten metal is poured, sometimes under pressure, into a mold or die. The die is made of metal and immediately after solidification of the casting the die opens and the casting is ejected.
Dry Blasting
A general name given to any form of blasting where the abrasive agent is not carried in water.
Dry-form Lubrication
A form of painting applied to steel surfaces of workpieces subject to light wear or abrasion. It generally uses colloidal graphite or molybdenum disulfide carried in a phenolic resin.
Electrocleaning
An electrochemical cleaning process by which a workpiece is first made the cathode in an electrolytic cell. When current is applied, the generation of hydrogen gas from the electrolysis of water at the surface of the workpiece results in a highly efficient scrubbing action. Following initial treatment as a cathode the circuit is reversed so that the workpiece is the anode. Oxygen gas, which is generated at the surface produces a final cleaning action.
Electroforming
A specific form of electroplating used where intricate shapes and relatively thin metal deposits are required. Molds of plastic, wax, or sometimes metals are made conductive by application of carbon or metallic powder and are plated by conventional methods. Nickel, copper or precious metals are generally selected for plating. The mold is generally removed at the completion of the plating process by one of a number of methods depending on the material from which the mold is constructed.
Electrogalvanizing
See Zinc Plating
Electroless Plating
When a metal is immersed in a solution of another metal with a higher electrode potential, that dissolved metal will displace the lower potential metal on the surface of a workpiece. The best known electroless plating process occurs when steel is placed in a copper sulfate solution. Copper is plated without the application an external electric current. In another common electroless process, aluminum, which rapidly forms aluminum oxide in conventional electrolysis, is plated with zinc. The zinc deposit can then be subsequently electroplated using conventional techniques.
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Electroless Nickel Plating
In this process an alloy of nickel and phosphorous can be applied to almost any metal, and to many plastic materials including glass. Prior to nickel deposition, the workpieces must be cleaned to a very high standard and then etched or sensitized before they are immersed in the electroless nickel plating solution. The solutions must be heated above 80 C for good adhesion to be achieved. Electroless nickel plating has found considerable use in two major applications. First it is employed where good corrosion resistance is required on intricate shapes, crevices, blind holes and deep cavities where conventional electroplating is not possible. Electroless nickel deposits occur in homogeneous, uniform manner on all surfaces as opposed to in electrolytic plating where there will always be areas of high current density, such as edges and points where deposits are thicker, and areas of low current density, such as recesses, where deposits are thinner. The second major area of use is where, after electroless plating, heat treatment is employed to obtain a high surface hardness.
Electrolytic Etch
A technique generally applied to steels which attacks the surface to produce a clean, oxide free material. It is often used prior to electroplating, especially chromium plating. Since it preferentially attacks edges it will open up minute cracks in the metal surface allowing electrolytic etching to be used as an inspection technique.
Electrolytic Polishing
An electrochemical process usually applied to steels and aluminum and its alloys which produces a bright surface with a highly reflective finish. In most instances this is used for decorative purposes and it often associated with some other form of metal finishing such as anodizing, plating, or lacquering. In electropolishing the workpiece is made the anode in an electrolytic cell. When current is applied metal is removed from the anode surface. Corners and peaks are preferentially dissolved because of the higher current density surrounding them. The result is the surface of the workpiece is smoothed. The electrolytes employed generally are sulfuric acid, phosphoric acid or chromic acid. Alternatives methods of polishing include barreling or other forms of mechanical polishing, and vapor blasting.
Electra-osmosis
See Reverse Osmosis
Electrostatic Painting
A form of spray painting using specially formulated paints with pigment particles which will accept a static electric charge and be carried in a nonpolar solvent. Paint guns eject the paint at a slight velocity. The particles
41
GLOSSARY
leaving the gun are given an electrostatic charge of anything up to 30,000 volts. Very small currents are employed so the safety hazard is negligible. The workpiece to be painted is at earth ground and thus there is considerable attraction between the paint and the workpiece. As the paint particles arrive at the workpiece, they are attracted and adhere to the surface. This results in the neutralization of the static charge, and added attraction of the paint particles to areas which have not been painted.
Emulsion Cleaning
A cleaning technique which acts by emulsifying contaminants. Emulsions are mixtures of two liquids, with one liquid holding the other one in a suspension similar to a colloidal suspension. The liquids will typically have different polarities and will dissolve different types of materials. One of the liquids is usually water and the other will have non-polar properties. They can therefore be used to dissotve non-polar contaminants like oil and grease from metal surfaces. With proper use emulsion cleaners can have a long useful life and produce very clean surfaces. They may have to be formulated specifically to clean certain soils.
Etching
Etching may be used as a surface preparation technique prior to electroplating (see Activation) or for removal of metal such as in the printed circuit industry where material not required on the finished product on the final printed circuit is removed by a chemical solution. It can also be used as an inspection technique due to its ability to accentuate surface cracks and defects. Even minute surface defects will be highlighted since the edges are preferentially dissolved.
Evaporation Process
See Vacuum Deposition
Ferrostan Process
A method of continuous electrolytic tin plating of steel strip in which cold reduced strip is continuously fed through the cleaning, etching, plating and rinsing processes. The solution is generally an acid sulfate which produces a matt finish.
Fire Gilt Process

A process confined to the jewelry trade in which gold dissolved in mercury (gold amalgam) is wiped on surfaces to be plated. When the article is heated the mercury is driven off leaving a gold film. The process represents a considerable health hazard due to the emission of the mercury vapor.
Fluxing
A process used in the heating of metals which may be intended to reduce or eliminate oxidation, confine the products of oxidation, reduce their melting point, and improve fluidity of surface metal layers. Fluxing is generally used in casting, welding and soldering.
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Frosting
A type of metal finishing where a fine matt finish is produced by using techniques such as acid-etching, blasting, scratch brushing or barreling.
Galvanic Protection
A general term used in the corrosion protection of steel. Technically, it refers to a metal used to protect a metal higher than itself in electrode potential. In practice, it refers to the use of zinc to protect steel.
Galvanizing
A corrosion protection technique applied only to mild steel, cast iron, and steel alloys in which workpieces are immersed in liquid zinc at 500o C. A zinc/iron alloy is formed at the surface of the workpiece giving it an adherent coating of zinc. Prior to galvanizing, the metal surface must be in a moderate state of cleanliness. This is generally accomplished by light acid pickling or blasting. Galvanized coatings are generally about 0.005 inches thick and can give a protection for 10 to 20 years.
Gilding
A process in which gold is coated on the surface of another base metal. Gold leaf, a layer beaten or rolled so thin it is porous to light, is glued or beaten onto the article to be gilded. A similar method applies a fine gold powder mixed with a flammable liquid solvent applied to the article like a paint. The solvent is allowed to evaporate or in some cases may be ignited.
Gold Electroplating
Gold has two specific properties which make it valuable in industrial and commercial uses, it resists oxidation and corrosion to a very high degree and it retains its attractive color. In industry, gold is now finding considerable use in the electronics field. While gold has a conductivity of only 60% that of copper, it has the advantage that it will retain that conductivity over a wide variety of conditions. Traditionally, gold has been plated from high concentration cyanide solutions which are often produced by immersing the gold in the cyanide dissolving the metal as gold cyanide. The solution may then be used as the electrolyte with an inert anode. The main advantage of gold plating over other methods of applying gold to surfaces, is that electroplated coatings do not have pores as gilded coatings do. This provides significantly greater life and corrosion resistance.
Grit Blasting
A technique of abrasive cleaning or surface preparation using sharp particles (e.g. cast iron shot, aluminum oxide). It covers such processes
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GLOSSARY
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as removal of scale, corrosion, paint and other surface films. Use of free silica presents a health threat and should be avoided.
Hard Chrome Plating

