Alternatives to Chromium for Metal Finishing

NCMS"

National Center for Manufacturing Sciences

Alternatives to Chromium for Metal Finishing

October 1995

Alternatives to Chromium for Metal Finishing

Final Report NCMS Report 0273RE95

Prepared under: NCMS Project No. 02-17-0403

October 1995

National Center for Manufacturing Sciences 3025 Boardwalk

Ann Arbor, Michigan 48108-3266

01995 National Center for Manufacturing Sciences, Inc

This document contains information which is proprietary to the NCMS. It is protected under both the U S . Copyright Act and applicable state trade secret laws and may not be used or disseminated without the express written permission of the NCMS. (NCMS members may use and disseminate in accordance with their membership contracts with the NCMS, and the NCMS Bylaws and Policies and Procedures.)

Neither the NCMS, members of NCMS, nor any person acting on behalf of them:

makes any warranty or representation, express or implied, with respect to the accuracy, completeness or usefulness of the information contained in this report, or that the use of any information, apparatus, method, or process disclosed in this report may not infringe privately-owned rights, or

apparatus, method, or process disclosed in this report. assumes any liability with respect to the use of, or from damages resulting from the use of, any information,

Effort sponsored by the Manufacturing Technology Directorate, Wright Laboratory (WUILITX), Air Force Materiel Command, WAF, under Cooperative Agreement Number F3361.5-94-2-4423. The US. Government is authorized to reproduce and distribute reprints for Governmental purposes notwithstanding any copyight notation hereon.

The views and conclusions contained herein are those of the authors and should not be interpreted as necessarily repre- senting the ofticial policies or endorsements, either expressed or implied, of Wright Laboratory or the U.S. Government.


Abstract

Many current users of chromate conversion coatings are seeking chromium-free alternatives, and coating suppliers are actively developing replacements. Participants in a collaborative research project sponsored by the National Center for Manufacturing Sciences obtained samples of 29 chromium-free coatings from 12 suppliers on test panels of 5

aluminum alloys. The test panels, together with control samples of standard chromate formulations, were evaluated for corrosion resistance, contact electrical resistance, and paint adhesion. This report presents the results of the testing, together with an environmental impact assessment of the alternatives as compared with chromate coatings now in use.

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Table of Contents Section Page

... Abstract ......................................................................................................................................... 111

List of Figures .............................................................................................................................. VII

List of Tables ................................................................................................................................ ix

Acknowledgments ......................................................................................................................... xi

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1 . Introduction and Summary ................................................................................................... 1-1 1.1 The Need for Alternatives to Chromium ........................................................................... 1-1 1.2 Project Background and Goal ............................................................................................ 1-2 1.3 Experimental Protocol ....................................................................................................... 1-3

1.3.1 Alloy and Coating Selection ................................................................................... 1-3 1.3.2 Test Panel Preparation ............................................................................................ 1-6

1.4 Test Protocols and Standards ............................................................................................. 1-6 1.4.1 Testing by NCMS Participants ............................................................................... 1-7 1.4.2 Additional Testing .................................................................................................. 1-7 1.4.3 Applicable Standards .............................................................................................. 1-7

1.4.3.1 Corrosion Resistance Attributes ................................................................ 1-8 1.4.3.2 Contact Electrical Resistance Attributes .................................................... 1-9 1.4.3.3 Paint Adhesion Attributes ........................................................................ 1-10

1.5 Test Results Summary ..................................................................................................... 1-10 1.5.1 Corrosion Resistance Test Results ....................................................................... 1-10 1.5.2 Contact Electrical Resistance Test Results ........................................................... 1-11 1.5.3 Paint Adhesion Test Results ................................................................................. 1-11

1.6 General Observations ....................................................................................................... 1-11

.............................................................................. 2 . Corrosion (Salt Spray) Resistance Tests 2-1 2.1 Test Conditions and Procedure .......................................................................................... 2-1 2.2 Observations and Discussion ............................................................................................. 2-5

3-1 3.1 Test Procedure ................................................................................................................... 3-1 3.2 Observations and Discussion ............................................................................................. 3-2

4 . Paint Adhesion Tests .............................................................................................................. 4-1 4.1 Test Procedure ................................................................................................................... 4-2 4.2 Observations and Discussion ............................................................................................. 4-3

...................................................................................... 3 . Contact Electrical Resistance Tests

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5 . Environmental Impact Assessment ...................................................................................... 5-1 5.1 Background of the Methodology ........................................................................................ 5-2 5.2 Phase 1: Environmental Performance Criteria ................................................................... 5-2

5.2.1 Number of Process Steps ........................................................................................ 5-2 5.2.2 Ozone Depleting Substances .................................................................................. 5-3 -~ ~

5.2.3 Hazardous Air Pollutants ........................................................................................ 5-3 5.2.4 Carcinogens ~~~ ............................................................................................................ 5-3 5.2.5 Regulated and Hazardous Chemicals ..................................................................... 5-3 ~

5.2.6 Resource Usage ...................................................................................................... 5-4

5.2.6.2 Water Usage ............................................................................................... 5-4

5.2.7 Solid Waste Generation .......................................................................................... 5-4 5.2.8 Potential for Airbome Contaminants ........................................................................ 5-5 5.2.9 Wastewater Generation ........................................................................................... 5-5 5.2.10 Worker Health and Safety ....................................................................................... 5-5

5.3 Phase 2 . Environmental Data Compilation and Data Sheet Completion ........................... 5-5 5.4 Phase 3 . Environmental Performance Assessment ............................................................ 5-6

5.4.1 Primary Selection Matrix ........................................................................................ 5-6 5.4.2 Secondary Selection Matrices ................................................................................. 5-7 5.4.3 Decision Matrix ..................................................................................................... 5-7

5.5 Environmental Impact Assessment Data Sheets ................................................................ 5-8

6 . References ............................................................................................................................... 6-1

5.2.6.1 Process Chemical Usage ............................................................................ 5-4

5.2.6.3 Energy Consumption ................................................................................. 5-4

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National Center lor Manufacturing Sciences

List of Figures Figure Page

1-1 Alloy 356 Corrosion (Salt Spray) Resistance Test Results Summary ............................... 1-13

1-2 Alloy 2024 Corrosion (Salt Spray) Resistance Test Results Summary ............................. 1-14




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1-7

1-8

1-9

1-10 Alloy 7075 Contact Electrical Resistance Test Results Summary .................................... 1-22

1-11 Alloy 356 Paint Adhesion Test Results Summary ............................................................ 1-23

1-12 Alloy 2024 Paint Adhesion Test Results Summary .......................................................... 1-24




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2-2

Alloy 356 Contact Electrical Resistance Test Results Summary ...................................... 1-18

Alloy 2024 Contact Electrical Resistance Test Results Summary .................................... 1-19



Panel Positions in L e m o n Avenue Salt Spray Test Chamber 1 ....................................... 2-3

Panel Positions in Lemmon Avenue Salt Spray Test Chamber 2 ....................................... 2-4

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List of Tables

Table

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1-5

1-6

2- 1

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5-10

5-1 1

Page

Alloy Composition by Weight Percent ............................................................................. 1-4

Coating Suppliers and Supplied Coatings ........................................................................ 1-5

Coating Suppliers Key Contacts ....................................................................................... 1-6

Test Standards .................................................................................................................. 1-7

Summary of MIL-C-81706 Performance Requirements .................................................. 1-9

Summary of MIL-C-5541E Process Control Performance Requirements ....................... 1-9

Corrosion (Salt Spray) Resistance Test Results ............................................................... 2-6

Contact Electrical Resistance Pre Salt Spray Test Results ............................................... 3-3

Contact Electrical Resistance Post Salt Spray Test Results ............................................. 3-7

Paint Adhesion Rating System, Based on ASTM D-3359, With Modifications ............. 4-2

Paint Adhesion Test Results ............................................................................................. 4-4

Environmental Performance Criteria and Related Sources of Regulation ....................... 5-3

Sources of Regulation Used to Reference Regulated and Hazardous Chemicals ............ 5-4

Primary Selection Matrix ................................................................................................. 5-8

Secondary Selection Matrix -Basic ................................................................................ 5-9

Secondary Selection Matrix - Numerical Valuation ...................................................... 5-10

Secondary Selection Matrix - Relative Valuation ......................................................... 5-11

Environmental Impact Decision Matrix ......................................................................... 5-12

Permatreat 611 Environmental Impact Data Sheet ........................................................ 5-15

Chemcote L497260A Environmental Impact Data Sheet .............................................. 5-17

E-CLPS 923 Environmental Impact Data Sheet ............................................................ 5-21

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E-CLPS 923X Environmental Impact Data Sheet .......................................................... 5-23

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National Center for Manufacturing Sdences

List of Tables (continued)

Table

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Alcoat 1470 Environmental Impact Data Sheet ............................................................. 5-25

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Alcoat 1500 Environmental Impact Data Sheet ...





GM 1 Environmental Impact Data Sheet ....................................................................... 5-39

GM 2 Environmental Impact Data Sheet ....................................................................... 5-41

Alodine 1200s Environmental Impact Data Sheet ......................................................... 5-45

Alodine 2000 Environmental Impact Data Sheet ........................................................... 5-49

Patclin 1910 A, B, C Environmental Impact Data Sheet ............................................... 5-53

Patclin 191 1B Environmental Impact Data Sheet .......................................................... 5-57

Sandia 1 and Sandia 2 Environmental Impact Data Sheet ............................................. 5-61

Alumicoat 6788 Environmental Impact Data Sheet ....................................................... 5-65

2438-28D Environmental Impact Data Sheet ................................................................ 5-67

Ce-Mo 2024 Environmental Impact Data Sheet ............................................................ 5-69



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National Center for Manulacturing Sciences

Acknowledclments This project would not have been possible without the enthusiasm and expertise of a number of individuals, and the support of their respective organizations. The core team included:

Concurrent Technologies Corporation Paul Brezovec

Eastman Kodak Mike Giglio Mitch Rakus

General Motors -Delphi Harrison Thermal Systems Bob Ahrens

Rensselaer Polytechnic Institute Mario Clarizia Nicholas Clesceri James DeMay Jacob Komgold James Specht

Sandia National Laboratories Rudy Buchheit

Texas Instruments Norm Carlson

United Technologies Research Corporation Mark Jaworowski

Many others also contributed their time, effort, and advice at various stages of the project. I would like to mention specifically Martin Kendig of Rockwell International (and his colleagues Eric Eichinger and Irene Drakos), and Michael Kane of the U.S. Army Materials Research Laboratory (with his former colleague Robert Huie), who are already extending the information base of this project beyond its original scope. Participants from NCMS member organizations who played key roles at crucial points include: Jerry Golden of United Technologies Research Corporation; Russell Hill of Texas Instruments; Rene Cooper, formerly with Rensselaer Poly- technic Institute; Paul Behrendsen of GM-Delphi Chassis; and Ravi Rungta of GM-Harrison. Thanks are also due Martha Swidersky of NCMS for bringing much needed insight and patience to the formidable task of eliciting clarity and order from a bewildering congeries of tables and text.

Paul D. Chalmer, Ph.D. Program Manager, Environmentally Conscious Manufacturing National Center for Manufacturing Sciences


1. Introduction and Summary This report documents work performed in conjunction with National Center for Manufactur- ing Sciences (NCMS) Project No. 17-0403, “Alternatives to Chromium for Metal Finish- ing.’’ The purpose of the project was to provide test data for a variety of chromium-free coating alternatives for conversion coating of aluminum. Samples of over 30 different coatings, including standard chromate controls, on five aluminum alloys were evaluated side-by- side on the following three widely used performance tests:

Salt spray corrosion resistance Contact electrical resistance Paint adhesion.

The resulting database, which project participants believe to be unique in its level of detail and in the degree of intercomparability made possible by the test protocols, is presented in this report.

Section 1 of the report is an overview of the study’s aims, methods, and results, to provide a broad perspective on the state of the art. An expanded description of each of the test protocols and a detailed compilation of all test results are in Sections 2, 3, and 4.

In addition to providing performance data, the project participants recognized the importance of including an environmental impact assessment of the alternative coating processes. This assessment can facilitate comparison with the chromium-containing coatings currently in use. The well-known difficulties associated with accounting for the full environmental impact of a particular choice of process or material preclude any definitive statement that one coating is environmentally superior to another under all circumstances. Nevertheless, participants felt that some guidance for readers who may be considering replacing their

present processes with any of the alternatives considered here would be useful.

Thus, Section 5 summarizes a framework for an environmental impact assessment, which was prepared by one of the project participants, Rensselaer Polytechnic Institute (RPI). This section presents the available information con- cerning the alternative coatings, and indicates how to generate an assessment based on these facts and on assumptions supplied by the reader. An example is presented of an assessment based on one possible set of assumptions. Readers are encouraged to supply an altema- tive set of assumptions to generate an assessment tailored to their own unique concerns.

1.1 The Need for Alternatives to Chromium

The search for alternatives to chromium for metal finishing processes has been stimulated by several interconnected developments. At the core of the problem is the demonstration of human health effects associated with exposure to hexavalent chromium. Because hexavalent chromium is considered a human carcinogen, concern exists not only about workplace exposure at high levels, but also about environmental exposure at much lower levels. [1]* This concern has produced a cascade of consequences, including:

Increased liability for claims of workplace and environmental exposure.

Increased costs for tracking inventories, monitoring emissions, reporting usage of chromium compounds, and disposal of solid wastes containing chromium.

More stringent disposal limits for discharges of dissolved chromium in wastewater.

* Numbers in brackets are references, listed in Section 6.

