UCRL-JC- 12480 1

c o / u f - q b o ' I ~ ~ o - - s

LLNL Metal Finishing and Pollution Prevention Activities with Small

Businesses

J. W. Dini C. P. Steffani

This paper was prepared for submittal to the 4th International Congress on Environmentally Conscious Design and Manufacturing

Cleveland, OH July 23-25, 1996

July 1996

'r DISCLAIMER

This document was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor the University of California nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or the University of California. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or the University of California, and shall not be used for advertising or product endorsement purposes.

DISCLAIMER

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LLNL Metal Finishing And Pollution Prevention Activities With Small Businesses

J. W. Dini C. P. Steffani

For: ECDM96 4th International Congress & Exhibition on Environmentally Conscious Design and Manufacturing Cleveland, Ohio July 1996

Abstract

Lawrence Livermore National Laboratory (LLNL) has been actively involved in collaborative pollution prevention programs with small metal finishing firms. This paper summarizes efforts to date on a variety of programs. Joint efforts with NCAMF (Northern California Association of Metal Finishers), Technic, Inc., EPA and UC Davis, all directed at pollution prevention will be reviewed.

Introduction

The Metal Finishing Facility of LLNL’s Mechanical Engineering Department has been very active for many years in embracing environmentally conscious manufacturing principles. Working in stages, the facility has adopted scores of improvements that included recycling strong acids, substituting Earth-friendlier materials, and eliminating cyanide in its operations. The advances have been made as part of a larger, LLNL-wide effort to encourage pollution prevention and waste minimization activities.

The operation’s environmental efforts have been so successful that the facility has decreased its discharge of water to the Livermore sewer system from 1 1.4 million liters (3 million gallons) to zero. And, whereas in 1991, the facility was producing 227,100 liters (60,000 gallons) of chemical waste to be trucked off site, it now produces only 3,785 liters (1,000 gallons) of this waste annually.

As a result of these accomplishments, facility personnel are sharing lessons learned with both Department of Energy and private firms on how to respond to tightened environmental regulations and waste disposal costs by minimizing wastes and substituting better procedures. Numerous presentations and publications have been presented on these efforts (1 - 16). In recent time, heavy emphasis has been placed on helping small firms and this is the subject of this paper. Also included will be results from others at LLNL who have also been actively involved in metal finishing waste minimization.

Pollution Prevention Initiatives

To set the stage for discussing the activities that have been directed at helping small firms, a review of pollution prevention activities at LLNL is appropriate. All but a few of the activities we’ve undertaken to date could be duplicated by small businesses at minimal expense. In most cases, where capital equipment is needed, we’ve deliberately kept this cost to less than 15K which we judge to be an affordable amount for small businesses. Table 1 provides a listing of pollution prevention initiatives that have been completed. They range from simple “picking the low hanging fruit” activities to new developments such as replacing cyanide silver with a non- cyanide formulation or hexavalent chromium with Ni-W-B alloy. Most of the activities can be accomplished at low cost (less than 15K).

Other efforts at LLNL have been directed at a variety of sensor technology initiatives. Glass et al. (17,lS) have developed a multi-ion detector system using micro-electrode sensor arrays that can detect copper, cadmium, lead, and cyanide ions in the ppm range. The system is capable of monitoring up to eight elements in a hand carryable system. It is an extremely versatile user- friendly analytical device suitable for process control, effluent monitoring, and on-site environmental analysis. Milanovich et al. (19) have developed a fiber optic chemical sensor system for environmental monitoring of trichlorethylene and chloroform with a sensitivity of 5 ppb. This unit recently became commercially available via a small business firm. Meltzer (20, 21) has a sensor for monitoring contamination levels on parts during cleaning operations which provides use l l feedback for reducing waste generation and air emissions due to over or under cleaning.

Substituting New Technologies

One of the our important materials substitutions was that of nickel-tungsten-boron for hexavalent chromium coating. The ternary alloy containing 59.5% Ni, 39.5% W, and 1% B has worked as a viable substitute for hexavalent chromium electrodeposition. It has excellent wear, corrosion resistance, and mechanical properties while posing much less of an environmental risk and reducing energy costs (6). U.C. Davis researchers are actively engaged in evaluating this coating and we continue to work with them.