See Chromium Plating
Hard Facing
A term referring to processes used to harden metal surfaces and impart wear resistance by a variety of heat treatments. Also see Metal Spraying
Hot-dip Coating
See Galvanizing
Hydrogen Embrittlement
A defect which occurs during the electroplating process. Atomic hydrogen is produced at the cathode of the workpiece being plated. This atomic hydrogen is extremely reactive and has the capability of entering the interstices of the metal. Being unstable in the atomic state, the hydrogen will combine as rapidly as possible with other atoms to form molecular hydrogen. This molecular hydrogen, having a higher unit volume than atomic hydrogen, results in internal pressure in the plated metal.
Immersion Plating
A plating technique similar to electroless plating where a more electropositive metal dissolved in an electrolyte is plated onto the surface of a less electronegative metal workpiece. The term immersion plating is used where a deposit is obtained and the plating process then stops. This is distinguished from electroless plating where the deposition of the metal being plated continues to be deposited as long as the workpiece remains in the solution.
Inchrom Process
See Chromizing
Indium Plating
lndium is a metal not unlike lead but with friction and corrosion resistant properties which are unique. In fact, the sole purpose of indium plating is improving the friction characteristics of very high-rated bearing.
Kanigen Plating
First proprietary process for electroless nickel plating. For more information see Electroless Nickel Plating
Lacquering
A term which refers to applying a clear non-porous varnish to protect an existing finish. Most lacquers are cellulose-based materials in which cellulose is dissolved in a solvent. They are generally applied by spray or brush. The solvent is allowed to evaporate leaving a thin film of cellulose remains on the metal surface.
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WASTE MINIMJZATION IN THE METAL FINISHING INDUSTRY
Lead Plating
Lead plating does not have many common uses except in the production of electrodes for lead acid batteries. Steel which has been plated with lead is much stronger mechanically and lighter than the same thickness of pure lead. It is also used as a base layer for indium plating. Lead plating solutions contain approximately 100 gm/l lead and 40 gm/l fluoboric acid.
Leveling
Electrodeposited metals tend to be concentrated at sharp corners, peaks and ridges, due to the fact that current distributed on a surface will tend to concentrate at these irregularities much more than in concave surfaces such as recesses. Therefore, when a workpiece with a rough surface is electroplated, the rate of deposition will be faster on these the convex irregularities. The result will be accentuation of the items original roughness. To counteract this effect, additives are added to the electrolyte solution which produce a polarization effect which is concentrated at the peaks and ridges. This polarization effect lowers the current density at the peaks and thereby reduces the rate of deposition. The net result is to smooth or level the metal surface.
Metal Coloring
Dyes applied after anodizing or plating to color-code (ie. identify) parts.
Metal Spraying
The general term is applied to the spraying of one of several metals onto a metal substrate. In general, it is intended to produce three effects. The first, corrosion protection, usually involves spraying zinc or aluminum on structural steel components. It is also used on high tensile workpieces such as those used in aircraft, which cannot be electroplated due to hydrogen embrittlement. The second purpose for metal spraying is hard facing. Materials used in hard facing are tungsten bearing or tungsten carbide materials, cobalt and nickel with small amounts of chromium, and high manganese chrome materials. These materials provide significant resistance to wear. The third application for metal spraying is for salvage purposes. When engineering components are found to exhibit wear while in service, technical and economic considerations may make metal spraying to replace the wear a better alternative to replacement. The most common method of metal spraying is flame impingement. The technique uses powdered metal continuously fed into a high velocity flame. The flame atomizes the metal powder into a molten state and the particles are then projected by the energy of the flame onto a prepared metal surface. Plasma coating is a similar method which employees radio frequencyinduced plasmas at temperatures up to 30,000o C. This method is limited to high integrity components where excellent adhesion or sophisticated materials are required.
GLOSSARY
45
Micro-Chem
A proprietary electrocleaning process used for brightening and passivating stainless steel. It is a form of electropolishing which gives a considerably smoother and shinier finish.
Nickel Plating
A very common form of electrolytic deposition which is generally used as an undercoating for subsequent deposits. There are three common solutions used in nickel electroplating; Watts solution, sulfamic acid, and electroless plating. For a complete discussion of the latter, see Electroless Nickel Plating. Watts solution typically contains nickel sulfate (300 gm/l), nickel chloride (50 gm/l) and boric acid (35 gm/l). The mixture of constituents is necessary to properly balance the solution. Nickel chloride is required to counteract nickel sulfates low conductivity. Without boric acid to act as a buffer, the plating process would make the solution increasingly more acidic. Baths are usually maintained at 40o C or above to achieve the best results. Nickel sulfamate plating is a more recent development. It uses a solution containing nickel sulfamate (500 gm/l), boric acid (30 gml) and nickel chloride (5 gm/l). Nickel plating is most often used to prior to deposition of bright chromium deposits for decorative purposes or where a very hard surface is required. For this reason nickel plating is usually applied in a bright condition. Because of the high cost of nickel it is often applied over a bright copper deposit. The bright copper deposit does the initial leveling of the surface of the workpiece so only a relatively thin layer of nickel is required.
Nitriding
A surface hardening process which is applied only to certain types of steel which results in the hardest surface attainable by heat treatment. The process consists of maintaining workpieces in a 500o C ammonia atmosphere for up to 100 hours. Under these conditions atomic nitrogen combines with surface iron to form iron nitride. The nitrogen slowly diffuses away from the surface as long as the proper temperature is maintained. The resulting case thickness is therefore dependent on length of the heat treatment.
Passivation
The cleaning of stainless steel with nitric acid to remove carbon and other impurities.
Phosphating
A process by which the surface of a steel workpiece is converted to iron phosphate usually as preparation for painting. Before phosphating, surface must be free from rust and scale. This is usually accomplished by acid pickling or mechanically by wire brushing or blasting. Phosphating takes a relatively short time, usually five to twenty minutes. Solutions are usually maintained between 60o C and 90o C. Workpieces are generally either painted or chromated within 24 hours after treatment since the corrosion resistance imparted by phosphating is poor.
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WASTE MIlNIMIZATION IN THE METAL FlNlSHlNG INDUSTRY
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Pickling
A chemical treatment which removes oxide or scale from the surface of a metal. It most often refers to the use of sulfuric or hydrochloric acid to remove scale formed on mild and low-alloy steel during hot forming operations. Treatment of stainless steel or high nickel alloys is done with hydrofluoric acid, a particularty hazardous material which must be handled with extreme care.
Reflowing
A technique used in the printed circuit board industry in which a component is heated in order to melt solder deposits and cause them flow. It produces a bright attractive looking material, but its main purpose is for quality control. With reflowing, any defect on the substrate will not wet, clearly indicating areas where solder is missing.
Rustproofing
A general term which refers to processes applied to steel. It may include painting or galvanizing, but most often refers to phosphating and similar low duty rust preventatives.
Sacrificial Protection
A corrosion protection technique which uses a metal of lower electrode potential to protect a metal of higher electrode potential. This is possible because in the presence of an electrolyte an electrochemical cell is established in which the lower potential metal acts as a anode and the metal to be protected acts as a cathode. The anode corrodes and deposits on the surface of the cathode. In practice, zinc and aluminum are the two metals most commonly for sacrificial protection
Sealing
A term commonly applied to any metal process having a subsequent treatment capable of affecting this previous process in order to give increased corrosion protection (i.e. anodizing, phosphating).
Sensitizing
A relatively non-specific term used to cover a range of metal finishing processes which improve the treatability of a metal surface-for a subsequent process. It often refers specifically to a part of the electroless plating procedure on plastics or non-metal surfaces. After the surface has been etched it is reacted with solution which deposits a very thin film of a metal or metallic compound. The surface is then referred to as sensitized.
Silver Plating
Silver, the easiest metal (for use in plating), is deposited for decorative purposes on household and jewelry items. It is sometimes used by the electrical industry where it is plated over copper to improve corrosion resistance. A typical silver plating solution contains silver cyanide (19 gm/l), potassium cyanide (15 gm/l) and potassium carbonate (25 gm/l).
47
GLOSSARY
Solder Plating
The term covers the deposition of an alloy of 60% tin and 40% lead which is widely used in the electrical and electronics industries. It provides two valuable features, corrosion resistance and solderability. A typical plating solution contains tin (stannous chloride, 55 gm/l), lead (25 gm/l) and free fluoboric acid (40-100 gm/l). Organic additives like glue are often added to the solution to reduce the amount of granular deposits
Solvent Cleaning
Solvent cleaning normally uses chlorinated hydrocarbons, methylated spirits, or methyl alcohol. Cleaning with carbon tetrachloride, benzene, toluene, xylene and ether should not be permitted because of health hazards posed by these substances. Workpieces are either wiped with a solvent soaked cloth or dipped in liquid solvent to remove soluble soils. The soil becomes dissolved evenly throughout the solvent and on the surface of the workpiece when it is removed and evaporated.
Solvent Degreasing
See Vapor Degreasing
Stop-off
Method of protecting portions of workpiece surface from chemical processes Waxes, lacquers or special tapes are applied to areas to prevent chemical attack or deposition.
Surface Hardening
A general term referring to methods for making the surface of steel workpieces mechanically harder than their inner portions. Also see: Nitriding, Carburizing, Cyanide Hardening, Carbonitriding.
Ultrasonic Cleaning
A sophisticated method of cleaning in which adherent soils are removed by ultrasonic energy applied through liquid. The energy takes the form of cycles of positive and-negative pressure in the surface of the workpiece. With a liquid acting as a working fluid, the high frequency (up to 10 KHz) pushing and pulling loosens even tightly adherent soils. It is particularly effective on surfaces placed directly in the line beam of energy. It has limited application where intricate shapes with many recesses require cleaning.
Vacuum Deposition
A process in which certain pure metals are deposited on a substrate. The technique relies on the fact that, in a vacuum, pure metals can be vaporized at a low temperature in a closed container. The metal vapor will condense evenly on all surfaces to give a metallic coating. Aluminum is the most successfully deposited material, producing a highly reflective finish.
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Vapor Degreasing
A form of cleaning which generally uses chlorinated solvents, which have excellent degreasing properties in their own right but also produce vapors which are heavier than air. In a typical vapor degreaser, a solvent is heated in an open-topped container and as it boils it produces a hot vapor which rises above the boiling liquid. The vapor is held within the container by means of cooling coil which runs around the inside of the container a short distance below the rim. When a cold workpiece is placed in the vapor zone, the vapor immediately condenses on the surface, producing a hot clean solvent. The solvent dissolves any grease on the surface and as more vapor condenses and runs off, carrying the grease with it into the sump at the bottom of the sump for re-boiling.
Wetting Agents
Chemicals which reduce the surface tension of water, allowing it to flow from work pieces without beading up.
Zinc Coating
See Galvanizing
Zinc Phosphating
A process applied to freshly zinc plated workpieces which are immersed in a zinc phosphate solution acidified with phosphoric acid. The zinc surface deposit is converted to zinc phosphate. The workpieces are then immersed in a dilute chromic acid solution to seal the zinc phosphate deposits and prevent formation of unsightly zinc oxide.
Zinc Plating
This very common form of plating is used to provide corrosion resistance for steels. There are three widely used types of plating solutions, two of which employ cyanide. In the first, a high cyanide solution, typically contains zinc (30 grn/l), sodium cyanide (85 gm/l) and caustic soda (25 gm/l). The second solution is a low cyanide solution. It typically contains zinc (8 gm/l), sodium cyanide (8 gm/l), and caustic soda (65 gm/l). The third is an acid zinc solution which typically contains zinc (30 gml), sodium chloride (25 gm/l), and boric acid (15 gm/I).
Zincate Treatment
A pretreatment necessary for aluminum and its alloys before electroplating. After cleaning, etching in chromic or phosphoric acid to remove oxide and dipping in nitric acid to activate the surface, workpieces are immersed in a sodium zincate solution. Metallic zinc is deposited on the surface of the workpiece. It is then rinsed and immediately brought to the final plating operation.
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GLOSSARY
SECTION III
Case Studies
CASE STUDIES FOR THE METAL FINISHING INDUSTRY