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These unavoidable facts multiply the problems and costs associated with the use of hexavalent chromium in metal finishing processes, and with disposal of chromium compounds of all types. One may argue that replacement coatings are not available for some applications, and that the risks (environmental and otherwise) of switching from a proven system to an unknown may, in many cases, outweigh the benefits. Whatever the technical merits of such a position may be, the fact remains that many current users of chromium for metal finishing applications are actively seeking ways to reduce or eliminate that use.

1.2 Project Background and Goal In January 1993, NCMS organized a workshop to explore possibilities for collaborative research projects in the general area of chromium alternatives. Such research, in which a group of independent, and possibly competi- tive organizations pool their efforts to develop precompetitive technology, has been found to be particularly well suited to the assessment and development of pollution prevention and source reduction technology. A project that assists in developing an understanding of the state of the art, and in identifying and focusing user needs, can benefit an entire industry. The commitment of time and resources necessary to provide a comprehensive overview for a particular pollution prevention issue might be difficult for any single company, acting alone, to justify, but might appear reasonable in the context of a collective effort.

With this understanding, a group of workshop participants decided to undertake a project with the goal of collecting data on the capahi- lities of a range of chromium-free alternative coatings for one specific process type: conversion coating of aluminum. The participants selected this process and substrate because of their specific interests, and because they knew that many development efforts to find

chromium-free replacement coatings for this process were already under way.

Participants also recognized that widespread interest would extend to many other process types in which chromium plays a key role (electroplating and anodizing, for example) as well as to coatings for many other substrates (such as steel, zinc, and magnesium). How- ever, the project team felt that conversion coating of aluminum would be a good place to start. A focused effort, if successful, could stimulate follow-on activities, which would cover other processes and materials.

Project participants included:

Concurrent Technologies Corporation (CTC) Delphi Chassis Division, General Motors (Delphi) Delphi Harrison Thermal Systems, General Motors (GM) Eastman Kodak (Kodak) National Center for Manufacturing

Rensselaer Polytechnic Institute (RPI) Sandia National Laboratories (Sandia) Texas Instruments (TI) United Technologies Research Corporation (UTRC).

Sciences (NCMS)

In addition to these organizations, Rockwell International and the U. S. Army Materials Laboratory participated in the project on an informal basis.

As is standard practice for NCMS collahora- tive research projects, each NCMS member organization that participated on this chrome project selected an individual to serve as its representative on the Project Steering Group. This group was responsible for all decisions involved in carrying out the project.

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At the outset of the project, the participants made several choices regarding the approach to be used in conducting the investigation into alternatives to chromium for metal finishing. These decisions were based on what the participants hoped to derive from the effort.

First, they decided to include both commercially available processes and processes still under development in the laboratory. The idea was to assess the state of the art, rather than to identify immediately available replacements.

Second, they decided to exclude processes that required large capital expenditures or acquisi- tion of completely new technologies, since these were felt to be too remote from the ideal of a drop-in replacement. Thus, technologies based on anodizing, ion beams, and other more “exotic” operations, were not included.

Finally, they re-evaluated the NCMS standard option of collaborative research projects keeping results proprietary up to 18 months after completion of a project before release to NCMS membership, and up to 30 months before release to the general public. Project participants decided to release all results to the public immediately upon completion of the project and of the report. They felt that the results would provide timely and important benefits to industry as a whole regarding cost and environmental issues related to the use of chrome and its altematives. Additionally, this information could stimulate further work on development of suitable alternatives to chromium and facilitate their acceptance.

1.3 Experimental Protocol In selecting the conditions under which samples of altematives to chromium would be obtained and tests conducted, participants attempted to treat each sample identically with the others, insofar as possible. Several choices were made with this criterion in mind

e Uncoated test panels for each alloy would be purchased from a single supplier to minimize variability of the base metal.

The coating suppliers would prepare the coatings and apply them to the test panels, even if the materials for producing the coatings were commercially available, to give each supplier a chance to provide optimal samples.

The handling and testing of panels and coatings would he conducted under “blind” conditions wherein: a) the panels would be engraved with code numbers before their distribution to the coating suppliers; and b) test personnel would not know the identity of the coating samples until after all tests had been completed and the data submitted.

As directed by the Project Steering Group, NCMS purchased the test panels. UTRC took responsibility for: receiving the blank test panels, marking them with code numbers, dis- tributing them to the coating suppliers, distri- buting the coated panels to the testing laboratories, and collecting and tabulating all test data.

Details of the procedures for obtaining samples and conducting the tests are given in the following subsections.

1.3.1 Alloy and Coating Selection

One of the first tasks was to decide which aluminum alloys would be used for the test panels. The specific interests of the participants largely determined the selections. How- ever, the participants also made sure that their selections covered a broad enough range of typical alloys that a general readership would find information relevant to a wide range of applications.

The project team ultimately selected five alloys:

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356 to represent cast alloys

2024-T3 to represent high-copper structural alloys, which are of primary interest for aerospace applications. They are considered to be among the most difficult of alloys for conversion coatings.

3003, a common stock used in manufacturing beverage cans, to represent the “easy” end of the spectrum. It has generally good corrosion resistance. Because a good deal of information on this alloy has already been generated, the project team selected this alloy as a useful baseline.

6061-T6 to represent an alloy of intermedi- ate coating difficulty. The 6000 series of aluminum is the most common alloy type used for extrusions. It is also used for structural applications.

7075-T6, also widely used in aerospace applications, to represent an alloy with somewhat of a coating challenge, but less than that of 2024.

The nominal compositions for these alloys, in weight percent, are given in Table 1-1.

Table 1-1. M o y Composition by Weight Percent

The next task was to identify potential coating suppliers. Participants generated an initial list based on their own knowledge of the industry. Announcements were also made at various meetings, conferences, and workshops to

involve as broad a spectrum of potential coating suppliers as possible. Potential suppliers were told of the goals of the study and its ground rules, which were relatively simple:

- Coatings were to be chromium-free. Coat- ings based on trivalent chromium were not eligible. -

Suppliers could reveal as little or as much as they cared to about the coating composition or process. The study would include no attempt to analyze the composition, other than to verify the absence of chromium, The project team wanted the study to be as inclu- sive as possible, and did not want proprietary issues to interfere with the availability of candidate coatings.

However, suppliers were told that an environmental impact assessment would be conducted. With more information available, the evaluators could assign a lower risk rating to the coating than would be given due to uncertainty. Also, the suppliers were reminded that readers would find process details useful in evaluating coatings as potential alternatives.

All information provided by the coating suppliers, and all test results, would be released to the public.

To provide a sufficient supply of panels for the range of tests to be conducted, 12 test panels of each alloy for each coating would be required. Coating suppliers could submit as many coatings as they wished, and could decline to provide samples on selected alloys. They could also designate certain coatings to be specifically intended for certain applications.

Ultimately, 12 coating suppliers provided 33 different coating types for evaluation, as identified in Table 1-2.

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Patclin Chemical Co., Inc. (Patclin)

Table 1-2. Coating Suppliers and Supplied Coatings

Alodine 2000D With 1000 deoxidizer.

191OA 19108 1910c 19118

Circle-Prosco)

Parker Amchem Chromium wnversion watings

Sanchem (Sanchem)

FP SD

Ell Atochem - Turco Products Division (Turco)

Sandia National Laboratories ISandia)

Alumiwat 6786 An organic, water-borne, non-chromated 'bash-primel' system that will pass 168- and 336.hr bare salt spray and 3000-hr paint adhesion salt spray. When painting, do not solvent wipe, paint as is.

2438-28D

Ce-Mo 7075

University 01 Southern Calilornia 1USCI

Of these 33 coatings, 29 were chrome free and 4 were standard chromate conversion coatings, which were included to provide a baseline control against which the non-chromium alternatives could be compared. The standard coatings were from the Alodine 600 and 1200s

series of chromate conversion coatings, supplied at both the low and high ends of the standard range of coating thickness.

Key contact information for the coating suppliers is presented in Table 1-3.

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Table -1-3. Coating Suppliers Key Contacts

Mitch Kasouff ~ Phone: 215-773-2822 Fax: 21 5-773-2800

I Company and Address I Key Contact

‘ David Enright Phone: 800-222-8819 Fax: 708-295-8748

Betz Laboratories, Inc. Beh Metchem Division 200A Precision Drive Horsham, PA 19044

Brent America, Inc. 921 Sherwood Drive Lake Bluff, IL 60044

Bulk Chemicals, inc. P.O. Box 186 Mohrsville, PA 19541

Circle-Prosco Inc. 2017 Yost Avenue Bloomington, Indiana 47403

Charles Ike Phone: 800-338-2855 Fax: 610-926-6125

Jack Manard Phone: 317-579-5353 Fax: 317-579-5354

General Motors Delphi Harrison Thermal Systems 200 Upper Mountain Road Lockport, NY 14094

Bob Ahrens Phone: 716-439-3750 Fax: 716-439-3168

Lord Corporation 405 Gregson Drive

Patclin Chemical Co., Inc. 66 Alexander Street Yonkers, NY 10701

Lynn Yanyo Phone: 919-469-3443 Fax: 91 9-460-9648

Ray Reinecke Phone: 914-476-7000 Fax: 91 4-476-0934

Parker Amchem 32100 Stephenson Highway Madison Heights, MI 48071

Jon Nylen Phone: 810-589-4893 Fax: 81 0-583-2976

Sanchem 1600 South Canal Street

Sandia National Laboratories MS 0340, P.O. Box 5800 Albuauerque, NM 87185

Jon Flicher Phone: 312-733-6100 Fax: 31 2-733-7432

Rudy Buchheit Phone: 505-844-6904 Fax: 505-844-1 543

Elf Atochem Turco Products Division 7320 Bolsa Avenue Westminster, CA 92684-3600

Frank Muller Phone: 714-890-3612 Fax: 714-892-7179

University of Southern California Dept. of Materials Science Los Angeies, CA 90089-0241

Fiorian Mansfeld Phone: 213-740-4428 Fax: 21 3-740-7797

1.3.2 Test Panel Preparation

NCMS ordered blank, uncoated panels from two test panel suppliers. One provided the 356 cast alloy panels, which measured 4 in. x 6 in. x 0.125 in. These panels were necessarily con-

casting a much thinner panel would have been impractical. Since not all coating suppliers chose to supply samples on the cast alloy, only 350 panels were needed.

The other panel supplier provided about 500 panels of each of the four sheet alloys. These panels were clean, with hanging holes, and were 0.025 in. thick. They measured 3 in. x 10 in. for the 2024,6061, and 7075 alloys, and 3 in. x 9 in. for the 3003 alloy.

The panel suppliers shipped the panels to UTRC for initial logging. UTRC stamped the panels with code numbers, which provided no indication of coating identity. Participants felt that “blind” testing would help minimize possible bias due to any preconceived notions on the part of test personnel, UTRC also inspected the panels and noted potentially significant features, such as water stains, before shipping the panels to the coating suppliers.

The coating suppliers prepared 12 panels of each alloy they received for each coating they were providing and returned the panels to UTRC. Upon receipt, UTRC re-inspected the coated panels, repackaged them, and shipped them to the test laboratories.

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siderably thicker than the sheet panels, since ~~

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1.4 Test Protocols and Standards Military Specification MIL-C-8 1706, “Chemi- cal Conversion Materials for Coating Alumi- num and Aluminum Alloys,” calls out three specific types of properties: corrosion resistance, contact electrical resistance, and paint adhesion. The Project Steering Group decided that the scope of the project would include testing in all of these areas.

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National Center lor Manulacturing Sciences

Corrosion (Salt Spray) Contact Electrical Resistance Paint Adhesion

Dly Wet

1.4.1 Testing by NCMS Participants

All testing was performed by project participants at their own facilities, using personnel experienced in carrying out the respective tests in conjunction with normal operations. TI performed the corrosion resistance testing, Sandia performed contact electrical resistance testing, and Kodak performed paint adhesion testing.

Of the 12 panels of each alloy that were coated:

5 were used for salt spray testing

1 was used for contact electrical resistance testing (and for electrochemical impedance spectroscopy (EIS) testing; see Subsection 1.4.2)

1 was used for paint adhesion testing

5 were archived, and may be used for additional study in subsequent projects.

Some exceptions were made to standard practice when participants felt that it would be more informative to do so. For example, in performing corrosion resistance testing, test samples are generally exposed to a corrosive medium for a specified number of hours, after which samples are rated as either pass or fail, depending on set criteria. For this study, the preferred procedure was to inspect the samples frequently, record their condition as it developed, and continue testing until the samples had clearly failed. This modification provided far more detail about the onset and rate of corrosion than would be available if the standard padfail criterion had been used.

Details on the specific protocols used for each of the test series are provided at the beginning of Sections 2 through 4.

1.4.2 Additional Testing

The electrochemical impedance spectroscopy tests have been proposed as a method of

ASTM 8117 [Z] Texas Instruments

MIL-C-5541 E [3] Sandia National Laboratories Eastman Kodak

ASTM D3359 [4]

Federal Test Method Standard 141, Method 6301 [6]

MIL-C-81706 [5];

indicating corrosion resistance more rapidly than is possible with the salt spray method. Rockwell International conducted EIS testing on a subset of the available samples to gauge how well the results of this method would correlate with the results of the salt spray testing.

The U.S. Army Materials Laboratory also carried out additional testing in conjunction with this study. Coating suppliers were given the opportunity to provide samples of their coatings on each of three armor alloys.

Information on the results of the EIS testing performed by Rockwell and on corrosion resistance and other testing performed by the U.S. Army Materials Laboratory will be available in separate publications. The staff of the Manufacturing Information Resource Center (MIRC) at NCMS (phone: 3 13-995-0300) can provide details on how to obtain this additional information.

1.4.3 Applicable Standards

One major objective of this report is to allow readers to determine which of the alternative coatings tested here may be suitable for their specific applications. To provide the most immediately usable data to a wide variety of readers, tests were generally performed according to commonly used ASTM, military, or federal specifications, as indicated in Table 1-4.