Much of the effort to adopt more environmentally friendly procedures and materials has centered on cyanide. Over the past several years, we have found substitutes for almost every process involving cyanide. For example, zinc-nickel has been substituted for cadmium cyanide plating and copper pyrophosphate has replaced copper cyanide. In the Spring of 1995, LLNL entered into a $2 million Cooperative Research and Development Agreement (CRADA) with Technic Inc. of Providence, Rhode Island and Eaton of Milwaukee, Wisconsin with the goal of providing industry with an environmentally benign alternative to the silver cyanide plating process for depositing thicknesses greater than 250 pm. This has been a highly successful endeavor. Thickness, stress, and hardness data coupled with metallographic and x-ray analysis have revealed that for the first time the electroplating industry can confidently plate thick silver from a formulation containing no cyanide (2).

Helping Small Finns

A successful project sponsored by the Small Business Initiative Program at LLNL is a collaboration with the Northern California Association of Metal Finishers (NCAMF). This partnership established a Model Metal Finishing Facility at LLNL’s Electroplating Facility to assist regional businesses in acquiring and implementing chemical processing technology and providing waste minimization consultation. This program had three phases: introductory, telephone access/facility tours, and hands-on. Phase 1 consisted of meetings with the NCAMF Board of Directors to develop projects of interest to their membership. Topics chosen as a result of these meetings became the phase three activities and will be discussed later. Phase 2 was a dedicated telephone access line that was staffed 10 hourdday. Questions received ranged from process substitution to training availability. Many of these calls resulted in immediate problem solving or provided a resource for further investigation. Some of the calls resulted in requests for a tour or for some prototype processing. The Phase 3 projects included :

- acid recycling via difision dialysis - electroless nickel recycling via electrodialysis - alkaline cleaner recycling via microfiltration

A key goal with these projects was to prove that recycling could be successfully accomplished with commercial equipment that could be purchased for $10,000-$15,000; a price range that is perhaps affordable for the small job shop plater. All of these projects were successful and are described in detail in references 4-7.

An outgrowth of this project is a new effort directed at ion exchange source capture and return. Dedicated systems on rinse tanks in a number of installations are under evaluation.

Summary

The Metal Finishing Facility at LLNL has placed heavy emphasis on utilizing environmentally conscious manufacturing principles. Key focus items have included minimizing hazardous wastes, minimization of water usage, material and process substitutions, and recycling technology, In recent years, efforts have been directed at helping small businesses improve their pollution prevention operations. Programs such as collaborative efforts with NCAMF, EPA, and U.C. Davis are examples that are covered in this paper.

This work was performed under the auspices of the U. S. Department of Energy by Lawrence Livennore National Laboratory under contract No. W-7405-Eng-48.

Table 1: Pollution Prevention Initiatives at LLNL*

Miscellaneous

Changing rinsing practices Inventory controVproduct return Reducing temperature of solutions during off-hours Reducing solution volume Precious metal recovery Rejuvenating gold plating solutions Energy conservation Combining physical vapor deposition and electroplating* * Ion exchange* * *

Substitution

Ni- W-B for hexavalent chromium Aqueous cleaning for solvent vapor degreasing Oxalic acid for sulfuric acid anodizing of aluminum Copper pyrophosphate for copper cyanide Non-cyanide silver for silver cyanide Ferric sulfate for HNO3/HF cleaning of aluminum Non-cyanide conversion coatings for cyanide containing coatings

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Recycling

Rinse water* * * * Acids Alkaline cleaners Electroless nickel

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Footnotes:

* Unless the activity is footnoted, it is a low-cost easily accomplished initiative.

* * Physical vapor deposition is an expensive process but provides a number of benefits not obtained fiom electroplating by itself. For more details on combining the two technologies see references 8,22-26.

** * Capital equipment for ion exchange can be expensive although we are presently evaluating individual tank units that are relatively inexpensive.

**** The unit we use for recycling cost $70K to purchase.

References:

1. J. W. Dini & C. P. Steffani, “Plating Shop Moves to Finish Off Waste,” Science & Technology News, May 1996

2. J. W. Dini, R. J. -Morrissey and D. R. Pacheco, “Non-Cyanide Silver Plating,” Proceedings 1 7th AESFRPA Pollution Prevention & Control Conference, Orlando, F1,269 (1 996)

3. B. R. Allenby, M. A. Gonzalez and E. Raber, “Implementing Industrial Ecology and Design for Environment Practices: Lawrence Livermore National Laboratory, Total Quality Environmental Management,” 5 (3), 37 (Spring 1996)

4. C. P. Steffani, “Waste Minimization: A Collaboration Between Lawrence Livermore National Laboratory and the Northern California Association of Metal Finishers,” Plating & Surface Finishing, 83,38 (January 1996)

5. C. P. Steffani and M. Meltzer, “Alkaline Detergent Recycling Via Ultrafiltration,” Lawrence Livermore National Laboratory, UCRL-ID- 12 1 1 3 8 (June 1995)