This appendix provides four case studies of waste minimization efforts in the metal finishing industry. The case studies provide examples that cover the range of pollution prevention options existing in this industry. Recognizing that waste disposal costs differ between Mexico and the United States (from where these case studies originate), the case studies provide examples of potential savings. Moreover, health and other benefits often result when a pollution prevention program is implemented. The four case studies in this appendix were derived from diverse sources, thus the material contained in each case study may differ slightly from the other three studies presented in this appendix. Numerous case studies, other than those presented in this appendix, have been written in the United States. The reference list in the back of this manual lists sources for additional case studies,
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CASE STUDY NO. 1: MANUFACTURER OF COMPONENTS FOR AUTOMOBILE AIR CONDITIONERS INTRODUCTION
Case Study No. 1 presents waste minimization efforts at a plant that manufactures three distinct product components for automobile air conditioners: (1) charged air coolers, (2) round tube plate fin (RTPF) condensers, and (3) air conditioning tubes.
WASTE GENERATION ACVITIES Charged Air Coolers

When manufacturing charged air coolers, sand-cast aluminum tanks are cleaned in an aqueous alkaline bath at 160 degrees Fahrenheit (oF), rinsed in successive stages, air dried, and inspected. Air and turbulator fins, headers, and side sheets are fabricated, hand-assembled into air coolers, brazed, and painted. The wastes generated by these processes include:
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Lubricating oil, generated (1) when coil stock is made into air fins, turbulator fins, headers, and side sheets and (2) when extruded aluminum tubes are cut to length and deburred Scrap metal, generated when headers and side sheets are made from aluminum coil stock Spent solvent (trichloroethane, perchlorethylene), generated during degreasing operations Paint booth waste containing solvent and paint, generated during paint gun cleaning; water, generated when water runs off the paint booths water curtain; waste paint solids; and overspray
Taken from. "Pollution Prevention Case Studies Compendium." U.S. Envronmental Protection Agency, Office of Research and Development. Washington, D.C. 20460, EPA/600/R-046, April 1992 CASE STUDIES
RTPF Condensers
When manufacturing RTPF condensers, steel headers, aluminum hairpins, and aluminum coil stock (for fins) are fashioned into parts, degreased using perchlorethylene, dried, assembled into the condenser body, brazed, flushed with hot water, leak tested, oven dried, and dip painted. These manufacturing operations generate wastes similar to those generated when charged air coolers are manufactured.
Air Conditioning Tubes

When manufacturing air conditioning tubes, aluminum coil tubing is cut to length, formed, and straightened. About 39 percent of the product is degreased using trichloroethane. The other 61 percent is welded, pierced, and welded again before being degreased, dried, and leak tested. Cutting oils and solvent wastes are generated by these processes.
WASTE MANAGEMENT ACTIVITIES

This plant generates several different types of waste annually. Approximately 40 barrels of spent oil are disposed of off site. Twenty-five barrels of still bottoms (one third of which is trichloroethene, the remainder of which is perchlorethene) are disposed of off site. Approximately 1.4 million gallons of process wastewater is treated at the facility and emptied into the sewer. Approximately 250,000 pounds of aluminum and steel scrap is sold as refuse. Twenty barrels of paint sludge are disposed of as hazardous waste. The plant presently has a solvent distillation unit used to recover spent solvent and a secondary still used to recover solvent from the bottom of the first still. The plant has virtually eliminated sludge from its wastewater treatment system. The plant sells scrap aluminum and steel generated on site for $146,500 per year.
WASTE MINIMIZATION OPPORTUNITIES

By replacing the chlorinated hydrocarbon solvents with degreasers that can be directly discharged to sewers, waste disposal costs would be reduced by $6,007 per year and raw material cost savings would amount to $62,640 per year. The payback period for the $20,700 implementation costs would be about 4 months. Note that of the 11,000 plus gallons of solvent used each year, 92 to 98 percent is lost to evaporation. By not feeding water to idle rinse tanks and by converting these tanks to a counterflow rinse system, $33,235 would be saved each year. The payback period for the $3,480 implementation cost would be about 1 month. By converting present painting operations to electrostatic powder coating, waste solvents and other wastes, including water, paint solids, used plastic liners, and spray booth coating, would be reduced or eliminated. Each year, waste disposal costs would be reduced $5,869 and raw material cost savings would amount to $22,885. The payback period for the $106,640 implementation cost would be 3.5 years. By fabricating lightweight plastic tops and using them to cover the degreasing units when not in use, solvent evaporation would reduce raw material costs by $26,375 per year. The payback period for the $3,600 implementation cost would be about 1 month.
CASE STUDY NO. 2 2 METAL RECOVERY DRAGOUT REDUCTION

Case Study No. 2 presents waste minimization efforts at an electroplating facility. These efforts were undertaken as part of the Minnesota Waste Management Boards MnTAP program, which is supported by a grant to the School of Public Health, Division of Environmental and Occupational Health, at the University of Minnesota.
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INTRODUCTION
New Dimension Plating is an electroplating facility that employs about 40 people in Hutchinson, Minnesota. While the plant plates a variety of metals, including gold and brass, most of the plating activities at the plant involve applying chromium to objects that have been previously coated with copper and nickel. Hazardous waste is generated by plating tank dragout. This waste contained a significant amount of chromium and smaller quantities of nickel, chlorine, and copper.
WASTE GENERATION ACTIVITIES

The plants original electroplating system used a stagnant rinse tank and three countercurrent rinses to remove excess chromium solution from newly plated parts. The initial stagnant rinse tank received a large portion of the chromium. The contents of this rinse water were then gradually returned to the plating tank to replace evaporated solution. Wastewater from the first, most concentrated, rinse in the countercurrent rinse series drained to the plants pretreatment system where chromium was removed during sludge production (see Figure 1).