Table 7-4. Test Standards

Test I Designation I Participant

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Nalional Center lor Manuladuring Sciences

The military specifications provided the basis for selecting the tests performed for this study:

MIL-C-81706 “Chemical Conversion Materials for Coating Aluminum and Aluminum Alloys”

MIL-C-5541E “Chemical Conversion Coatings on Aluminum and Aluminum Alloys”.

The ASTM test methods were used to estab- lish test conditions and procedures, but they do not specify performance standards and are not discussed further in this section. Sections 2 through 4 include more detailed discussion of the methods.

The following discussion summarizes the intent of the two military specifications, which call out the test procedures and the performance standards. Readers may find this information helpful in determining how the test results relate to their own requirements.

The military specifications define performance levels, processing methods, and materials (chemicals) acceptable for military applications. They are also widely used, in whole or in part, in establishing requirements for many non- military applications. The main performance attributes defined in these specifications are: corrosion resistance, contact electrical resistance, and paint adhesion.

MIL-C-81706 defines two classes of coatings that are distinguished by the main coating performance attributes:

e Class 1A coatings are intended for maximum protection against corrosion in situations where the conversion coated surface is either painted or unpainted.

e Class 3 coatings are intended for use where corrosion protection and low contact electrical resistance are required.

In the case of chromate conversion coatings, the primary difference between Class 1A and Class 3 coatings is thickness: Class 3 coatings are typically thinner than the more corrosion- resistant Class 1A coatings. -

MIL-C-81706 also defines two performance ~~

levels for these coatings: ~

Higher performance is required for “qualification.” Coatings must meet qualification requirements to be placed on the MIL-C-81706 Qualified Products List.

Lower performance is acceptable for “quality conformance.” Quality conformance requirements are typically used for lot inspection and quality control.

Performance requirements for each combination of class and performance level, as specified for each of the three tests, are summarized in Table 1-5.

MIL-C-5541E defines performance criteria for process (quality) control and for lot acceptance. These performance requirements are summarized in Table 1-6.

1.4.3.1 Corrosion Resistance Attributes

To obtain a pass ranking according to MIL-C- 81706 for corrosion resistance, all panels (for 5 panels, a total of 150 in.*) “shall show no evidence of corrosion whatever when compared to unexposed panels with the naked eye except in those areas within 1/4 in. from the edges ...” when subjected to salt spray exposure testing.

The MIL-C-5541E performance requirements are less stringent than those in MIL-C-81706. To obtain a pass ranking per MIL-C-5541E, a single panel can have “no more than 5 isolated spots or pits, none larger than 0.031 in. in diameter ...” after salt spray exposure testing.

__

- L__

1-8 Use and dimmination 04 he InIoRMfim wntained in this document 818 subjen to m t W i m s on the mWnsht Page.


Corrosion Resistance

Table 1-5. Summary of MIL-C-81706 Performance Requirements

For Qualification No evidence of corrosion after 168 hours of ASTM B i 17

For Quality Conformance No evidence of corrosion after 168 hours of ASTM B i 17

For Qualification

No intercoat separation in the as-painted condition, and after water immersion and scribing

Table 1-6. Summary of MIL-C-5541E Process Control Performance Requirements

(5 panels) than 15 spots per 5 panels after 168 I 6061-T6 or 2024-T3 hours of ASTM 61 17 Salt SDrav 3

Property I Class I Alloy Substrates I Performance Requirement I 1A I 2024-T3 I Less than 5 spots per panel and less

I . .

(5 panels) I Exposure I i A I 2024-T3 I NO intercoat separation after wet tape

I 2 panels adhesion procedures per Federal 1 A z % I 3 60611T6 or 2 0 h 3 1 Test Method Standard 141. Method (2 panels) I6301

In addition all test panels can have, “no more than 15 isolated spots or pits, none larger than 0.031 in. in diameter on the combined surface area of all five specimen panels, subjected to the salt spray test.” As a rule, a spot is count- able if it leaves a visible corrosion product stain or “tail” on the panel surface.

The lot acceptance criteria for MIL-C-5541E are essentially visual inspection of as-coated

surfaces to ensure that conversion-coated surfaces are uniform and free of flaws.

1.4.3.2 Contact Electrical Resistance Attributes

MIL-C-8 1706 directs that contact electrical resistance measurements be made on coated alloy surfaces with a contact area of 1 in.’ and load of 200 lb. The average contact resistance shall be less than 5 mQ/in.* for as-coated

Use and dissemination Otthe information contained in this document are subject Io restrictions M the mpyright page.

1-9


surfaces, and less than 10 mQ/in.* for panels exposed to ASTM B117 salt spray for 168 hr. Individual readings greater than 20% of the specified maximum are acceptable provided the overall average for the set of measurements is below the specified limit. For MIL-C-81706 Class 3 coatings qualification, measurements are to be made on five individual 6061-T6 panels. No contact electrical resistance measurements are required for quality conformance inspection. The contact electrical resistance requirements for MIL-C-8 1706 are summarized in Table 1-5.

MIL-C-5541E does not specify performance requirements other than to indicate that the performance level is to suit the needs of the application for the procuring activity.

1.4.3.3 Paint Adhesion Attributes

MIL-C-81706 provides instructions for determining acceptable paint adhesion performance. To prepare the panels for testing, conversion coated 2024-T3,7075-T6, and 6061-T6 surfaces are to be primed using a MIL-P-23377 epoxy polyamide primer, then painted with two coats of a MIL-L-81352 acrylic lacquer. When the lacquer is fully dried, dry paint adhesion is tested by scribing (using a sharply pointed tool to make a mark) through the paint to bare metal. The paint should peel away without chipping or flaking.

MIL-C-81706 and MIL-C-5541E specify testing of wet paint adhesion according to Federal Test Method Standard 141, Method 6301 [6]. Painted panels are immersed in distilled water for 24 hours, then removed into ambient air. Two parallel scribe marks, 1 in. apart, are made through to bare metal using a sharp knife. Adhesive tape is laid perpendicular over the scribes and is removed immediately. If any paint is removed as the tape is withdrawn, the panel is given a fail ranking. If no paint is removed, the panel is given a pass ranking.

The MIL-C-8 1706 performance requirements for both qualification and quality conformance inspection and the MIL-C-5541E process control performance requirements are identical. Paint adhesion performance requirements arc summarized in Tables 1-5 and 1-6.

-

~~

1.5 Test Results Summary ~

This section provides an overview of the study results, and serves as a reflection of the state of the art. The information is presented in a format that should facilitate general conclusions about the degree to which chromium- free alternatives are now able to be considered as potential replacements for a range of applications and, conversely, about how much remains to be done for other applications.

Results for corrosion resistance, contact electrical resistance, and paint adhesion tests for the individual alloys are presented graphically in Figures 1-1 through 1-15.* In these figures, coating suppliers and coatings are listed along the vertical axis. The performance level is indicated on the horizontal axis. Vertical lines are drawn corresponding to the performance levels required by the military specifications.

The figures indicate, at a glance, the distribution of performance levels represented in the study, and the performance of the altematives and the control samples with respect to the military specification levels. Comparing the figures for a given test can also convey an impression of the relative degree of difficulty in finding alternatives for each of the various alloy types.

1.5.1 Corrosion Resistance Test Results - Figures 1-1 through 1-5 summarize the results of the corrosion resistance tests for each alloy. The summary data represented by the

-

* These figures are included at the end of Section I

1-10 Use and disseminalion of ihe inlormalion contained in his dawmsnt are subject lo reslticliQns on h e copytight page.


horizontal bars show the performance of each of the five panels tested for each coating. The bar length corresponds to the number of hours at which the panels would have failed the MIL C-5541E criterion (greater than five spots per panel). The coatings are listed in order of decreasing average time per panel. (In this summary, no distinction was made between panels that failed at the maximum inspection time, 1008 hours, and panels that were still good at that time. The full results table in Section 2 provides details.) Readers can use these charts to judge both the overall performance levels and the spread of values observed for each coating.

1.5.2 Contact Electrical Resistance Test Results

Figures 1-6 through 1-10 summarize the contact electrical resistance values (in mQ/in.’) obtained for each coating, with a separate chart for each alloy. The values shown here were for coatings that were tested before any exposure to salt spray. Values were also measured after exposure, but the results are not meaningful for comparison since all panels were run to failure and thus were subjected to different exposure times. The post-exposure values are therefore not summarized here. See Section 3 for further discussion.

Since the specification requires that measurements fall below a maximum value, the coatings have been listed in order of increasing contact resistance. As with the corrosion resistance test results, both an average value and a spread can be read from the charts.

Ten measurements were made for each coating, and the high and low value discarded. The following list is the key to the symbols used on Figures 1-6 through 1-10,

A diamond indicates the average of the

x An “x” indicates high and low values.

- The horizontal line through the diamonds and “x’s” indicates the measurement range.

I A tick mark to the right of the mean indicates the standard deviation of the eight measurements.

eight remaining measurements.

Values falling below 0.1 mWin.* were rounded up to 0.1 for presentation purposes. (The full results table in Section 3 provides details.)

1.5.3 Paint Adhesion Test Results

Figures 1-1 1 through 1-15 summarize the paint adhesion measurements. Since both wet and dry adhesion were measured, two charts are presented for each alloy. Within each performance rating of 0 to 5 (where 0 is the highest level of paint removal when the tape is withdrawn and 5 is no removal), the coating order is alphabetical by supplier. Section 4 provides the details on the rating system.

The vertical bar at rating 5 indicates that only panels performing at level 5 would be considered acceptable according to the military specifications.

1.6 General Observations The results indicate both that much progress has been made in finding chromium-free alternative conversion coatings for aluminum and that many challenges remain. On the one hand, several of the coatings tested here are already suitable candidates for evaluation as replacements to chromium in a wide range of applications. On the other hand, particularly in the case of alloy 2024 and related aerospace

~~

Use and dissemination 01 be inlowlion contained in this drmment am sublea to restticbns M the copyright page.

1-11


alloys, the alternatives studied here provide few options capable of approaching the most stringent performance levels required by the military specifications.

As discussed further in the following sections, the testing carried out in conjunction with this study was rather rigorous. Although the control samples (standard chromate conversion coatings) performed reasonably well, none of the control coatings on alloy 2024 successfully passed all the requirements for MIL-C-5541E. Those chromate conversion coatings that passed the corrosion resistance criteria failed the wet adhesion tests and vice versa. One of the alternative coatings passed both the corrosion resistance and wet adhesion criteria for alloy 2024, but did not meet the contact electrical resistance standard.

On the positive side, using for example a less stringent criterion, all test panels of two of the chromium-free coatings survived at least 96 hours of salt spray exposure for both the 2024 and 7075 alloys, as did six of those coatings for alloy 3003, and nine for alloy 6061. For somewhat less demanding applications than those covered by the military specifications, a reasonable selection of chromium-free coatings may already be available.

In many cases, the performance of at least some of the panels with alternative coatings was remarkably good. If the best-performing panel among the five test panels for each coat-

amounts to the worst-performing panel (equivalent to the coating failing if any one of the panels has more than five spots), a different picture emerges.

Two of the alternative coatings had individual panels that survived at least 168 hours of salt spray exposure for both the 2024 and 7075 alloys (one of the latter lasted through the maximum 1008 hours of the test). For alloy 3003, six of the coatings had individual panels that survived 168 hours; in fact, the best panels of five of the coatings survived the 336-hour specification; two of them lasted until the end of the test. Of nine coatings on alloy 6061, for which the best panels survived at least 168 hours, four met the 336-hour standard; one of them lasted until the end of the test. These coatings clearly indicate a potential for becoming acceptable replacements for even the most demanding applications. What remains to be developed is consistency.

ing is considered, rather than considering what -~

~~

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1-12

National Center tor Manufacluring Sciences

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1-15


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1-19

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National Cenler lor Manulacluring Sciences

1-23

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Lord: Paintable

Parker: Alcdine €03 heavy

Sanda: Sandia 1

Parker: Alcdine heavy

Patdin: 19106

Patdin: 191OC

Patdin: 19116

Parker Alodine 12Ms

Sandia: Sanaa 2

USC: CeMo 7075

GM: GM 2

Lord NcmpaintaMe

C i r d e - P m : Alwat 1470

Cirde-Prosm: Alcoat Zoo0

Turm: 2438280 0 1 2 3 4 5

a) DryAdhesion

Betz Permatreat 611


Bulk: E-CLPS 923):

cirde-Prosco: Almt 3wo

GMGMZ

Parker Alodine 12OCs

Parker. Alcdine 12Ms heavy

Parker: Alcdine €03 heavy

Sanchem: FP

Turw: Alumimat 6788

USC: CeMo 7075

Parker Alodne €03

Patdin: 19108

Patdin: 1 9 1 K

Bulk E-CLPS 923

Circle-Pmsar: Almt 4033

Cirde-P": Almt 5wO

Parker: Alcdine 2wO

Patdin: 191OA

Patdin: 19116

Sandia: Sandia 1

Sanda: Sandia 2

Circle-Prm: Alml 15W

Circle-Prosm: Almt 1470

Circle-Prosm: Almat 2WO

Lord Nonpaintable

Lord: PaintaMe

TUM: 243828D 0 1 2 3 4 5

b) Wet Adhesion

Figure 1-15. Alloy 7075 Paint Adhesion lest Results Summary

/ I I

National Center for Manuladuring Sciences

The salt spray corrosion test has the virtue of being a direct test of corrosion resistance under parameters that approximate a plausible set of real-world conditions. However, it has its share of problems. Some are discussed in the test method itself (ASTM B 117-90, Sec- tion X2). Although the test conditions provide a fair simulation of a marine environment, the same relative performance cannot be guaran- teed under other conditions. The first para- graph of ASTM B117 states:

... It should be noted that there is seldom a direct relation between salt spray (fog) resistance and resistance to corrosion in other media, because the chemistry of the reactions, including the formation of films and their protective value, frequently varies greatly with the precise conditions encountered. [2]

Results may also depend on the quality of the base alloy, the coating thickness, and a host of other variables.