6 . C. P. Steffani and M. Meltzer, “Electrodeposited Nickel-Tungsten-Boron: A Replacement for Hexavalent Chromium,” Lawrence Livermore National Laboratory, UCRL-ID- 1206 1 1 (May 1995)

7. C. P. Steffani and M. Meltzer, “Electroless Nickel Recycling Via Electrodialysis,” Lawrence Livermore National Laboratory, UCIU-ID- 1206 12 (May 1995)

8. C . P. Steffani and J. W. Dini, “Environmentally Conscious Electroplating at Lawrence Livennore National Laboratory,” International Journal of Environmentally Conscious Design & Manufacturing 3 (2), 43 (1994)

9. J. W. Dini, “Aqueous Cleaning Can Provide Better Results Than Vapor Degreasing,” International Journal of Environmentally Conscious Design and Manufacturing, 2 (2), 33 (1 993)

10. J. W. Dini and C. P. Steffani, “Environmentally Conscious Operations in an Electroplating Facility,” Riotech Proceedings, ECM 93 Workshop, April 1993

11. J. W. Dini and C. P. Steffani, “Reducing Wastewater in Metal Finishing at Lawrence Livennore National Laboratory,” Pollution Prevention Advisor, 3, (30, 1 (Summer 1993)

12. J. W. Dini and C. P. Steffani, “Electroplating Waste Minimization at Lawrence Livermore National Laboratory,” Spectrum 92 Proceedings, International Topical Meeting, Nuclear and Hazardous Waste Management, 142 (August 1992)

13. J, W. Dini and C. P. Steffani, “Pollution Prevention Performers: Livermore’s Plating Shop,” Pollution Prevention Advisor, 2 (3),6 (Summer 1992)

14. J. W. Dini and C. P. Steffani, “Plating Waste Minimization at LLNL,” Proceedings U. S. Dept. of Energy Office of Environmental Restoration and Waste Management Waste Reduction Conference, Albq, NM, D5 1 (1 992)

15. J. W. Dini, “Waste Minimization Activities in the Materials Fabrication Division at LLNL,” RESIDUES AND EFFLUENTS: PROCESSING AND ENVIRONMENTAL CONSIDERATIONS, R. G. Reddy, W. P. Imrie and R. B. Queneau, Editors, TMS, 667 (1992)

16. J. W. Dini and C. P. Steffani, “Waste Minimization in a Non-Production Oriented Metal Finishing Facility,” Proceedings 13 th AESFEPA Conference on Environmental Control for the Surface Finishing Industry, Orlando, F1,43 (January 1992)

17. R. S. Glass et. al., “Electrochemical Array Sensors for Plating Waste Stream Monitoring,” UCRL-JC.108819 (Mach 1992)

18. R. S. Glass, G. B. Balas. D. R. Ciarlo and D. L. Hargrove, “Multielement Microelectrode Array Sensors and Compact Instrumentation Development at Lawrence Livermore National Laboratory,” UCRL-JC-117619 (August 1994)

19. F. P. Milanovich, S. B. Brown, B. W. Colston, Jr., P. F. Daley and K. C. Langry, “A Fiber- Optic Sensor System for Monitoring Chlorinated Hydrocarbon Pollutants,” Talanta, 4 1, 2189 (1994)

20. M. Meltzer, “Real-Time Cleaning Performance Feedback,” UCRL-JC- 1 191 35 (December 1995)

21. M. Meltzer and H. Gregg, “In-Process Cleaning Analysis,” UCRL-JC- 122883 (January 1996)

22. J. W. Dini, “Synergism of Electroplating and Vacuum Processes,” Proc. 1st International SAMPE Metals and Metals Processing Conf., Cherry Hill, NJ, 91 (1987)

23. J. W. Dini, “Benefits From Combining Electroplating and Physical Vapor Deposition Technologies,” Surface Modification Technologies 111, T. S. Sudarshan and D. G. Bhat, Editors, The Minerals, Metals and Materials SOC., 171 (1989)

24. T. G. Beat, W. K. Kelley and J. W. Dini, “Plating on Molybdenum,” Plating & Surface Finishing, 75,71 (Feb. 1988)

25. J. W. Dini, “Providing Adherent Coatings on Tungsten and Tungsten Alloys,” Proc. International Conference on Tungsten and Tungsten Alloys, Crystal City, Virginia (Nov. 1992)

26. J. H. Lindsay and J. LaSala, “Vacuum Preplate Process for Plating on Acrylonitrile- Butadiene-Styrene (ABS),” Plating & Surface Finishing, 72,54 (July 1985)