New Dimension Plating redesigned its electroplating system and hazardous waste pretreatment system to meet the following goals:
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Maintain high quality plating Reduce the amount of chromium dragged out of the plating bath Reuse chromium in the plating bath Reduce sludge production Reduce the use of treatment chemicals
To reduce the amount of chromium dragout, New Dimension Plating decided to install a drip bar in a spray rinse tank. New Dimension built the spray rinse tank and drip bars in the original systems stagnant rinse tank. The new system allows the company to reduce dragout by providing longer drip time, thus avoiding the possibility of staining. By adjusting the size of the nozzles and the length of spraying time, the amount of rinse water solution can also be controlled. By increasing evaporation in the chromium tank, all of this solution can be returned to the plating tank on a daily basis, thereby reducing the amount of dragout that continues through the rinse system (see Figure 2).
Taken from, "MnTAP," Minnesota Technical Assistance Program. date unknown
CASE STUDIES
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Figure 1 - Original System
New Dimension Plating was meeting current regulations for wastewater discharge, but the operation of the system was very expensive. The company wanted to reduce chromium waste and cut treatment chemical costs, but maintain a high level of plating quality.
The approximate cost of the new equipment is as follows: Evaporators Pumps Spray nozzles, racks PPS2 Purifier Installation Total Cost $1,000 $1,000 $50 $350 $500 $2.900
The operating cost of the new system is minimal, with no added costs for utilities or supplies. Additional labor consists of approximately 1 hour every 2 weeks. The first of the three original countercurrent rinse tanks was converted to a stagnant rinse tank, and the last two were combined into one large continuous rinse tank. New Dimension built evaporators to reduce the volume of water in the plating tank. The stagnant rinse tank was built to allow all of the spray rinse solution and some of the stagnant rinse water to be returned to the tank each day. An electropurification module was installed directly into the plating bath to remove contaminants from the returned dragout solution without interrupting the plating process. New Dimension Plating chose the Model PPS2 porous pot chrome solution purifier, manufactured by Hard Chrome Plating Consultants of Cleveland, Ohio. The company is completely satisfied with how this unit functions and felt that other manufacturers could obtain similar results with this type of unit.
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Figure 2 - New System
As a result of the new system, the amount of chromium dragout fed into the stagnant rinse tank was reduced from 7 pounds to 1 pound per day.
RESULTS AND DISCUSSION

Change: Installation of the spray rinse and drip bar in the existing stagnant rinse tank Results: This initial rinse following the chromium plating reduces dragout in the system because all of the rinse water is returned to the plating tank. The new rinse system reduces water flow from 1.2 gallons per minute (gpm) to 1.0 gpm. The large rinse tank makes rinsing of the large parts more efficient. The unit allows reuse of the dragged out chromium by removing contaminants from the rinse water returned to the plating tank
Conversation of countercurrent rinses into one stagnant rinse and one large continuous rinse
Installation of the electro-purification unit (the Mode I PPS porous potchrome solution purifier) in the chromium plating tank.
CASE STUDIES
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By using a spray rinse system with a drip bar following the chromium plating bath, New Dimension Plating has reduced dragout from 7 pounds to 1 pound daily. When combined with in-tank electropurification of metal contaminants, this reduction reduced sludge production and saved an estimated $7,000 associated with the purchase of chromium and treatment chemicals. New Dimension has been quite satisfied with the results of the new system.
CASE STUDY NO. 3: WASTE MINIMIZATION ASSESSMENT FOR A MANUFACTURER OF SHEET METAL CABINET5 AND 3 PRECISION METAL PARTS INTRODUCTION
Case Study No. 3 presents waste minimization efforts at a plant that manufactures sheet metal cabinets and precision metal parts. Approximately 1.15 million parts are produced annually by 140 employees who operate the plant 2,210 hours per year. To make the cabinets, sheet metal is cut to size, bent, welded, and polished. The surface of the metal parts is then treated and painted. The machined parts are produced from bar stock that is cut, drilled, milled, and ground as needed. Most of the waste at the facility is generated by the chromate conversion and iron phosphate coating processes. These processes are used to prepare the parts for painting.

When making the metal cabinets, sheets of aluminum and steel are cut to the proper size and shape, and holes are punched into the metal. The metal is then bent and welded together as needed. Rough edges and surfaces are polished using power sanders and buffers. Scrap metal is shipped to a scrap metal dealer for recycling. Spent cutting fluid and waste hydraulic oil are combined and shipped off site for recycling or incineration. Before painting, the surface of the metal parts is treated to improve paint bonding and provide corrosion protection. Aluminum parts receive a chromate conversion coating, and steel parts receive an iron phosphate coating. During treatment, aluminum parts are dipped in a caustic cleaning solution and rinsed in a continuous-flow tap-water rinse. The parts are then dipped in a third tank containing a desmut solution and rinsed again in another continuous-flow tapwater rinse. Next, the parts are placed in a chromic acid-based chromate conversion solution, rinsed in another continuous-flow tap-water rinse, and finally placed in a tank containing a heated dead rinse of tap water. The caustic cleaner, desmut, and first rinse tanks are dumped monthly; the chromic acid tank is dumped every 3 to 4 years; and the remaining solutions are dumped every 5 months. In addition, sludge accumulates in the caustic cleaner tank, which is cleaned monthly. When coating steel parts with iron phosphate, the parts are dipped in a caustic cleaning tank and then rinsed with a continuous-flow tap-water rinse. The parts are then dipped in a tank that contains an iron phosphating solution and subjected to another continuous-flow tap-water rinse. The parts are finally dipped in a deoxidizing solution. All of these baths are dumped and replenished on a monthly basis. Combined wastewaters from the iron phosphate and chromate conversion
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Taken from, from "Environmental Research Brief," U.S. Environmental Protection Agency, Research and Development. Risk Reduction Engineering Laboratory. Cincinnati, OH 45268, EPA/600/S-92/019, May 1992 WASTE MINIMIZATION IN THE METAL FINISHING INDUSTRY
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lines drain to an overflow tank. These wastewaters are then drained to the sewer as industrial wastewater. Typically, the wastewaters are not pretreated prior to discharge because the wastewater meets discharge limits set by the publicly owned treatment works (POTW). Sludge accumulates in the caustic cleaner and iron phosphate tanks and is disposed of monthly. Solvent-based paint is applied to metal parts in dry paint booths. Waste paint, generated when the paint mixture becomes too thick, is shipped to a hazardous waste treatment, storage, or disposal facility (TSDF). Spent paint thinner is also shipped off site. Painted parts are dried and cured in ovens. The plant uses powder-based paint coatings on a few parts. The type of paint used is dictated by the customers requirements. When producing machined parts, bar stock is cut, drilled, milled, and ground as needed. Finished parts are assembled (if required) and shipped to customers. Metal scrap is shipped to a scrap metal dealer for recycling. Spent cutting fluid and waste hydraulic oil are combined with similar wastes and shipped off site for recycling or incineration.

This plant takes the following steps to manage its wastes:
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Scrap metal is segregated on site and sold to a recycler. To contain spills, all reagent tanks in the phosphating and chromating lines are located in a large pit with a central drain. Drain boards are used between surface treatment tanks to reduce dragout. Reagent solutions in the surface treatment lines are agitated with air to increase their effectiveness. Dry paint booths are used to paint metal parts, thus avoiding the aqueous paint-laden wastes that are generated by wet paint booths. A small powder coating unit is used to paint some products, thus avoiding the use of solvent-based paints. Tank dumps are coordinated to achieve neutralization so that the effluents discharged to the POTW meet wastewater requirements.
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Table 1 shows the opportunities for waste minimization at the facility. The present practices, recommended actions, and waste reductions and their associated savings are also given in Table 1. The quantities of hazardous waste currently generated by the plant and possible waste reduction depend on the plants production level. All values should be considered in this context. It should be noted that, in most cases, the economic savings associated with waste minimization opportunities result from the need for less raw material and from reduced present and future costs associated with the treatment and disposal of hazardous waste. Other savings that are not quantifiable include future costs related to changing emissions standards as well as costs associated with liability and employee health. It should also be noted that the savings given for each opportunity reflect the savings achievable when independantly implementing each waste minimization opportunity; they do not reflect the duplicate savings that would result when theopportunities are implemented as a package.
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In addition to the opportunities recommended and analyzed in Table 1, several additional measures are presented below. These measures were not analyzed completely because of insufficient data, implementation difficulty, or a projected lengthy payback. Since one or more of these approaches to waste reduction may become more attractive over time, they were brought to the plants attention for future consideration.
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Install filtration units for the iron phosphating and caustic cleaner solutions to increase solution life. Use deionized water to make-up and maintain the caustic cleaner and iron phosphating solutions, thereby reducing sludge formation. Substitute nonchromate conversion coating for conversion coating currently used on aluminum parts. Increase drainage times over the tanks in the iron phosphating and chromate conversion lines in order to reduce dragout. Segregate and recycle waste oil from the spent cutting fluid. Implement a preventive maintenance program in the machine shop to reduce the quantities of spent cutting fluid and waste oil.
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CASE STUDY NO. 4: WASTE MINIMIZATION ASSESSMENT FOR A MANUFACTURER OF METAL-PLATED DISPLAY RACKS4
INTRODUCTION
Case Study No. 4 discusses a plant that manufactures metal-plated display racks. The plants 200 employees process approximately 10 million pounds of metal annually and operate the plant 4,160 hours per year. During this process, steel wire, tubing, and sheets undergo machining operations, and the resulting parts are nickel and brass-plated, nickel-plated, zinc-plated, nickel and chrome-plated, or painted. The various finished parts are then assembled into display racks. The majority of waste at the facility is generated by the plating lines.