Apart from the problems cited in the test method, practical experience has indicated a variety of additional disadvantages. The test takes a long time, making it unsuitable for rapid screening. Test chambers vary, and even within a single chamber, uniform conditions for all positions is notoriously difficult to achieve. Nevertheless, for all its shortcomings, salt spray testing remains one of the most widely used methods for comparing coating performance.

2.1 Test Conditions and Procedure In designing the experimental protocol to be followed in this study, project participants attempted to do everything possible to maximize the intercomparability of coatings. Neverthe- less, inevitable compromises had to be made.

Two test chambers, each with a capacity of 400 panels, were available for the study. The chambers are located at Texas Instruments’ Lemmon Avenue facility in Dallas, Texas. To minimize interchamber variability, all panels of a given alloy were to be tested in the same chamber. Ultimately, the number of coated test panels submitted exceeded the capacity of these chambers, and a third chamber was needed. A chamber located at a different TI facility, in Sherman, Texas, was used. The panels tested at the Sherman facility were those samples that arrived last from the coating suppliers.

To assist in evaluating the uniformity of the test chambers, control samples were distri- buted randomly throughout the chambers. For control samples, Parker, the coating supplier, provided panels coated with two typical chromium conversion coatings, Alodine 600 and Alodine 120Os, for each alloy. When it became necessary to use the Sherman facility chamber, additional control samples were prepared by TI personnel. Using their normal practice for preparing control samples, they coated test panels cut from stock samples of each of the four sheet alloys with the commercially available Alodine 600 coating. They then labeled these additional control samples with the alloy number followed by Roman numerals I through V (for example, 2024IV) or by letters A through E (for example, 7075D).

To provide the most information from this testing, project participants decided to modify the MIL-C-81706 test procedure. Rather than exposing samples for a specified number of hours and recording only whether a given sample passed or failed, TI personnel ran all samples to failure (to a maximum of

USB and disssminalion d the inlomaliar con$ined in his document are subiecl Io ~SLr ic l ion~ on the mpyighl pa@.

2-i


1008 hours, is . , six weeks), with frequent inspections to determine the progress of each sample. Inspectors recorded the number of corrosion spots appearing on each panel at each inspection (see details below). In addition, the position of each panel in its chamber was recorded (see Figures 2-1 and 2-2). The inspectors returned each panel to the same chamber location after each examination.

The advantage of this modification of the test procedure is that a wealth of information is thereby made available. The reader may use the data not only to obtain an overall impression of the performance of a given coating on a given alloy, but also to obtain a sense for the degree of variability across the five test panels of each coating and alloy combination, as well as the rapidity with which corrosion proceeded on each panel once it had begun.

The disadvantage of this modification is that the results may not be directly comparable to those of testing that had been done strictly according to MIL-C-81706. In particular, since the chamber was opened periodically and the samples removed for inspection, the test was effectively a cyclic exposure to salt spray, inter- spersed with periods of exposure to dry air.

As specified in ASTM B 117, a neutral solu- tion of 5% salt was used for the spray mixture.

Two inspectors working together carried out the panel examinations. Prior to examining the test samples, they “pre-calibrated” their judgments by examining separate Alodine control panels (previously prepared by TI and pro- cessed in the TI chambers). This initial “calibration” consisted of both inspectors agreeing on the amount of corrosion that constituted the various padfail criteria.

Each panel was run to failure or to 1008 hours (42 days), whichever occurred first, and inspected at intervals of 24,48,96, 168,240,336,

504,672, 840, and 1008 hours (1 ,2 ,4 ,7, 10, 14,21,28,35, and 42 days). At each interval, the inspectors recorded the degree of corrosion observed on each panel. Inspection and quality

for spot size and quantity. The inspectors had to agree on all determinations of “failure,” defined as the presence of more than five spots per individual panel (a modified MIL-C- 5541E criterion). The ranking and degree of corrosion for the padfail criteria were:

criteria followed MILC-5541E specifications -~ ~~

~

Pass: PO = no spots P1 = 1 spot P2 = 2 spots P3 = 3 spots P4 = 4 spots P5 = 5 spots

Fail: F1 = 6 to 50 spots F2 > 50 spots to 33% corroded F3 = 33 to 74% corroded F4 = 75 to 99% corroded F5 = 100% corroded

The inspectors documented borderline failures and returned the panels to the chamber until failure was certain. Because the condition of each panel was recorded at each inspection interval, the reader may compare corrosion performance against either the MIL-C-8 1706 qualification and quality conformance requirements or against the MIL-C-5541E process control requirements.

Each day, the inspectors logged all chamber conditions and other data required by ASTM B117. All inspection data were recorded by panel serial number, since the inspectors were not told the identity of the coatings until the testing had been completed. In addition, the length of time for which salt spray was inter- rupted was recorded for each inspection.

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....... Back

30 in.

... Front

Row I Row11 Row 111 Row IV RwV Row VI Row VI1 Row Vlll

, L*L ,

I i

29 in.

Figun, 2-1. Panel Positions in Lemmon Avenue Salt Spray Test Chamber 1 (viewed down from top of chamber)

c- 'U! 6

National Center for Manulacluring Sciences

2.2 Observations and Discussion

A detailed compilation of the corrosion (salt spray) resistance test results of this study is given in Table 2-1.

The results show a wide range of performance among the alternative coatings as well as some variation in the performance of standard chromium coatings. A number of the test panels, including most but not all of the control panels, exceeded the minimum 168-hour salt spray requirements of MIL-C-5541E (no more than five spots per panel). However, none of the coatings, including the controls, passed the corrosion resistance qualification test for materials conforming to MIL-C-81706 (that is, no spots at all during 336 hours of salt spray tests).

As noted previously, chamber conditions vary, both within and among chambers. Therefore, results of salt spray testing are not generally expected to be exactly repeatable. Some chambers appear to be “harder” than others. Such effects might be due to slight differences in the size of droplets from the spray nozzles between one chamber and the next, or to other minor differences, the effects of which mani- fest themselves during long exposures. In reviewing the data from these tests, including the control panel performance, some partici-

pants concluded that the TI chambers subject the panels to relatively harsh conditions. The cyclic nature of the exposure resulting from the frequent inspections may also have increased the level of harshness. This relative harshness is probably just as well for present purposes, since it has the result of providing a more rigorous, and perhaps more meaningful, test regime. However, it also implies that readers should pay more attention to relative than absolute performance in this test series, and should not rule out coatings for specific applications because they may not meet preconceived expectations.

In a few cases, the number of spots recorded for a particular panel decreased from one inspection to the next. This was the actual obser- vation of two experienced inspectors working together and being in agreement. Whether the spots somehow actually became less visible or whether this simply indicates an unavoidable uncertainty in judgment as to what constitutes a spot cannot be determined. It should be noted that the corrosion spots associated with some of the alternative coatings did not have the distinctive tail characteristic of chromate conversion coatings. This somewhat unfami- liar appearance may account for some of the uncertainty. The situation was rare enough that the overall conclusions would not be affected.

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Table 2-1. Corrosion (Salt Spray) Resistance Test Results

Performance Key: Pass Fail PO = no spots P I = 1 spot P2 = 2 spots P3 = 3 spots P4 = 4 spots P5 = 5 spots

F1 = 6 to 50 spots F2 > 50 spots to 33% corroded F3 = 33 to 74% corroded F4 = 75 to 99% corroded F5 = 100% corroded

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Table 2-1. Corrosion Results (continued)

2-7

National Center lor Manulacluring Sciences

Table 2-1. Corrosion Results (continued) I

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2-9


Table 2-1. Corrosion Results (continuedJ

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2-1 1



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Table PI. Corrosion Results (continued)

cessing at Circle-Prosco. Panelr will probably perlorm as well as panels 34274432, but some

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2-13



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2-15



iulk E-CLPS 923: mntinued)

Alcoat 1500

~

Alcoat 2000 r I

Alcoal3000

Alcoat 4000

Alcoal5000

~

- Pane No.

1075 107E 1077 1078 1079 1085 1086

1088 1089 1277 1278 1279 1280 1281 1217 1218 1219

- __ __ I_

- __ - 1087 - - - - - __ - - - __

- 1220 1221 __

1097 1098 1099 1100 1101 1193

-

__ 1194 1195 1196 1197 !289- 1290

1292 1293

1291 __

lym PO P1 P i F1

A-

sm.2 3 P2 P3 P2 P3

6 P i P i P1 P3 1 PO P2 P2 P2 5 P2 P2 P2 P3

168

96 Minor streaking 01 coating near edges, probably due to handlinc at Circle-Prosco. Should be ok,

4a

but corrosion protection may be compromised.

168 Minor streaking 01 coating near edges, probably due to handlinG at Circle-Prosco. Should be ok, but corrosion protection may be com romised.

~~

3 F1

3 F1

2-1 6



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2-17



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Table 2-1. Corrosion Results (wntinued)

at Circle-Prosco. Should be 01

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2-21



2-22 Use and dissaminalion of the infomkm EOnPined in this dowmsnlare subjecllo reslrieBonaon lhs mpyighl page.

National Center for Manufacluring Sciences

3. Contact Electrical Resistance Tests

Contact electrical resistance becomes an issue when items such as electronic components are mounted on a coated part. If the part is a hous- ing or a chassis, a connector or a connector seat, or a similar unit for which reliable electrical connection or adequate grounding is essential, the coating cannot interfere with that requirement. Contact electrical resistance testing ensures that a coating will not present a problem of this type.

Military specifications MIL-C-5541E, “Che- mical Conversion Coatings on Aluminum and Aluminum Alloys,” [3] and MIL-C-81706, “Chemical Conversion Materials For Coating Aluminum and Aluminum Alloys,” [5] require contact electrical resistance testing both on coatings as applied and on coatings after exposure to salt spray for 168 hours.

For this study, the contact electrical resistance of the as-applied (pre salt spray) coatings was measured in a manner consistent with the military specifications. However, the post-salt spray measurements were performed under a modification of the specifications. Because the test panels were exposed to salt spray until failure, rather than for a specified time (see Section 2.1), the post-salt spray measurements were performed on panels with a wide range of exposure times. Therefore, although the results provide information about the contact resistance behavior of a particular coating when exposed to salt spray, they should not be used to compare one panel with another, or to infer results expected under the standard test procedure where exposure times are the same.

3.1 Test Procedure

Sandia National Laboratories conducted the contact electrical resistance tests for this study. Sandia received one panel of each alloy for

each coating for the pre salt spray measurements. These panels were not used subse- quently for the corrosion resistance or paint adhesion tests. However, unused portions of these panels were provided to Rockwell for electrochemical impedance spectroscopy testing (see Subsection, 1.4.2).

Sandia developed the apparatus and detailed test procedures used for this study to provide measurements consistent with MIL-C-554 1E and MIL-C-81706 requirements. Test personnel used a Chatillon USTM load frame with a 500-lb load cell and a Keithley Model 580 Micro-ohmmeter (accurate to 0.000lQ) with model 5806 test leads. Two copper electrode platens, each 1 in?, were also fabricated. The surface of the electrodes was mill finished and then polished to a mirror finish. The electrodes gave a resistance reading of less than 1 when polished and cleaned with methyl alcohol.

The test personnel made contact electrical resistance measurements on each panel in 10 locations by impinging the electrodes onto the coated panel surface under a 200-lb load [7]. The highest and lowest of the 10 measurements were eliminated, and the remaining 8 were used to determine an average contact electrical resistance value for the panel.

The general test procedure was as follows [8]:

1. The load frame was configured for a direct reading of load on the “Hi Load” scale. The ohmmeter was zeroed when no load was applied.

2. A calibration check was performed periodically to verify the zero calibration under load and to confirm that the electrode surfaces remained smooth and clean. To

3-1


conduct this check, the ohmmeter was set to the 200-pQ range, the test leads were connected to the upper and lower electrodes without a test panel between them. A 200-lb force was then applied, and a reading taken to confirm zero resistance.

3. A small corner of each panel was cleaned with an abrasive on both the front and back to remove the coating and provide the clip lead a good connection to the alloy.

4. The test panel was mounted in the frame between the electrodes so that the top electrode was located over the first area of the 10 areas to be tested.

5. A 200-lb (+5 lb) force was applied. One test lead was connected to the upper electrode, and another lead connected to the cleaned area of the test panel.

6. The reading was recorded on the test panel data sheet.

Steps 4 to 6 were repeated for each of the remaining locations on the test panel.

3.2 Observations and Discussion Tables 3-1 and 3-2, for pre and post salt spray respectively, list the mean, the minimum and maximum readings, and the standard deviation of the 8 contact electrical resistance measurements retained for each panel (after omitting the highest and lowest of the 10 readings taken).

In some instances, unexpectedly high resistance values were observed. In the post salt spray data, these high values can be ascribed to the salt exposure procedure, wherein all

sured. The data from the pre salt spray mea-

anomalously high, with no immediate explanation. To ensure that a systematic error in the measurement protocol was not contributing to the high readings, procedures were reviewed and a second set of measurements collected. These latter values were substantially identical, to within experimental error, with those obtained in the first set. Thus, these high readings are believed to be accurate. (Table 3-1 presents the second set of results.)

In retrospect, a possible explanation for the high readings on alloy 7075 may be related to its relatively high content of magnesium and zinc. (See Table 1-1 for the nominal compositions of each of the alloys used in this study). If the coating process used on the test panels produced an accumulation of zinc and magnesium oxides on the panel surfaces, high contact resistance readings would be plausible.

Such high readings might not ordinarily be observed, since the contact electrical resistance test is normally conducted on the 2024 and 6061 alloys and not on alloy 7075. This effect might only become evident in systematic studies using a range of alloys such as the study conducted under this project.

panels were run to failure before being mea-

surements on alloy 7075 also appeared to be

-~ .~ ~

~

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Table 3-1. Contact Electrical Resistance Pre Salt Spray Test Results

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Table 3-1. Pre Salt Spray Results (continued)

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Table 3-1. Pre Salt Spray Results (continued)

* UTRCnote: Water stained.


USC I Ce-Mo 7075 I5066 I 66.0 8.50 226 73.2

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Table 3-2. Conrad Electrical Resistance Post Salt Spray Test ResuMs

Sanchem

Sandia

Betz Permatreat 61 1 25 I 30,200 I 596 I 217,000 I 75,600

Bulk E-CLPS 923 49 I 1,540 1,280 2,310 326 Brent Chemcote L497260A 14 1 1,770 I 222 I 2,970 I 964

1911B 85 681 126 1,690 639 FP 133 47.3 3.74 114 44.2

Sandia 1 325 4,710 924 9,760 3,470 Sandia 2 337 2,760 766 6,650 2,060

SD 145 201 76.0 462 138

1910B I 97 I 1,750 I 1,002 I 2,280 I 524 191oc 1 7 3 1 546 42.4 1,320 443

Alcoat 5000 I4241 I 3,350 I 2,040 I 5,920 I 1,210 Lord Paintable I4181 I 104 40.7 216 53.8

Nonpaintable I4193 I 20.4 11.4 47.5 12.3

L *An asterisk lollowing a panel number indicates that a note relevant to that panel is listed in Table 2-1, last column

Uss and dissemination of the information mlained in lhis document are subject to rnslnclions on Ih8 mpynght p g e

3-7

National

3-8

'An asterisk lollowing a panel number indicates that a note relevant to that panel is listed in Table 2-1, last column,

Use and dissemination of the inlormallon contained in this dmument 818 subjsa lo reslricsans on Uis copyright page.


Tab/e 3-2. Post Salt Spray Results (continued)

'An asterisk following a panel number indicates that a note relevant to that panel is listed in Table 2-1, last column.

Natimal Center lor Manulacturing Sciences

Table 3-2. Post Salt Spray Results (continued)

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4. Paint Adhesion Tests

Not all applications require that a coated part be painted. For those applications that do, paint adhesion to the coated surface becomes an important consideration. But why coat a part that is to be painted? The paint will provide corrosion protection by itself. Is this merely redundancy? In fact, painting over conversion coatings can provide a useful synergy.

A paint layer functions primarily as a barrier, preventing corrosive media from contacting the metal surface. However, paint is susceptible to scratching, and once the barrier is breached, the metal becomes vulnerable. The standard chromium conversion coating affords some measure of chemical protection even in the vicinity of scratches. Furthermore, as pointed out in MIL-C-5541E, Class 3 chemical conversion coatings (relatively thin, elec- trically conductive coatings) will improve paint adhesion in areas surrounding electrical contacts.

Several approaches are currently used to gauge the quality of paint adhesion under various conditions.

MIL-C-8 1706 specifies that paint adhesion testing is to be conducted per Federal Test Method Standard 141, which describes two test methods:

Method 6304, the “knife” method is used on dry panels. A ribbon of paint is cut from the surface to ascertain whether the adhesive force holding the paint to the surface ex- ceeds the cohesive force holding the paint to itself. To pass, the paint must not flake or separate beyond the cut.

Method 6301, the “tape” method is used for wet adhesion tests (see Subsection 1.4.3.3). In this procedure, test panels are immersed in distilled water, removed, and dried. With-

in 1 minute of removal, two parallel scribe marks are made and an adhesive tape applied across them. To pass, no paint separation may occur between coats or from the panel surface when the tape is removed.

MIL-C-5541E also refers to Federal Test Method Standard 141, Method 6301 for wet adhesion tests. However, it does not contain any dry test procedures.

ASTM D-3359, “Standard Test Methods for Measuring Adhesion by Tape Test,” specifies two methods, A and B. Unlike the simple pass/fail criteria in the military specification, these methods use a rating scale of 5 to 0, as shown in Table 4-1, that represent the amount of paint removed.

In Method A, used for wet adhesion tests, an x-shaped scribe mark is made, and tape is applied over the scribe and removed. The repeatability* of this method is 1 rating level; reproducibility** is 1.5 rating levels.

In Method B, used for dry adhesion tests, the panel is scribed with multiple cross- hatched lines, and tape is applied over the crosshatch and removed. Paint adhesion is also rated on the 5 to 0 scale. The repeatability of this method is 1 rating level; reproducibility is 2 rating levels.

Project participants reviewed these approaches, and selected the combination of methods that would provide the greatest amount of useful information.

* The expected difference in rating level when the test is repeated in the same laboratory by the same technician.

**The expected difference in rating level when the test is reproduced in a different laboratory.

Use and dissemination 01 he inlormatim contained in this dmument are subjea to mstdc&m m the copyright page.

4-1


Table 4-1. Paint Adhesion Rating System, Based on ASTM 0-3359, With Modifications

Rating I Method A- Wet Adhesion

Description of Coaling After Tape Removal

5 4

I Jagged removal along scribes up to i H 6 in. (1.6 mm) on either side. 3

I No peeling or removal. I Trace peeling or removal along scribes.

2 1

1 Jagged remova, along most 01 the scribes LP to 118 in. (3.2 mm) on either side. I Removal from most of the area oetween tne scribes unaer the tape.

0 I Removal oeyona the area of tne scrioes. Method B - Drv Adharion I

I 5 I Edges of cuts are completely smooth; none of the squares of the crosshatch lattice is detached. ~ ~~~~~~ ~

4 3

I Small flakes 01 tne coating are aetached at intersections; less than 5% of tne area is affected. I Small flanes of tne coatina are detached alona edaes and at ntersections of c ~ t s . Tne area affected s 5 to

2 1

I Coating has flaked along the edges and on parts of the squares. The area affected is 15 to 35% of the lattice. I Coatina has flaked alona the edaes of the cuts in larae ribbons and whole sauares have detached. The area I affecte; is 35 to 65% ofihe lattice. I Flaking and delamination are worse than rating 1.

1

0

The combinations of test procedure and rating method selected for this study were as follows:

Dry adhesion testing

- Procedure: ASTM D-3359 Method B - Ratings: ASTM D-3359 Method B

Wet adhesion testing

- Procedure: Federal Test Method Standard 141C, Method 6301.2

- Ratings: ASTM D-3359 Method A.

The ASTM rating scales were used for both the dry and wet tests because they provide a comparative rating system, thereby conveying more information than the simple padfail criteria of MIL-C-81706 and MILC-5541E. In the military specifications, any evidence of paint removal by the tape is considered a failure. Since some applications may not require such a stringent criterion, the researchers performing this test felt that a rating scale that indicated the relative degree of paint removal would be more useful.

4.1 Test Procedure Eastman Kodak conducted the paint adhesion tests at its Elmgrove facility in Rochester, New York. The paint mixture used on the panels consisted of the following components:

Sherwin Williams White Polane T+F63W77 -4 parts by volume

V66V44-1 part by volume

by volume.

Sherwin Williams Isocyanate catalyst

Sherwin Williams Reducer R7K84-1 part

To prepare the conversion-coated panels for testing, Kodak test technicians sprayed them directly with the mixture (without a primer), using a Binks Mack 1 HVLP spray gun. The panels were air set for 30 min, baked for 30 min at 140°F. and cured for at least 14 days before testing. The technicians measured paint thickness using an eddy current thickness meter calibrated to alloy 3003. Based on an average of 51 readings, paint film thickness was 0.00243 in. M.00044 in.

-

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To conduct dry adhesion testing, test personnel used a Paul N. Gardner adhesion tester with 1.5-mm spacing blades to make the cross- hatched scribes. To ensure a sharp cutting edge, several blades were used during the test. An ASTM-qualified, 1-in. wide, semi- transparent, pressure-sensitive adhesive tape was used. Its average adhesion, or “tack,” was 38 k5 oz per inch of tape width.

For the wet adhesion tests, Kodak immersed the scribed panels in distilled water for 24 hours, then removed and dried them. An ASTM-qualified adhesive tape was used for this test, and its tack was tested and confirmed against the specification (average adhesion of 60 oz per inch of width). The tape was then laid across the scribe marks and pulled away using a continuous, even motion. A Kodak technician visually determined the amount of paint removed with the tape.

Each panel was rated for paint adhesion using the ASTM D-3359 rating scale of 5 to 0.

4.2 Observations and Discussion

The results of both the wet and dry adhesion tests are compiled in Table 4-2.

Inspectors noted that many of the panels showed adhesion loss within 1/4 in. of the panel’s bottom edge, where a drip shadow was observed.

In many cases, the degree of adhesion observed for the wet and the dry tests appeared to be correlated. However, for a number of cases, good dry adhesion corresponded to poor wet adhesion. and vice versa.

Although MIL-C-81706 requires no coating loss for the wet adhesion test (equivalent to a rating of 5 for the procedure used here), a rating of 3 is considered to be acceptable for many commercial applications, according to an engineer familiar with the use of the tests by industry. A rating of 3 allows for the expected error in repeatability and reproducibility of the test.

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4 3


Table 4-2. Paint Adhesion Test Resulfs

Descriptions of the ratings for dry and wet paint adhesion tests are given in Table 4-1,

4-4

Nalionai Center for Manufacturing Sciences

Table 4-2. Paint Adhesion Test Results (continued)

I Coater I Coating I Panel I Dry Test I Wet Test I Notes from Coater, Tester, or UTRC - I No. I Rating j Rating 1 (Tester noles are relatea to we1 aoheson tesls) - MoyiW4 (ContinueCO

4 1 Coafer A I coatings per specillcallon Palmer 1 Aiodine 600 I 1 4451 I 4 I_ I Aiodine600heavy 4295 I 5 I 4 Aiodine1200sheavy I 4380 I 3 1 4 I Alodine 12005 4487 2 5 Alodine 2000 4283 5 5 Jester: Peeling 112 in. from scribe on edge of panel.

Patciin 191OA 4091 5 4 19108 4067 3 4 191oc 4079 2 5

! I19118 I 4055 I 3 I 1 Coa1er:Caustic chemical damage due to mishandling. coating

Sanchem FP 4043 5 4 Sandia Sandia 1 4463 3 3 Jester:Some peeling 1/2 in. from scribe, 1/8 in. from edge.

Sandia 2 4475 3 3 Turco 2438-28D 4019 3 0 Coa1er:Originai panels miscoated, CUI new set lrom our thicker

Aiumicoat6788 4031 5 5 stock. usc 1 Ce-Mo 2024 14007 1 1 3 1 Allov30aP Bet2 1 Permalreat 611 I3043 I 5 I 5 I Jester: Peeling 1/8 in. lrom scribe (drip line). Brent I Chemcote L497260A I 3019 I 5 3 1

191oc 3115 I 4 I 5 19118 3139 I 4 I 0

Sanchem FP 3151 I 5 I 5 SD 3163 5 4

Sandia Sandia 1 3403 0 3 Sandia 2 3415 0 3

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4-5



I Coater I Coating I Panel I Dry Test I Wet Test I Notes from Coater, Tester, or UTRC I No. Rating 1 Rating I (Tester noies are re ate0 to wet adnes,on teas)

I Nonpaintable I 1151 3 I Parker [Aiodine 600 I 1139 I 4 I 5 I Coater: All coatings per specilication. UTRC: Water stained.

UIB and dissemination of the information conlained in this document are subjecl to resttic6cns on me copytight page.

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5. Environmental Impact Assessment The intent of this section is to provide readers with information that will assist them in selecting environmentally sound alternatives to chromium conversion coatings for aluminum alloys.

A wealth of process information provided by the coating suppliers is compiled in the environmental impact data sheets (see Section 5.5). Of course, these sheets do not include every aspect that might be of interest to readers who are considering replacement of their current processes with one of these alternatives. The emphasis is on information that is significant to assessing the environmental impact of each process. This information is meant to include the immediate, indoor “environment” of the process-those issues often labeled “health and safety”-as well as the environment in the larger sense.

In confronting this mass of information, and particularly in comparing one alternative process with another, or with the standard chromate processes, one is apt to be overwhelmed by the sheer number of tradeoffs. Some means must be found for consolidating these data if any progress at all is to be made toward a con- clusion. A framework for doing so is offered here, although several caveats are in order at the outset, as follows.

First, the inevitable “apples and oranges” problem arises-that of trying to compare related yet unlike issues. For example, how can a pound of sludge from process A be compared to a unit of risk from process B? A user might be able to reduce the amount of sludge by applying some clever process engineering, but the risk might be beyond technological control. Conversely, risk is as much a measure of perception and assumption as of fact; it relies on extrapolations of uncertain validity and is susceptible to revision by legislation or decree. Any system that projects two incom- mensurable quantities to a common numerical

basis automatically contains implicit value judgments. The best that can be done is to make those judgments explicit, thereby allowing readers to substitute their own.

Second, the information base is necessarily incomplete, since coating suppliers were invited to disclose as little or as much as they wanted about their processes. This option raises a particularly troublesome issue, which also occurs in many regulatory situations. The more a supplier discloses, the greater the potential for finding some environmentally objectionable item. How does one avoid penalizing openness?

The approach used in this assessment was to regard unknowns as especially risky. Thus, the presence of an unknown constituent in a process should entail a sufficiently adverse impact on the assessment that, by revealing the identity of the unknown constituent, the coating suppliers could only improve their scores. On the other hand, a proprietary formulation is not necessarily an environmentally unfriendly one, and some readers may be willing to accept a supplier’s assurance of that fact. Therefore, the environmental impact information is presented in such a way that the reader may readily determine how much of each assessment is based on both known and unknown risk factors.