The raw materials used to make the display racks include steel wire, tubing, and sheets; nickel, zinc, and brass plating anodes; cleaning agents and plating solution chemicals; and powder and liquid paints. Approximately 40 percent of the finished products are nickel and brass-plated, 26 percent are nickel-plated, 24 percent are zinc-plated, and 10 percent are nickel and chrome-plated. The steel wire, tubing, and sheets undergo stamping, bending, forming, shaping, welding, and riveting. The parts to be plated are then sent through one of the three following plating lines. Other parts are sent to the paint line, which is also described below.
Taken from. "Environmental Research Brief," U.S. Environmental Protection Agency, Office of Research and Development. Risk Reduction Engineering Laboratory, Clnclnnatl. OH, EPA600/S-92021, May 1991 WASTE MINIMlZATION IN THE METAL FINISHING INDUSTRY
Table 1 Waste Minimization Recommendations

Solvent-based paints are used to coat the majority of this plants products. Waste paint, paint sludge, and spent thinner are disposed of offsite. Replace solvent-based painting with powder-based painting for a portion of the plants products. Cost savings will result from reduced disposal costs and reduced raw material costs. Installation of a batch spray booth for powder coating will be required. Waste reduction = 72 gallons per year (gal/yr) (waste paint and paint sludge) + 66 gal/yr (spent thinner); Waste management cost savings = $740 per year; Net raw material cost savings = $14.230 per year; Total cost savings = $14,970 per year; Implementation cost = $20,600; Simple payback = 1.4 years Waste reduction = 72 gal/hr (waste paint and paint sludge) + 66 gal/yr (spent thinner); Waste management cost savings = $740 per year: Net raw material cost Savings = $10,930 per year; Total cost savings = $11,670 per year
Replace solvent-based painting with water-based painting for a portion of the plants products (a separate portion from previous. WMO). Cost savings will result from reduced disposal costs and reduced raw materials costs. This change requires the purchase of new paint application equipment and may require increased curing times. A solvent recovery unit in the plant currently is not operational because of oil and water leaks. Overhaul the solvent recovery unit to permit reuse of spent paint thinner. Cost savings will result from reduced disposal costs and reduced purchases of thinner.
Waste reduction = 660 gal/yr; Waste management cost savings = $3,890 per year; Net raw material cost savings = $1,780 per year; Operating cost of recovery unit = $430 per year; Net cost savings = $5.240 per year; Implementation cost = $2,500; Simple payback = 2.1 years Waste reduction = 425 gal/yr; Waste management cost savings = $2,920 per year; Net raw material cost savings = $570 per year: Operating cost of filtration unit = $370 per year; Total cost savings = $3,120 per year; Implementation cost = $7,060; Simple payback = 2.3 years
Cutting fluid is used until it becomes malodorous or until its viscosity and lubricity are unacceptable. Average fluid lifetime is about 3 months.
Institute a program to recycle tie cutting fluid onsite. Fluid should be filtered periodically to remove metal chips and particulate matter, thereby extending the life of the cutting fluid. In addition, the spent cutting fluid can be treated with acid to reduce the volume of wastes that must be shipped offsite. The addition of add will cause a phase separation; the aqueous phase can be neutralized and sewered and the organic phase should be disposed of offsite. Install a flow reducer and flow meter in the water supply line upstream of the rinses in the chromate conversion and iron phosphating lines, thus reducing the quantity of water purchased and sewered.
Rinse water rates set by operators exceed flow rates required by the rinses in the chromate conversion and phosphating lines.
Waste reduction = 331,500 gal/ yr; Waste management cost savings = $1,000 per year; Net raw material cost savings = $510 per year; Total cost savings = $610 per year; Implementation cost = $100; Simple payback = 0.2 year
CASE STUDIES
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BARREL PLATING LINE

Small fabricated parts are cleaned prior to plating to remove residual oils and grease by using either a vibrating cleaning unit or a rotating abrasive tub. The vibrating tub cleans parts by vibrating them in a chemical solution. Spent cleaning solution and rinse water are sent to the plants wastewater treatment facility. In the rotating abrasive tub, the parts and abrasive pellets are placed in small rotating tubes. Spent abrasive pellets are disposed of in a landfill. The cleaned parts are placed in hollow barrels that are attached to an overhead conveyor system. The barrels, which have holes along the length of their surfaces, are then slowly rotated while submerged for a specified amount of time in the plating lines various tanks. Each batch of parts to be plated undergoes specific steps in the line. All of the pieces pass through most of the same preparatory stages, while later stages in the line are reserved for one type of plated part only. Plated parts are then sent to other areas of the plant for assembly. Spent solutions in all the tanks, except the plating baths, are dumped to the plants wastewater treatment facility.
ZINC PLATING LINE

Larger-size metal pieces are manually hung on racks attached to an overhead conveyor system that is used to dip parts in the 22 tanks that make up this line. Plated parts are transferred to the assembly areas of the plant. All spent tank solutions are piped to the plants wastewater treatment facility.
FRAME PLATING LINE

The frame plating line is used to plate nickel, nickel and chrome, and nickel and brass onto large display rack frames. Parts are hung on racks as in the zincplating line. Some of the tanks in this line are bypassed, depending on which type of plating is required. Finished parts are transferred to the assembly areas of the plant. Spent tank solutions are sent to the plants wastewater treatment facility.
PAINT LINE
Miscellaneous metal pieces that do not require plating are sent to the three-stage washer and paint areas. The parts are hung on a small conveyer system that transports the parts through an enclosed washer line containing three different solution-filled tanks. Spent solutions are dumped directly to the municipal sewer. After cleaning and drying, parts are painted using electrostatic powder coating or liquid dip painting. Overspray powder is collected and reused. Dragout from the dip painting process is collected on cardboard or plastic sheets that are disposed of in a landfill. After drying, the painted parts are transferred to the assembly areas of the plant.

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The plant operates an electrostatic powder paint system to reduce the amount of paint wastes it generates. The plant uses water-based, nonhazardous liquid paints. Filtering systems recover zinc and nickel from spent plating solutions.
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Cyanide-laden brass plating water is stored in a holding tank and used as rinse water by several of the plating line stages. All wastewater is treated on site before release to the municipal sewer. A natural gas-fired dryer is used to reduce the volume of sludge resulting from the filter press operation.
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Table 2 shows the opportunities for waste minimization at the plant. The type of waste, the minimization opportunity, the possible waste reduction, and its associated savings and implementation cost, including its payback time, are presented in the table. The quantities of waste currently generated by the plant and possible waste reduction depend on the plants production level. All values should be considered in this context. It should be noted that the economic savings associated with each waste minimization opportunity, in most cases, results from the need for less raw material and from the reduced present and future costs associated with treatment and disposal. Other savings that are not quantifiable include a wide variety of possible future costs related to changing emissions standards as well as the costs associated with liability and employee health. It should also be noted that the savings given for each opportunity reflect the savings achievable when independently implementing each waste minimization opportunity; they do not reflect duplication of savings that would result when the opportunities are implemented as a package. Table 2 Waste Minimization Recommendations (Sheet 1 of 2)
Present Practice Proposed Action Waste Reduction and Associated Savings
Contaminated plating, wash, and rinse water from the barrel, zinc, and frame plating lines and contaminated wash and rinse water from the paint line are treated on site and sewered.
Install a piping system to recycle treated wastewater within the plant to reduce purchases of water. If necessary, improve the current methods of wastewater filtering to provide sufficiently clean water.
Estimated waste reduction = 3,114,290 gallons per year (gal/ yr); Net raw material cost savings = $11,120 per year; Operation cost = $3,840 per year; Total cost savings = $7,280 per year; Implementation cost = $56,380 per year; Simple payback = 7.8 years Estimated waste reduction = none; Waste disposal cost savings = $24,460 per year; Net raw material cost savings = $6,250 per year; Operating cost = $8,000 per year: Total cost savings = $22,710 per year; Implementation cost = $70,000; Simple payback = 3.1 years
As the nickel plating baths in the barrel and frame plating lines become contaminated, they are emptied into dedicated filtering units used to recover a larger portion of the particulate nickel in the solutions. The filtering units are periodically backflushed with a weak acid solution. The acid solution,, which contains contaminants. is sent to the plant's wastewater treatment facility. Currently, a significant amount of nickel is discharged in the wastewater sludge which, as a result, is classified as a hazardous waste.
Modify the plating lines in question to incorporate the utilization of a zero discharge recovery (ZDR) system. It is recommended that the system use reverse osmosis technology to recover plating bath solutions at plant-specific concentration levels. The system will operate in a closed-loop manner. Therefore, the amount of nickel discharged to the wastewater treatment facility will be reduced. A portion of the chemicals required by the baths and by the water treatment facility will no longer be needed. Approximately the same amount of sludge will be generated, but it will be classified as nonhazardous.
CASE STUDIES
11
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Table 2 Waste Minimization Recommendations (Sheet 2 of 2)
Present Practice Acid wash tanks, which are used in each of the plating lines for cleaning of metal parts, are sent to the wastewater treatment facility as they become contaminated. Proposed Action Recover and reuse the spent salt/ acid solution from the contaminated wash tanks. It is estimated that 70 percent of the acid salt can be recovered using an evaporator and reused. Implementation of this recommendation will lead to a reduction in the amount of acid and salt purchases. Wherever possible, modify the zinc and frame plating lines to use spray rinsing techniques instead of dipping objects in tanks. Waste Reduction and Associated Savings Estimated waste reduction = 42 gal/yr (waste solids) + 30,860 gal/yr water; Waste management cost savings = $390 per year; Net raw material cost savings = $7,700 per year; Total cost savings = $8,090 per year, implementation cost = $29.440. Simple payback = 3.6 years Estimated waste reduction = 617,760 gal/yr; Net raw material cost savings = $2,200 per year; Implementation cost = $16.900; Simple payback = 7.7 years
Rinsing in the plating lines is accomplished by dipping parts in rinse tanks. As a result, considerable dragout and contamination occur. Spent water from the rinsing tanks is dumped to the onsite wastewater treatment facility, treated. and released to the municipal sewer. Dragout in the three plating lines current accounts for an estimated 10 percent loss in chemical solutions.
Install rinse devices above each plating and wash tank in the zinc and frame plating lines to spray water on parts as they are removed from tanks. As a result, plating solutions will be returned to their tanks before dragout occurs. Install individual heat exchangers to serve each heated wash tank and plating bath. The proposed units should transfer heat from the main steam line to smaller lines feeding each tank. Therefore, the steam will not come in contact with any process fluids and can be returned to the boiler.
Estimate waste reduction = none; Net raw material cost savings = $2,800 per year; Implementation cost = $17,940; Simple payback = 6.4 years
Various tanks in the plating and paint lines are steam heated. Condensate is not returned to the boiler because of concerns about possible contamination. It is sent to the waste treatment facility.
Estimated waste reduction = 262,000 gal/yr; Net raw material cost savings = $940 per year; Energy cost savings = $370 per year; Boiler feedwater chemical cost savings = $3,500 per year; Total cost savings = $5.310 per year; Implementation cost = $33,700; Simple payback = 6.3 years
12
ATTACHMENT A
Information on Accessing Pollution Prevention Information Clearinghouses
ATTACHMENT B
Survey
Name : Position: Phone: Fax:
Organization: Address:
SURVEY:
Please help us by answering the following questions:
A.
PROFILE OF YOUR ORGANIZATION

Trade association / / Business / / Governmental office
/ / Other What product or service does your business/organization provide?
How
old
is
your
business/organization? years
How many employees work in your business/organization?
B.
TRAINING NEEDS
U.S. EPA and SEDESOL plan to add sections to this manual to support other industries in the border area. Which industries should be addressed next? / / Agricultural Chemicals / / Wood Finishing / / Other
What type of training would you attend? / / Technical workshops / / General training / / None / / Other
U.S. EPA and SEDESOL are considering holding training sessions on "pollution prevention." What information would be useful to you in this area?
-2C. USEFULNESS OF MANUAL

/ / Yes / / No / / No
Did you find the format of this manual useful? Did you find its content useful? How would you improve it? / / Yes
What other information should be included?
Who else should receive this manual? Name : Address:
D.
ADDITIONAL COMMENTS
Please provide any additional comments on this manual and its usefulness.
Please fold on the dotted line and mail. If you have any questions regarding this publication or would like additional information, you may contact U.S. EPA (415)744-1500, or SEDESOL 525-553-6421.
----Place stamp Here -----
HILARY LAUER POLLUTION PREVENTION COORDINATOR US EPA (H-1-B) 75 HAWTHORNE ST SAN FRANCISCO CA 94105-3901
(Place tape here)
APPENDIX A
Referencing Additional Information
APPENDIX A: ADDITIONAL INFORMATION