Third, many of the process variable assumptions (part size, bath size, rinse overflow rate, energy consumption, and so forth) may depend as much on the user as on the coating supplier.

Finally, the project team made every attempt to obtain, record, and process the data accu- rately. Nevertheless, possibilities for misunder- standings and miscommunications can be numerous in a study of this type. Many of the processes are in a highly developmental stage, and may have changed significantly between the times when the coatings were fabricated,

Use and disminalion 01 lhe inlomation contained in this document are subjecl lo r e s t c k h s On he cowoghl page

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when the information was provided, and when this report was published.

As a consequence, the reader is cautioned that none ofthe results ofcomputations in this section should be taken as recommendations. The results are meant to exemplify the methodology developed for this assessment under one reasonable set of assumptions. Alternative assumptions might well generate completely different rankings having equal validity for other situations.

Rensselaer Polytechnic Institute (RPI) researchers developed the methodology for this environmental impact assessment, gathered the information from the coating suppliers, and supplied the weighting factors on which the computations are based. Many of these factors are, frankly, judgment calls, and attempting to rationalize them on any other basis would be disingenuous. Nevertheless, by providing at least a point of departure, this analysis may stimulate further efforts in developing environmental assessment protocols.

5.1 Background of the Methodology RPI researchers demonstrated the methodology they developed for this assessment on the Parker Alodine 1200s chrome system [91. Project participants were given the opportunity to review and comment on the approach. The assessment system was then applied to the alternative coatings. RPI personnel developed the system in three phases [lo] by:

1. Establishing the environmental performance criteria against which the candidate coatings could be compared

2. Compiling information and completing the data sheets that summarized the environmental information on each of the candidate coatings.

3. Completing the environmental impact assessment by developing a means for comparing the environmental characteristics of the candidate coatings on a unified basis.

The work accomplished under each phase is described in the next three sections.

5.2 Phase 1: Environmental Performance Criteria

The environmental performance criteria were selected to provide a concise overview of the impact of the alternatives in the following areas: health, air, water, and land. These four categories were chosen to represent the environmental consequences of most interest.

Health addresses the long- and short-term consequences on human health of exposure to the coating chemicals.

Air encompasses possible impacts of the process on the atmosphere, and is exempli- fied by the generation of hazardous air pollutants (HAPS) and ozone depleting substances (ODSs).

Water considers any adverse effects on water systems.

Land represents the impact of the processes on the land, since landfills are required to dispose of any solid waste that may be generated, assuming burning is not allowed.

Sources upon which the environmental criteria are based [9] are summarized in Table 5-1. The motivation for, and the source of regulation of, each criterion are discussed below.

5.2.1 Number of Process Steps For this criterion, the assumption was made that each step in a process increases the overall amount of raw material usage. This increase in turn poses a greater impact on the environment in general. Every required step adds to the total cost and environmental impact of the process. This represents an increase in the overall capital investment for equip- ment, process materials, and personnel. The possibility for increased amounts of hazardous wastes also exists, which translates to greater cleanup costs and environmental risks.

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Table 5-1. Environmental performance Criteria and RdatedSwrces of Regulation

' Letters indicate items on the Environmental Impact Data Sheets in Section 5.5.

Each process was evaluated on the basis of how many steps the user requires to prepare and coat a heavily soiled (molybdenum grease and metal cutting fluids) and oxidized aluminum panel. This panel is referred to as the assessment standard panel.

5.2.2 Ozone Depleting Substances

Because of the deleterious effect of ODSs on the atmosphere, their presence in each alternative coating process was noted. Information identifying ODSs was obtained from an EPA publication [ 111 and the Clean Air Act, Section 602 [12], which includes a listing of Class I and Class I1 ODSs. Each process step was examined for any chemical constituents that are regulated as ODSs.

5.2.3 Hazardous Air Pollutants Air pollutants are substances that may ad- versely affect the health of humans, animals, plants, and microbial life [13]. As a result of growing regulations and standards controlling chemical emissions, HAPS were included in this assessment. Information on HAPS was gathered from the Clean Air Act, Section 112b [ 141 and from New York State 6 NYCRR Part 201 [15]. Each process step was examined for the presence of any chemical constituents known to be HAPs, which might be inhaled by

persons in the vicinity of the process. Any HAPs detected were noted, and the total number recorded.

5.2.4 Carcinogens

Carcinogens (substances capable of causing cancer) were identified through information from EPA/600/8-89/053 [16] and the Material Safety Data Sheet (MSDS) for each chemical. (MSDSs are required to list carcinogens by Section 313, Title 111, of SARA Part 372.)

5.2.5 Regulated and Hazardous Chemicals

For this criterion, the assumption was made that each regulated or hazardous chemical used in the process increases the potential risk. Thus, an alternative that can accomplish an adequate coating with fewer such ingredients is considered more environmentally sound.

"Regulated" chemicals, in the context of this study, were those hazardous chemicals identified from the MSDSs and referenced to the California Environmental Protection Agency (Cal-EPA) Chemical Cross Index (List of Lists) [17] to identify the source(s) of regulation. Cal-EPA was selected because California has some of the most restrictive environmental

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b. c. d. e.

laws in the nation. The Chemical Cross Index identifies the chemicals that are subject to the 14 regulation programs listed in Table 5-2, codes a through m. (The code is used on the data sheets in Section 5.5) “Hazardous” chemicals, those listed on the MSDS but not on the Chemical Cross Index, were also considered to be “regulated” for the purposes of this assessment.

5.2.6 Resource Usage This assessment assumes that the use of process chemicals, water, and energy creates a degree of environmental impact that is propor- tional to the quantity used. Although coating suppliers may specify temperatures and concentrations, such variables as bath sizes, rinse volumes. and thermal insulation are more a

Chemicals EPA List Of Priority Pollutants AB 1803 -Well Monitoring Chemicals SARA Section 313 Toxic Chemicals SARA Section 302 Extremely Hazardous

Table 5-2. Sources of Regulation Used to Reference Regurated and Hazardous Chemicals

g. h.

I Code I Source of Regulation

. . Contaminants AB 2588 -Air Toxics “Hot Spots’ Chemicals D~Dartfnent of Health Services (DHS) Drinking

I a. I California OSHA Carcinogen User Register I

i. i.

. . Water Action Levels AB 1807 -Toxic Air Contaminants National Emission Standard lor Hazardous Air

-

[ Substances I Maximum Contaminants Levels (MCL) List of f.

m.

n.

0.

. . Hazard Chemicals ’

Permissible Exposure Limits for Chemical Contaminants Hazardous Substances List (also known as “The Director’s List”) Hazardous Air Pollutants (1990 Amendments to

I Pollutants (NESHAP) Specific Chemicals k. I Proposition 65 Chemicals I. I DeDartment of Transportation (DOT) Inhalation

function of the user than the coating. In each case, certain baseline assumptions about the coating operation have been established to provide a basis for comparison.

5.2.6.1 Process Chemical Usage

The calculations for the required quantity of process chemicals were based on what would be needed to treat the assessment standard panel (defined in Section 5.2.1). The quantity of each chemical used for each process step was considered to be that amount needed to reach the specified concentration in 100 gallons of bath water. These amounts were summed (pounds and gallons were treated as equivalent units in these calculations).

5.2.6.2 Water Usage

Each rinse bath requiring water was assumed to contain 100 gallons of water. Continuous overflow rinse stages were considered to con- sume 200 gallons.

5.2.6.3 Energy Consumption

The energy consumption ascribed to each process step was limited to the energy required for bath heating. Although other possible areas of energy usage exist, such as pumps, stirrers, and parts dryers, the total energy consumption due to such devices was assumed to be negli- gible compared to that for bath heating. The energy required to maintain bath temperatures was also not counted. Thus, the energy con- sumed for each process step was simply considered to be that amount required to raise the bath from room temperature (20°C) to the appropriate temperature.

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5.2.7 Solid Waste Generation The potential for generating solid waste de- pends on the process chemistry, as well as on the type of metal to be coated. For this assessment, the solid waste considered to be generated was based on coating an aluminum panel. Solid wastes may arise from metals present in

- __

5-4 Use and diswmination of the informah mtained In this document am rubjecl to reslmions on he mpyright page.


the process chemicals, such as cadmium, zinc, nickel, copper, tin, or chromium. To determine whether specific metals would be present in the waste sludge, the process chemistry would have to be known. The information on solid waste was collected from appropriate MSDSs, and by consultation with academic and industry experts, and the coating suppliers.

Each step that involves solvents was assumed to possess the capability to produce a contami- nated solvent sludge, especially when used for degreasing. However, any solid soil contamination carried in with the grease on the panel was neglected.

5.2.8 Potential for Airborne Contaminants

Air emissions include vapors from degreasing, solvent cleaning, and mists from chromium or other plating operations. Any process step that contains solvents or recommends positive ventilation was considered to produce airborne contaminants. Information was obtained from MSDSs and technical process bulletins. Each process chemical was evaluated to determine its potential for airborne contamination.

5.2.9 Wastewater Generation

Typically, the largest amount of wastewater is generated by rinse steps. Rinse water generally contains low concentrations of process chemicals, which are carried with the part into the rinse (called dragout). All baths were assumed to result in some dragout, although no attempt was made to quantify the amount (the concentration of chemicals in the process and rinse bath must be known for such a quantification).

When judging wastewater generation, this assessment took into account the number of rinse steps in a process, the need for neutralization, and the need to remove hazardous compounds from the rinse water. It was assumed that any hazardous material found in the wastewater would be present in sufficient concentration to require waste treatment. If no

rinse step is required after a given process step, it was assumed that that step does not generate wastewater.

5.2.10 Worker Health and Safety

The worker health and safety evaluation was determined by the relative risk each process chemical would pose to the worker. This criterion took into account the acute and chronic toxicological effects of the hazardous constituents. These effects were taken primarily from available MSDS information. The National Fire Protection Association (NFPA) or Haz- ardous Material Identification System (HMIS) health ranking is supplied in the MSDSs as a general indicator of the toxicity of each process chemical. A summary of potential effects associated with each process chemical is included in Section 5.5.

5.3 Phase 2. Environmental Data Compilation and Data Sheet Completion

The coating suppliers were asked to provide process information on how to prepare a heavily oxidized panel for each coating tested. A heavily oxidized panel was chosen as the standard to provide information on the most extensive treatment that might be anticipated.

Several suppliers provided environmental process data in the form of MSDSs and technical process bulletins. Others chose to provide only limited information or none at all, particularly in cases where processes are in an early stage of development, or where patent or other proprietary issues are still being resolved. For these reasons, some processes were more difficult to characterize, and the associated data sheets are, necessarily, correspondingly less informative. In particular, for most of the alternative coatings, adequate information was not available on solid waste generation. In many cases, suppliers dealt with numerous re- quests for information on multiple occasions; their patience is appreciated.

Use and diwminalion of the inlormatim mlained in this document are subject to sstriclions on the copyright page.

5-5


It should also be noted that the quality of this environmental assessment is dependent on whether the reported process was the actual one used on the panel prior to testing. This is difficult to ascertain, despite the best inten- tions of the suppliers, particularly when coatings are undergoing active development and process changes are rapid and frequent.

The information was incorporated into data sheets that were developed using the criteria chosen in Phase 1. These sheets allowed the criteria to be assigned quantitative values, which were ultimately used to rank the process.

5.4 Phase 3. Environmental Performance Assessment

This section contains the heart of the quantitative comparison framework. To compare the environmental performance of the coatings, the information from the data sheets was put into matrix form. These selection matrices were designed to present the data sheet information in a clear and concise format.

The data sheet criteria were separated into primary and secondary matrices to distinguish the major environmental and health hazards (such as ozone depleting substances and carcinogens) from other assessment criteria (such as process steps and resource usage). The matrices were designed such that the altematives may be easily compared to the baseline reference, the Modine@ 1200s system.

Where some information was not obtainable from the suppliers, an “unknown” designation was used, together with a number indicating how many process steps contain an unknown material. (Coatings from suppliers who chose to provide no process information were omitted from the evaluation.)

A default algorithm was developed to quantify the unknowns. This algorithm was standard- ized for all the criteria used in the data sheets.

The default algorithm is summarized below and is included on the appropriate matrices.

5.4.1 Primary Selection Matrix

The Primary Selection Matrix gives an initial filtering of categories considered to be high hazard parameters. The three parameters considered most hazardous for the purposes of this assessment are:

Ozone depleting compounds Hazardous air pollutants Carcinogens.

The numbers in each of the first three columns of the Primary Selection Matrix (Table 5-3)* reflect the number of compounds falling within each respective criterion. For example, the number “3” in the No. of HAPs column means that the coating process has three separate HAPs. If compounds are unknown for any given process step, the number of unknowns is also recorded. If the same compound is used in more than one process step, it is counted once for each step in which it appears.

The fourth column lists the sum of the known compounds appearing in the first three columns. This total represents the contribution of known compounds to the score.

The fifth column contains a weighted sum of the unknown compounds, using the weighting factors specified at the bottom of the table. Thus, the score appearing in the fifth column equals the number of unknown ODSs multi- plied by 1, plus the number of unknown HAPs times 3, plus the number of unknown carcinogens times 2. (As noted previously, these weighting factors represent the relative hazard judgments assigned by the RPI researchers. A different set of weights will, of course, result in a different score.)

The total score assigned to each coating, equal to the sum of the scores from the known and

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*Matrix tables begin at the end of the section

5-6 Us8 and dissaminalion of the inloimalim carlained in his document are subject 10 restticlions on he mpyrighl page.


unknown compounds, appears in the rightmost column in the matrix. Here, and in general throughout this assessment, a lower total score represents a more environmentally friendly process.