The following are additional documents on pollution prevention that you may find useful. Unfortunately, at this time they are only available in English. Copies of documents with EPA document numbers may be obtained from EPA Center for Environmental Research Information (CERI) or the Pollution Prevention Information Clearinghouse (PPIC). Copies of documents with Pollution Prevention Information Exchange System (PIES) numbers may be obtained through PPIC/PIES.
EPA CERI Publications Unit 26 West Martin Luther King Drive Cincinnati, OH 45268 (513) 569-7562 PPIC 401 M Street Mailcode PM221 A Washington, D.C. 20460 (202) 260-1023 PIES Technical Support Office SAIC 7600-A Leesburg Pike Falls Church, VA 22043 (703) 821-4800
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GENERAL INFORMATION:
1. Guides to Pollution Prevention: The Metal Finishing Industry U.S. EPA Office of Research and Development EPA/625/R-92/011 October 1992 2. Waste Minimization in Metal Parts Cleaning U.S. EPA Office of Solid Waste and Emergency Response EPA/530-SW-89-049 1989 3. Waste Audit Study-Metal Finishing Industry California Alternative Technology Section and U.S. EPA PIES #005-073-A 1988 4. Waste Audit Study-Printed Circuit Board Manufacturers California Alternative Technology Section and U.S. EPA PIES #005-006 1987 5.
Source Reduction of Chlorinated Solvents-Electronic Products Manufacture and Solvent Cleaning Metropolitan Water District of Southern California &The Environmental Defense Fund PIES #609-008-A and PIES #609-005-A 1990
6. Facility Pollution Prevention Guide U.S. EPA Office of Research and Development EPA/600/R-92/088 May 1992
MACHINING
7 . J. T. Johnson, Cincinnati Milacron Products Division. A Comprehensive Strategy for an Overall Program of Metal Working Fluid Management. Cincinnati, OH, 1985.
SURFACE PREPARATION
8 . R. Schecter and G. Hunt, North Carolina Pollution Prevention Pays Program. Case Summaries of Waste Reduction by Industries in the Southeast. Raleigh, NC. 1989. Page 40. (PIES #112-003-A)
APPENDlX A
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SOLVENT USAGE
9 . L. Traverse, Massachusetts Office of Safe Waste Management, Creative Source Reduction Techniques. Third Annual Massachusetts Hazardous Waste Source Reduction Conference Proceedings. Boston, MA. October 23, 1986. (PIES #022-012) 10. R. Schecter and G. Hunt, North Carolina Pollution Prevention Pays Program. Case Summaries of Waste Reduction by Industries in the Southeast. Raleigh, NC. 1989. Page 39. (PIES #112-003-A) 11. C. H. Fromm, S. Budaraju and S. A. Cordery, Jacobs Engineering Group. Minimization of Process Cleaning Waste. So/vent Waste Reduction Alternatives Seminar, Speaker Papers. Washington, DC. March 1988. (PIES #005-012-A-000) 12. E. A. Rodzewich. Source Reduction-Parts Cleaning. Solvent Waste Reduction Alternatives Seminar, Speaker Papers. March 1988. (PIES #005-012-A-000) 13. Jacobs Engineering Group, Inc. for (U.S. EPA), Hazardous Waste Engineering Research Laboratory, Off ice of Research and Development. Waste Minimization Audit Repory: Case Studies of Solvent Wastes from Parts Cleaning and from Electronic Capacitor Manufacturing Operations. Cincinnati, OH. (PIES #010-003-A) 14. Institute for Local Self-Reliance. Engine and Plumbing Parts Manufacture, Case Study 60, Proven Profits from Pollution Prevention: Case Studies in Resource Conservation and Waste Reduction, Volume II. Washington, D.C. 1989. (PIES #306-001-A) 15. North Carolina Department of Environment, Health, and Natural Resources: Pollution Prevention Program. Managing and Recycling Solvents in the Furniture Industry. Raleigh, NC. May 1986. (PIES #034-018-A) 16. Hackney, Pollution Prevention Challenge Grant Program, North Carolina Department of Natural Resources. Pilot Study of Solvent Recovery for Use in Paint Equipment Cleanup. December 1986. (PIES #034-050-A-000) 17. N. H. Frick and G. W. Gruber, PPG Industries, Inc. Solvent Waste Minimization by the Coatings Industry. Pittsburgh, PA. March 1988. (PIES #800-01) 18. California Department of Health Services, Alternative Technology Section, Toxic Substances Control Division, Waste Audit Study: Automotive Paint Shops. January 1987. (PIES #005-005) 19. M. Drabkin and P. Sylvestri, U.S. EPA Hazardous Waste Engineering Research Laboratory, Off ice of Research and Development. Waste Minimization Audit Report: Case Studies of Minimization of Solvent and Electroplating Wastes at a DOD Installation. Cincinnati, OH. 1989. (PIES #101-036-B)
AQUEOUS CLEANERS
20. K. B. Patterson and D. E. Hunt, U.S. Air Force, AGMC/MAQSE, Newark Air Force Base, OH. The Cyl-Sonic Cleaner: Aqueous Ultrafiltration Cleaning Using Biodegradable Detergents. Process Technology 88: The Key to Hazardous Waste Minimization, Air Force Logistics Command. Sacramento, CA. August 15-18, 1988. (PIES #100-100-D) 21. T. Smietana, Off ice of Safe Waste Management "Trichloroethylene Elimination Case Study: Electric Furnace #2 Bright Anneal Line Industrial Metals Department of Texas Instruments, Inc., Third Annual Massachusetts Hazardous Waste Source Reduction Conference Proceedings. October 23, 1986. (PIES #022-012)
WASTEWATERS
22. Massachusetts Department of Environmental Management, Office of Safe Waste Management. Preliminary Report: Phase I Source Reduction Activities, Southeast Platers Project. Case Study B. July, 1988. Page 3. (PIES #022 003-A)
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23. North Carolina Department of Natural Resources and Community Development. Water Conservation for Electroplaters: Counter-Current Rinsing. Raleigh, NC. 1985. (PIES #034-024A) 24. North Carolina Department of Natural Resources and Community Development Water Conservation for Electroplaters: Rinse Tank Design. Raleigh, NC. 1985. (PIES #034026A) 25. Office of Safe Waste Management, Massachusetts Department of Environmental Management. "The Robbins Company: Wastewater Treatment and Recovery System, A Case Study. Raleigh, NC. 1985. (PIES #034-026B)
DEGREASING
26. G. Hunt, North Carolina Department of Natural Resources and Community Development. Accomplishments of North Carolina Industries-Case Summaries Raleigh, NC. January 1986, p. 22. (PIES #034-010) 27. Hazardous Waste Reduction Program of the Oregon Department of Environmental Quality. The Tektonix Payoff. Salem, OR. June 1988. (038-003-A-000) 28. United Nations, Economic and Social Council, Economic Commission for Europe. Compendium on Low- and Non-Waste Technology: Elimination of Chlorine by the Use of Fumeless In-line Degreasing in the Aluminum Industry. Geneva, Switzerland. 1983. (PIES #400-103) 29. New Jersey Hazardous Waste Facilities Siting Commission, Hazardous Waste Source Reduction and Recycling Task Force. A Study of Hazardous Waste Source Reduction and Recycling in Four Industry Groups in New Jersey. Newark, NJ. April 1987. Case study D4.1, p. 30. (PIES #031-001 -A) 30. S. P. Evanoff, et. al. Alternatives to Chlorinated Solvent Degreasing-Testing, Evaluation, and Process Design Process Technology 88. Sacramento, CA. August 15-18,1988. (PIES #100-100-D)
SURFACE TREATMENT AND PLATING