5.4.2 Secondary Selection Matrices

The secondary selection matrices summarize the evaluations for those categories considered to be important for environmental performance, but less immediately critical than the high hazard criteria in the Primary Matrix. The Secondary Matrix is presented in three forms.

The first, the Basic Matrix (Table 5-4), indicates the values for the known quantities and the number of unknown quantities associated with each criterion. The purpose of this matrix is to indicate, at a glance, to the reader both the comparisons among the baseline and the alternative coatings for known quantities, and the present degree of ignorance regarding various aspects of the alternative processes for the unknowns.

The second, the Numerical Valuation Matrix (Table 5-5), indicates the scores as calculated, via the default algorithm given at the bottom of the table, from the known and unknown values. Its purpose is to supply the numerical input to the Decision Matrix (see below).

The third, the Relative Valuation Matrix (Table 5-6), allows the reader to see readily how a particular alternative coating scores, according to this assessment, relative to the baseline reference. This matrix is meant to give a qualitative indication of possible advan- tages and disadvantages involved in replacing a typical, presumably familiar, standard process with an alternative process. In keeping with the “lower means better” convention, a positive score indicates worse overall performance than the baseline, and a negative score indicates better performance, as evaluated by the RE‘I researchers.

5.4.3 Decision Matrix The Decision Matrix (Table 5-7) provides the reader with a comprehensive listing of all the scores assigned to an alternative coating for each of the environmental assessment criteria, combining data from both the Primary and the Secondary Selection Matrices.

The default algorithm was again applied to all metrics with unknowns. As with all other matrices in this assessment, the Decision Matrix has been generated such that an alternative with the lowest score will demonstrate the least amount of overall environmental impact.

In combining the data from various criteria, a weighting scheme was selected to reflect the judgment of the RPI researchers on the appropriate way to combine various levels of risk. The environmental criteria were separated into four groups based on:

1. Economic considerations 2. Severe health risk 3. General health risk 4. Toxicity.

To generate the Decision Matrix, the weights for Groups 1,2, and 3 were set at a value of 2. The weight for Group 4 was set at 1, lower than the other groups because the information obtained is considered to be subjective. One indication of this subjectivity is the inconsis- tency among MSDSs from diffefent coating suppliers. The information upon which Groups 1,2, and 3 were based is considered to be more significant by the WI researchers, and was weighted accordingly. Alternative weighting schemes, depending upon the intended application for a given coating, might be selected at the reader’s discretion.

It is important to note that although the total score is intended to provide an indication of environmental performance, the best method of determining this performance involves careful examination of the scores for each criterion, considered independently. These

U s and dissamina6on d the information contained in mis dwmsnl am subject to restrictions on the copyright page.

5-7

National Center lor Manulactuflng Sciences

individual scores, used in conjunction with the data sheet information, will help provide the reader with a detailed appreciation of the consequences involved in replacing a standard chromium conversion process with an alternative.

5.5 Environmental Impact Assess- ment Data Sheets

Tables 5-8 through 5-29 summarize the raw data on which the environmental impact

Table 5-3. Primary Selection Matrix

0 = all values are known

Alternative Coating2

Baseline Reference

Alcoat3000 Alcoat 4COO

19118 I 0 I 3 Sandia Sandia 1 0 0

Sanaa 2 0 0 Turco A l m m ” 6788 3u 3u

2438.281) 3u 3u USC CeMo 2024 1u 4t1U

CeMo 6061 tu 4 1 tu Ce-Mo 7075 1u 4+1U

assessment is based. (The data sheet tables begin on page 5-15, and each table begins on a right-hand page.) This material will also provide the reader with useful background information, with the understanding that the data are based on input from the coating suppliers,

descriptions of the processes. ~

The data sheets are presented in alphabetical order, by coating supplier and by coating.

and are not intended to represent complete ~ ~~

= values include unknowns‘

No. of Points Total from Unknown

Carcinogens Substances Points Substance@

0 ’ 4 0 4 0 4 0 4 0 4 0 4 0 1 0 1 0 4 0 4

1 The wmbination of a number lollowed by a “u” represents the number of unknown chemicals or process steps in the metric 2 No information lrom Lord and Sanchem.

3 The points assigned to an unknown substance are as follows: Category: ODS 1 HAP 3 Carcinogen 2

No. 01 points lor each unknown:

5-8 Use and dissamination dtha information contained in this dwumant are subject lo raslrictions on the wpyright page.


Table 5-4. Secondary Selection Matrix - Basic

0 = all values are known = values include unknowns1

Chrome Alternative

1 The combination 01 a number lollowed by a " U represents the number of unknown chemicals or process steps in the metric. (Weighted values lo r "U are given in Table 5-5.)

2 No information from Lord and Sanchem.

Use and dissemination of the inlormatim cantained in lhis dowment are subjed to restrictions on the copyright page.

5-9


Table 5-5. Secondary Selecfion Matrix - Numerical Valuation 0 = all values are known = values include unknowns1

Coater and Chrome Alternative

Coating2

BasellneReference t I ..

Resource U I

33.8 I 900

200 600

le l

45,815 I 4

2

3 3 3 2 4 3

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~

4 4 4

- -

1 The values that include unknown quantities (shown in Table 5-4) were calculated from x t yUwhere x =the quantity in Table 5-4 associated with known chemicals or process steps in the metric y = the number of unknown chemicals or process steps in the metric U E a weighted value lor each unknown, as given below:

Category: Value lor each unknown:

No. of Regulated & Hazardous Chemicals Resource Usage -Process Chemicals 10 per production chemical'

No. of Process Steps 1 3 per step

-Water 100 gal per step -Energy 10,OW Btu per step

Solid Waste Generation -No. of Solid Compounds No. 01 Airborne Contaminants Waste Water Generation - No. of Compounds to Neutralize Worker Health - NFPA or HMlS Hazard Ranking *production chemical = manufacturer's trade chemical (e.g., Deoxidizer 6)

1 per production chemical 1 per production chemical 1 per production chemical 4 per production chemical

I I

2 No information from Lord and Sanchem,

5-10 Use and disseminalion of the informatiw mtainsd in lhis dwumenl are subject lo rsslriclionr on Ihe mpyriphl page.


Table 5-6. Secondary Selection Matrix - Relative Valuation

0 = all values are known = values Include unknowns

Symbols reflect comparison between baseline and alternative coatings in Table 5-5, with: 0 =same as baseline - = better than baseline t =worse than baseline

Coater and Chrome Alternative

Coating'

Baseline Reference Parker Alcdine 1200s

let2 Permatreat 611 lrent Chemcute L497260P lulk ECLPS 92:

E-CLPS 923) :ircle-Prosco Alcoat 147C

Alcoat E O (

Alcoat ZOO( Alcoat 300( Alcoat 400( Alcoat 50M.

2M GM 1

GM : Jarker Aiodine 2OM.

Jatclin 1910A, B, ( 19111

Sandia Sandia ' Sandia 2

lurco Alumiwat 6781 2438-28[

usc Ce-Mo 202,

Ce-Mo 606 Ce-Mo 7071

Resource Usage

1 No information lrom Lord and Sanchem.

2 Negative number = lower environmental score (better) than baseline. Positive number = higher environmental score (worse) than baseline.

82 ?.is 0 %

$8 c

- 1 - 1 -

-

Total2

U~8anddi~1~minationolmsiniorma~oncontsinedinlhis 5-1 1 document are subject to res1ticlions an !he mpyrighl page.

Table 57. Environmental Impad Decision Matrix Key to process numbers 0 lo 26 by Coater Coating:

0. Baseline: Parker Alodine 1200s 6. CircleProseo Alcoat 1500 12. GM GM 2 18. Sanchem FP 24. USC CeMo 2024 19. Sanchem SD 25. USC Ce-Mo 6061 1. Betz Penatreat 61 1 7. CirclePrasco Alcoat 2000 13. Lord Paintable 20. Sandia Sandia 1 26. USC Ce-Mo 7075 2. Brent Chemcote L4972WA 8. CircleProsco Alcoat 3000

3. Bulk E-CLPS 923 9. Circle-Prosco Alcoat 4OCQ 15. Parker Alodine 2000 21. Sandia Sandia 2 22. Turco Alumimt 6788 U = No information submittf 4. Bulk E-CLPS 923X 10. CirclePmco A b a t 5000

5. CircleProsm Alcoat 1470 11. GMGM1 17. Patclin 19118 23. Turco 243828D

14. Lord Nonpaintable

16. Patclin 1910A, B, C

(See cont nJation page lor key 10 shaaed areas.)

i I I

Table 5-7. Environmental Impact Decision Mafrix (continued)

=The values that include unknown quantities (shown in Table 5-4) were calculated from

X + " U

x = the quantity in Table 5 4 associated with known chemicals or process stew in the metric

_- -number of points scored

where y the number 01 unknown chemicals or process steps in the metric

U = a weighted value for each unknown (see below)

I= a base unit (see below)

m: Group One No. 01 Process Steps

Resource Usage -Process Chemicals -Water -Energy

Solid Waste Generation -No. of Solid Compounds No. 01 Rinse Steps

Group Two Ozone Depleting Substances Hazardous Air Pollutants Carcinogens Worker Health - NFPA or HMlS Hazard Ranking

GroupThree No. of Regulated & Hazardous Chemicals Waste Water Generation -No. of Compounds to Neutralize 'No. of Airborne Contaminants

Group Four Acute Effects Chronic Eflects

Value for each unknown: 1 10 per production chemical' 1W gal per step 10,WO Btu per step 1 per production chemical' Not Applicable

1 per step 3 per step 2 per step 4 per production chemical'

3 per step 1 per production chemical' 1 per production chemical'

15 per chemical" 5 per chemical"

Base. 1

1 (Not applicable) 1W gal 10,m Btu 1 1

1 1

1 1 (Not applicable)

1 1

1

1 1

* production chemical = manufacturer's trade chemical (e.g., Deoxidizer 6) ** chemical =general chemical (e.g., nitric acid)

I I ' I


Step 1 2 3 4

Tab/e 5-8. Permatreat 611 Environmental lmpact Data Sheet

Process Type: Alternative Chrome Conversion Coating Company: Betz Laboratories, Inc

a) Number of Process Steps

Descrlptlon - Surface cleaning: Betz Kleen 156 t Betr Sol 104 Water rinsing: unknown if continuous overllow required (assuming so) Non-chrome conversion coating: Permatreat 61 1 Drying: type unknown

~rocess Chemicals' Water Step Chemical Amount Continuous Gallons

Name Usage? 1 Betz Kleen 156 I unknown no 100

b) Ozone Depleting Substances (ODSs), Hazardous Air Pollutants (HAPS), and Carcinogens

Energy'

Q,," T"", Q"", @tu) (BtU)

unknown unknown unknown unknown

c) Regulated and Hazardous Chemicals

Bet2 Sol 104

no Total

- 200 ambient N/A ambient N/A I

100 ambient N/A ambient NIA 400 Total unknown Total unknown

U WetTotal I unknown 1 ' II the manulacturer specified a range lor the chemical concentration, the largest value was used.

Reference temperature = 68°F Specilic heat capacity of water = 8.983 Btu/lb mol "F Moles of water per 100 gal = 46.365 Ib mol

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5-15


Step

1

3

- Chemical Solid Posrlble Wastewater

Name Waste Generated Alrbome Neutralization Compounds Requiring Contaminant? Required? Treatment

Betz Kleen 156 unknown yes yes none Betz Sol 104 unknown no no none

, Permatreat611 unknown yes yes , unknown

Chemlcal Name

HMlS Health Total Number Ot Effects Protective Gear Carcinogens? Hazard Ranking Acute I Chronic Required?

g) Raw Material Toxicity and Personal Protection Data

Betz Kieen 156

Bet2 Kleen 156

Acute Elfects: HMlS hazard ranking I 3

I May cause irritation to upper respiratory tract and bums to the skin and eyes.

3 3 2 yes no

b t z Sol 104

Bek Sol 104

Acute Effects: HMlS hazard ranking = 2

/ Skin, uuuer resulratotv tract. and eve irritation.

3 3 2 yes no

Chronic Effects: Personal Protection:

Permatreat 611 Acute Effects:

HMlS hazard ranklng 3 I Skin and uuuer resuiratotv tract irritation: eve burns.

May cause tissue necrosis andlor dermatitis.

Chemical goggles or face shield required. Rubber gloves and appropriate protective clothing (aprons) required. Approved lilter mask or respirator required recommended. Eye wash station and emergency shower should be in close proximity. Ventilate as necessary to keep concentrations below the threshaid limit value.

Chronic Eflects:

Personal Protection:

5-1 6 Use and dSsemination of the inlomticn conlained io his dOcumsnt an subiecl lo reslrinicns on he copyright paw.

Primary irritant dermatitis.

Splash-proof face shield or goggles required. Rubber gloves required. Respirator use recommended. Eye wash facility and emergency shower should be in dose proximity. Must have adequate ventilation.

Chronic Eflects: Personal Protection:

Primary irritant dermatitis and lung damage.

Splash-proof face shield or goggles required. Respirator required. Neoprene gloves, acidmistant suit. Eye wash facility and emergency shower should be in close proximity. Ventilation below the threshold limit value required.


Table 5-9. Chemcote L497260A Environmental Impact Data Sheet

Process Type: Alternative Chrome Conversion Coating Company: Brent America, Inc.