ELECTROPLATING
31. G. Hunt, et al., North Carolina Department of Natural Resources and Community Development. Accomplishments of North Carolina Industries-Case Summaries. Raleigh, NC. January 1986, p. 22. (PIES #034-010) 32. United Nations, Economic and Social Council, Economic Commission for Europe Compendium on Low- and Non-Waste Technology: A Low-Waste Electroplating Process. Geneva, Switzerland. 1985. (PIES #400-125) 33. D. Huisingh, L. Martin, H. Hilger, N. Seldman, The Institute for Self-Reliance. Proven Profit from Pollution Prevention. Washington, D.C. 1985, Case Study 26, Page 103. (PIES #306-001-A) 34. G. F. McRae. In-Process Waste Reduction: Part 1-Enviroscope, Plating and Surface Finishing, June 1988. 35. David Wigglesworth, et.al., Alaska Health Project. Waste Reduction Assistance Program (WRAP) On-Site Consultation Audit Report: Electroplating Shop. Anchorage, Alaska. April 7, 1987, pp. 17. (PIES #002-016-A-001) 36. Edward Saltzberg, Ph.D., Science Applications International Corporation. Methods to Minimize Wastes From Electroplating Facilities, Process Technology 88: The Key to Hazardous Waste Minimization, Air Force Logistics Command. Sacramento, CA. August 15-18, 1988. (PIES #100-100-D)
APPENDiX A
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37. Hubbard Enterprises, San Diego County, Department of Health Services. Minimizing Waste from an Electroplating Operation, Pollution Prevention, A Resource Book for Industry. San Diego, CA. 1990. (PIES #005-079-A-000) 38. Jerome Kohl, et. al., North Carolina State University, School of Engineering. Reducing Hazardous Waste Generation with Examples from the Electroplating Industry. Raleigh, NC. 1986. 39. Off ice of Safe Waste Management, Massachusetts Department of Environmental Management. Source Reduction Recommendations for Precious Metal Platers. Boston, MA. April 1988. (PIES #002-012)
ELECTROPLATING--CHROMIUM
40. D. Achman, Minnesota Technical Assistance Program. Reducing Chromium Losses from a Chromium Plating Bath, Minnesota Technical Assistance Program Summer Intern Report. Summer 1987. (PIES #709-030) 41. United Nations Economic and Social Counsel. Use of an Evaporator in Chromium Electroplating, Compendium on Low- and Non-Waste Technology. Monograph ENV/ Wp.2/5/Add.47. Geneva, Switzerland. 1988. (PIES #400-125)
ELECTROPLATING--CYANIDE-CONTAINING WASTES
42. L. E. Vaaler, Off ice of Safe Waste Management. Prospects for Developing Substitutes for Cyanide-Containing Electroplating Baths, Third Annual Massachusetts Hazardous Waste Source Reduction Conference Proceedings. Boston, MA. October 23, 1986. (PIES #022-012) 43. U.S. EPA Research and Development, Risk Reduction Engineering Laboratory. Waste Minimization Audit Report: Case Studies of Minimization of Cyanide Waste from Electroplating Operations, Project Summary. Cincinnati, OH. January 1988. (PIES #101-023-B)
ELECTROPLATING--NICKEL
44. Minnesota Technical Assistance Program. Metal Recovery: Metal Finishing Shop. Minneapolis, MN. September 1988. (PIES #709-017) 45. P. Pajunen, Eco-Tech Ltd., and E. Schneider, Hewlett Packard, American Electroplaters and Surface Finishing Society and U.S. EPA. Copper and Nickel Removal in Printed Circuit Board Processing by Ion Exchange and Electroforming, Ninth AESF/EPA Conference on Environmental Control for the Metal Finishing Industry. January 25-29,1988. 46. T. Nadeau, et. al. Copper, Nickel and Chrome Recovery in a Jobshop to Eliminate Waste Treatment and Sludge Disposal, Third Annual Massachusetts Hazardous Waste Source Reduction Conference Proceedings, Office of Safe Waste Management. Boston, MA. October 23, 1986. (PIES #022-012) 47. Minnesota Technical Assistance Program. MetalRecovery: /on Exchange. Minneapolis, MN. September 1988. (PIES #709-019) 48. T. V. Tran, et al. Recovery of Nickel Salts by Electrodialysis Reversal Process, Presented at 73rd Annual AESF Technical Conference and Exhibit of Surface Finishing. The American Electroplaters and Surface Finishers Society Bulletin: TP 334ST. June 23, 1986. (PIES #222-001-A-001)
ELECTROPLATING CADMIUM
49. North Carolina Pollution Prevention Program. Potential Recovery and Reuse of Cadmium from an Electroplating Bath. Pollution Prevention Challenge Grant Program. Raleigh, NC. December 1987. (Pi ES #034-050-A-000)
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50. Hazardous Waste Reduction Program, Oregon Department of Environmental Quality. Guidelines for Waste Reduction and Recycling: Metal Finishing, Electroplating. Printed Circuit Board Manufacturing. Eugene, OR. July 1989. (PI ES #038-010) 51. Tom Nadeau, et. al. Copper, Nickel and Chrome Recovery in a Jobshop to Eliminate Waste 52. Treatment and Sludge Disposal, Third Annual Massachusetts Hazardous Waste Source Reduction Conference Proceedings, Office of Safe Waste Management. Boston, MA. October 23, 1986. (PIES #022-012)
CONTINUOUS HARDENING
53. United Nations, Economic and Social Council, Economic Commission for Europe. Compendium on Low- and Non-Waste Technology: Continuous Hardening and ZincCoating. Geneva, Switzerland, 1981. (PIES #400-103)
ZINC COATING
54. United Nations, Economic and Social Council, Economic Commission for Europe Compendium on Low- and Non-Waste Technology: Continuous Hardening and ZincCoating. Geneva, Switzerland, 1981. (PIES #400-103)
55. Institute for Local Self-Reliance. Engine and Plumbing Parts Manufacture, Case Study 60, Proven Profits from Pollution Prevention: Case Studies in Resource Conservation and Waste Reduction; Volume II. Washington, DC. 1989. (PIES #306001 -A)
56. Minnesota Technical Assistance Program, University of Minnesota. Metal Recovery: Etchant Substitution. Minneapolis, MN. 1989. (PIES #709-014-A-000) 57. A. Boyce, Tekronix, Inc. and D. J. Kavanaugh, CH2M Hill Industrial Design Corporation. Electrolytic Regeneration of Chromic/Sulfuric Acid Etchant, Ninth AESF/ EPA Conference Environmental Control for the Metal Finishing Industry. American Electroplaters and Surface Finishing Society and U.S. EPA, Washington, DC. January 25-29, 1988. 58. V. R. Sellers. Waste Management Alternatives for Electroplating and Printed Circuit Board Manufacturing Operations, Third Annual Massachusetts Hazardous Waste Source Reduction Conference Proceedings, Office of Safe Waste Management. Boston, MA. October 23, 1986. (PIES #022-012) 59. Thaddeus Smietana. Trichloroethylene Elimination Case Study: Electric Furnace #2 Bright Anneal Line Industrial Metals Department of Texas Instruments, Inc., Third Annual Massachusetts Hazardous Waste Source Reduction Conference Proceedings, Off ice of Safe Waste Management. Boston, MA. October 23, 1986. (PIES #022-012)
CHROME CONVERSION
60. New Jersey Hazardous Waste Facilities Siting Commission, Hazardous Waste Source Reduction and Recycling Task Force. A Study of Hazardous Waste Source Reduction and Recycling in Four Industry Groups in New Jersey, Case Study D6.1, p.33. Newark, NJ. April 1987. (PIES #031-001 -A)
APPENDIX A
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PAINTING
61. K. Weigel. Developments in Powder Coating Technology, Metal Finishing. April 1989, pp. 41-44. 62. D. S. Tyler, Volstatic, Inc. Electrostatic Powder Coating: Finishing for the Future, Metal Finishing, January 1985, pp. 23-26. 63. Hans Sutter, Umweltbundesamt. Low-Waste Technologies in the Federal Republic of Germany, The Environmental Professional, Volume II, pp. 190-198. Berlin, Germany. 1989. (PIES #458-006-A-001) 64. North Carolina Department of Environment, Health, and Natural Resources: Pollution Prevention Program. Managing and Recycling Solvents in the Furniture Industry. May 1986. (PIES #034-018-A) 65. Hazardous Waste Reduction Program of the Oregon Department of Environmental Quality. The Tektonix Payoff. Salem, OR. June 1988. (PIES #038-003-A-000) 66. Mark Manzione, Brown and Caldwell Consulting Engineers. Waste Minimization for Electroplating and Aircraft Paint-Stripping Wastewater Treatment, Process Technology 88: The Key to Hazardous Waste Minimization, Air Force Logistics Command. Sacramento, CA. August 15-18, 1988. (PIES #100-100-D) 67. Hackney, Pollution Prevention Challenge Grant Program, North Carolina Department of Natural Resources. Pilot Study of Solvent Recovery for Use in Paint Equipment Cleanup. Raleigh, NC. December 1986. (PIES #034-050-A-000) 68. California Department of Health Services, Alternative Technology Section, Toxic Substances Control Division. Waste Audit Study. Automotive Paint Shops. Sacramento, CA. January 1987. (PIES #005-005) 69. United States Environmental Protection Agency, Hazardous Waste Engineering Research Laboratory, Office of Research and Development Waste Minimization. Audit Report: Case Studies of Minimization of Solvent Waste from Parts Cleaning and from Nectronic Capacitor Manufacturing Operations. Cincinnati, OH. November 1987. (PIES #101-008-A).

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POLLUTION PREVENTlON

Waste Minimization for the Metal Finishing Industry

The Goals and Benefits of Pollution Prevention

Waste Minimization in the Metal Finishing Industry

Attachment A Information on Accessing Pollution Prevention Information Clearinghouses

Referencing Additional Information

SECTION 1: THE GOALS AND BENEFITS OF POLLUTION PREVENTION

BENEFITS OF A POLLUTION PREVENTION PROGRAM

WASTE MINIMlZATlON IN THE METAL FINISHING INDUSTRY

PROTECTING HUMAN HEALTH AND ENVIRONMENTAL QUALITY

REDUCING OPERATING COSTS

IMPROVING EMPLOYEE MORALE AND PARTICIPATION

ENHANCING THE COMPANYS IMAGE IN THE COMMUNITY

REDUCING THE POTENTIAL FOR PENALTIES AND FINES

WHAT IS POLLUTION PREVENTION?

WASTE MlNMlZATlON IN THE METAL FINISHING INDUSTRY

The following are examples of improved operating practices:

WASTE MlNlMlZATION IN THE METAL FINISHING INDUSTRY

WASTE MINIMIZATION THE METAL FINISHING INDUSTRY

WASTE MINIMIZATION ASSESSMENT PROCEDURES MODULE III

JON W. KINDSCHY, M.B.A., CHWS

DAVID RINGWALD, B.S. MOLLY CARPENTER, M.A.T.

DESCRIPTION OF METAL FINISHING

CHAPTER 2. WASTE MINIMIZATION OPTIONS FOR THE METAL FINISHING INDUSTRY

Recycling and Resource Recovery in Cleaning and Stripping.. .................. 25 25 25

WASTE MlNlMIZATlON IN THE METAL FINISHING INDUSTRY

INTRODUCTION AND PURPOSE

Reduce Reduce Toxicity

INTRODUCTION AND PURPOSE

WASTE MlNlMlZATlON IN THE METAL FINISHING INDUSTRY

DESCRIPTION OF METAL FINISHING SYSTEMS

Large and small shops contribute to waste streams

METAL CLEANING AND STRIPPING

DESCRIPTION OF METAL FINISHING SYSTEMS

The cleaning process selected depends upon the form of contamination

ORGANIC SOLVENT CLEANING

Metal cleaning methods

DESCRIPTION OF METAL FINISHING SYSTEMS

ABRASIVE AND THERMAL METHODS

1,1,1Trichloroethane methanol, & acetone

Vapor degreasing, immersion, wiping

High material costs; worker exposures & flammability

High COD & TDS in wastewater; creates metal sludges

Grit, sand, ceramic and plastic media;

Grinding, tumbling, blast cabinets;

High capital costs, APC equipment required

High energy costs, APC equipment required

SURFACE TREATMENT AND PLATING

Modifying the metals surface

Table 2 - PRIMARY SURFACE TREATMENTS

DESCRIPTION OF METAL FINISHING SYSTEMS

WASTE MINIMIZATION IN THE METAL FINISHING INDUSTRY

IIIIIIIIlIlIIIlIllIIIIIIII PRINTED CIRCUIT BOARD MANUFACTURING

Catalysts Electroless copper bath

DESCRIPTION OF METAL FINISHING SYSTEMS

WASTE MINIMIZATION OPTIONS FOR THE METAL FINISHING INDUSTRY

PREVENTING THE NEED FOR CLEANING

Substitute non-hazardous coatings

SOLVENT SOURCE REDUCTION

Substitute alkaline cleaners

Extending the useful life of the cleaning solution bath

ABRASIVES SOURCE REDUCTION

Using greaseless buffing compounds

SOURCE REDUCTION IN SURFACE PLATING AND RELATED PROCESSES