6 I Waler nnsng conin.ods overllow req-ire0 7 I hon-chrome 8 9 I Dlying (assumed)

1 Water rinsing; continuous overflow required


I 8 I None detected I None detected I None present I 9 I None detected I None detected None present

Total: I 1 unknown 1 3 t 1 unknown I 1 t 1 unknown


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5-1 7


step

Table 5-9. Chemwte L497260A (continued)

d) Resource Usage -Process Chemicals, Water, and Energy

Chemical Solid Possible Wastewater Name Waste Generated Airborne Neutralization I Compounds Requiring

' II the manulacturer specified a range for the chemical concentration, the largest value was used. Reference temperature = 68°F Specific heat capacity of water = 8.983 BtuAb mol "F Moles of water per 100 gal = 46.365 ib mol

1 3 5 7

e) Solid Waste Generation, Potential for Airborne Contaminants, and Wastewater Generation

Contaminant? Required? Treatment Chem-Clean 1220 unknown yes yes none Chem-Etch 7002 unknown yes yes aluminum I

Chem-Cid 2213 unknown yes yes metals Chemcote L497260A unknown unknown unknown unknown

Chronic Elfects: Personal Protection:

- swallowed. Nasal or respiratory damage il inhaled. None.

OSHA-approved respirator and splash goggles. Chemical-resistant gloves and appropriate protective clothing (aprons) required. Boots and face shield required. Eye wash station and emergency shower should be in close proximity. Ventilate as necessaryto keep concentrations below the threshold limit value.

-

-

9 Worker Health


Chem-Clean 1220 Acute Ellects:

HMlS hazard ranking = 3

I May cause burns or irreversible damage lo eyes. Corrosive to skin. May cause severe gastrointestinal damage if

5-18 Us and disseminalion d l h e inlormalim contained in this dwment are subincl 10 restrictions on lhe cawright page.

National Center tor Manufacturing Sciences


Table 5-9. Chemcote L497260A (continued)

g) Raw Material Toxicity and Personal Protection Data (continued)

OSHA approved respirator and splash goggles. Chemicabresistant gloves and appropriate protective clothing (aprons) required. Boots and face shield required. Eye wash station and emergency shower should be in close proximity. Ventilate as necessary to keep concentrations below the threshold limit vaiue.

Chem-Etch 7002

Acute Ellects:

HMlS hazard ranking = 3 I May cause burns or irreversible damage to eyes. Corrosive to skin. May cause severe gastrointestinal damage if

Cnronic Effects: Personal Protection:

I I swallowed. Nasal or resolraton damaae if inhaled. I

_I

cause stomacn pain ancvor nausea, ana may i n a m vomh ng.

Resp ratory I ness. ttidney aamage. asthma symptoms resembl ng rneumal sm S.specleo cancer nazaro N OSHA-approvea canister-type respirator. Cnemcal goggles an0 lace sh eo req.,reo. ho contact lenses.

-.

I Chronic Effects: I None I

Acute Ellects: Chronic Effects: Personal Protection:

Unknown

Unknown Unknown

I Chem-Cld 2213 HMlS hazard rankina = 3 I I Acute Effects: / Irritation to skin, nose, throat, and mucous membrane, and chest discomlorl. irritation or damage to eyes. May I

I . . .. . .~

Impermeable gloves and protective clothing required. Eye wash facility and emergency shower should be in close I oroximitv. Ventilate to keeo concentrations below the threshold limit value.

USB and disseminafian of be information mtained in this dOcumen1 are subjm to restrictions on he copyright page.

5-1 9

j


Table 5-10. E-CLPS 923 Environmental Impact Data Sheet

Process Type: Alternative Chrome Conversion Coating Company: Bulk Chemicals, Inc.


b) Ozone Depleting Substances (DDSs), Hazardous Air Pollutants (HAPs), and Carcinogens


d) Resource Usage - Process Chemicals, Water, and Energy

' If the manulacturer specified a range lor the chemical concentration, the largest value was used. Reference temperature = 68'F Specific heat capacity of water = 6.983 Btullb mol "F Moles of water per 100 gal = 46.365 Ib mol

5-21 Use and diSSBmination of the inloimation contained in ais dacument are subjecl Io restrictions on the copyright page.


-

Step

1 1

Chemical Solid Possible Wastewater Name Waste Generated Alrborne Neutralization Compounds Requiring -~

Contaminant? Required? Treatment

~~

Bulk Kleen 692 none yes yes none Bulk Kieen 678 none yes yes fluoride

~ LL none es es none


Chemical Name

Bulk Kleen 692 Bulk Kieen 678 E-CLPS 923

Bulk Kleen 692

Acute Effects: HMlS hazard ranking E 3

I May cause irritation or bums to the skin and eyes.

HMlS Health Total Number of Effects Protective Gear Carcinogens?

3 4 1 yes no 3 4 3 yes no 3 3 2 yes no

Hazard Ranking Acute Chronic Required ?


I Bulk Kleen 678 HMlS hazard rankina = 3 I

Respiratory irritation. Chemical goggles or face shield required. Neoprene or polyvinyl gloves and appropriate protective clothing (aprons) required. Approved filter mask or respirator required if vapor mist is present. Eye wash station and emergency shower should be in close proximity. Ventilate as necessary to keep concentrations below the threshold limit vaiue.

Acute Elfects: Chronic Eflects:


E-CLPS 923

Acute Effects: HMlS hazard ranking = 3

I Possible eye and skin irritation and tissue damage.

Eye, skin, throat, and nose bums. Lung inliammation. Pulmonary edema. Calcium depletion which leads to bone damage. Chemical face shield or goggles required. Neoprene or polyvinyl gloves and full acid suit with rubber boots required. Bureau of Mines scheduled 21B acid mist carlridge respirator required for misting operations. Do not wear contact lenses. Eye wash facility and emergency shower should be in close proximity. Ventilate as necessaly to keep exposure below the threshold limit value.

- -. Cnronic Elfects: I DecalciCcat on of wnes. E m s to sens live tissues.

Personal Protection: I Salety goggles requirea. Ruboer gloves ana protective cofhinq reqJireo Eye wash facil tv ana emerpencv snower I

. . .. . . - . I I should be in close'uroximitv. Ventilate as neksa ly to keep ConcentratlonS below the threshold limit vaiue.

5-22 Use and disseminalion of he information conlained in lhis docvmenl am subisa lo mslddions on lha mpyrighl page.


Step 1 2 3

Description Surface cleaning; Bulk Kieen 692 recommended, Bulk Kieen 695 optional Water rinsing; continuous overflow required Deoxidizelacid conditioning, Bulk Kieen 678 recommended

4 I Water rinsing 5 I Nonchrome conversion coating: E-CLPS 923 plus additive I

1 2 3 4

I 6 I Dying; heat cure I

None detected 1 detected None present None detected None detected None present None detected 1 detected None present None detected None detected None present

5 6

Total:

Unknown Unknown / Unknown None detected None detected I None present

2 + 1 unknown I 1 unknown , 1 unknown


Use and dissemindon of the inlormatiion contained in this document are subject to lllsldctions M ths mpyi$hl page.

5-23


1 3 5

Table 5-17. E-CLPS 923X (continued)


Contaminant? Required? Treatment Bulk Kleen 692 none yes yes none Bulk Kleen 678 none yes yes fluoride E-CLPS923 none yes ’ yes none Additive unknown unknown unknown unknown

.- Chemical Solid Wastewater

Name I/ Waste Generated 11 11 Neutralization I C o m p o u m l s R e q u i A

Acute Effects: Chronic Effects: Personal Protection:

Possible eye and skin irritation and tissue damage. Decalcification of bones. Bums to sensitive tissues Safety goggles required. Rubber gloves and protective clothing required. Eye wash facility and emergency shower

f) Worker Health



Unknown Unknown Unknown

Bulk Kleen 692 Acute Effects:

HMIS hazard ranking 3 I Mav cause irritation or bums to the skin and eves.

Chronic Effects: Respiratory irritation. Chemical goggles or face shield required. Neoprene or polyvinyl gloves and appropriate protective clothing (aprons) required. Approved lilter mask or respirator required il vapor mist is present. Eye wash station and emergency shower should be in close proximity. Ventilate as necessary to keep concentrations below the threshold limit valua

Bulk Kleen 678 Acute Eflects: Chronic Effects Personal Protection:

HMlS hazard rankino 3 I ~ ~~~~~~ ~~~~~

Eye, skin, throat, and nose bums. Lung inflammation. Pulmonary edema. Calcium depletion which leads to bone damage Chemical face shield or goggles required. Neoprene or polyvinyl gloves and full acid suit with rubber boots required. Bureau of Mines scheduled 21 B acid mist cartridge respirator required for misting operations. Do not wear contact lenses. Eye wash facility and emergency shower should be in close proximity. Ventilate as necessary to keep exposure below the threshold limit value.

/ should bein close proximity. Venlilate as necessary to keep concentrations below the threshold limicvalue.

5-24


2 3 4

Table 5-12. Alcoat 1470 Environmental impact Data Sheet

Process Type: Alternative Chrome Conversion Coating Company: Circle-Prosco Inc


None detected I None detected I None present None detected I 2 detected I None present None detected I None detected I None present

Descrl tion Surface cleanin ; Aicoat 1470C

Aicoat 14700 , Water rinsin

5 None detected None detected None present 6 None detected None detected None present

I

Total: 0 4 0

t ; watery j Alcoat 1470s Oven d at 250°F for 10 min

b) Ozone Depleting Substances (ODSs), Hazardous Air Pollutants (HAPs), and Carcinogens

Step 1 ODSs I HAPs I Carcinogens 1 I None detected I 2 detected I None present


I if the manufacturer specified a range for the chemical concentration, the largest value was used. ‘ Reference temperature I: 68°F Specific heat capacity of water = 8.983 Btullb mol “F Moles of water per 100 gal = 46.365 ib mol

us and dissemination 01 lhe information conlained in lhis document are subjed lo reSldCliOnS M lhe capytighl pap .

5-25


Chemical Solid Possible Wastewater Step Name Waste Generated Airborne Neutrallzatlon Compounds Requiring

Contaminant? Required? Treatment 1 Alcoat 1470C unknown yes 3 Alcoat 14708 unknown yes yes unknown

, 5 , Alcoat 14705 unknown yes yes , unknown

Chemical Name

Aicoat 147OC Alcoat 14708 Alcoat 1470s

5-26 Use and dissemination d the intormatim mlained in his document am subject to restrictions on h e mpynght page.

HMlS Health Total Number of Effects Protective Gear Carcinogens? Hazard Ranking Acute Chronic Required 7

unknown unknown unknown yes none unknown unknown unknown yes none unknown unknown unknown yes none

Acute Effects: Chronic Effects:

Personal Protedion:

Unknown Unknown Chemical goggles and neoprene Nbber gloves are required. Chemical boots and other proledive clothing (aprons) required. Approved filter mask or respirator required. Ventilation is necessary to keep concentrations below threshold limit values.


Step I OD%

Table 5-13. Alcoat 1500 Envlmnmental Impact Data Sheet

HAPs I Carcinogens

Process Type: Alternative Chrome Conversion Coating Company: Circle-Prosco Inc.


I Step I Description

Water rinsin


cl Reaulated and Hazardous Chemicals . -


' If the manufacturer specified a range lor the chemical concentration, the largest value was used. Reference temperature E 68'F Specific heat capacity of water = 8.983 Btullb mol OF Moles of water per 100 gal = 46.365 Ib mol

Use and diswminalion of Ihe inlwmation contained io this drmmsnl are subjsd lo msld&ns on Ihs copyright page

5-27


Chemical Solid Possible Wastewater Step Name Waste Generated Airborne Neutrallzatlon Compounds Requiring

Contaminant? Required? Treatment 1 Alwat1500C unknown yes yes unknown 3 Alwat15008 unknown yes yes unknown 5 , Alwat15OOS unknown yes yes , unknown

~~

~

Chemical Name

Aimat 150OC Alwat15008 Aiwat 1500s


Alcoat 15M)C, 15008, and 1500s Acute Effects: I Unknown

HMlS hazard ranking = Unknown

HMlS Health Total Number d Effects Protective Gear Carcinogens? Hmrd Ranking Acute Chronic Required ? no

unknown unknown unknown yes no unknown unknown unknown yes no unknown unknown unknown yes no

I Chronic Effects: I Unknown 1 required. Approved filter mask or respirator required. Ventilation is necessary to keep concentrations below threshold limit values.


Table 5-14. Alcoat 2000 Environmental lmpact Data Sheet



Step I Description 1

1 1 hone Detected I 2 deteneo 1 None presenl 2 j hone aetenea I hone deteaed 1 hone presenl

c) Reaulated and Hazardous Chemicals

d\ Resource Usaae - Process Chemicals, Water, and Energy

I It the manufacturer specilied a range for the chemical concentration, the largest value was used. Relerence temperature = 68°F Specific heat capacity of water = 8.983 Btu/ib mol "F Moles 01 water per 100 gal = 46.365 Ib mol

5-29 Use and dissemination of Ihs informah contained in this dmumenlare subjea Io asltidons on the copytight pags.


Chemical Name

Table 5-14. Alcoat 2000 (continued)


HMlS Health Total Number of Effects Protective Gear Carcinogens? Hazard Ranking Acute I Chronic Required?

Alcoat 20M)S unknown I unknown I unknown I no

Acute Effects: Chronic Ellects: Personal Protection:

5-30 Use and disseminalbn 01 the information w h i n e d in this document are subiect 10 restrictions on the mwright page.

Unknown Unknown

Chemical goggles and neoprene rubber gloves are required. Chemical boots and other protective clothing (aprons) required. Approved filter mask or respirator required. Ventilation is necessary to keep concentrations below threshold limit vaities


Table 5-15, Alcoat 3000 Environmental lmpact Data Sheet

Process Type: Alternative Chrome Conversion Coating Company: Circle-Prosco inc.


Alcoat 30008 Water rinsin




U WetTotal I 200 gal ' If the manufacturer specified a range for the chemical concentration, the largest value was used.

Relerence temperature 68°F Specific heat capacity 01 water = 8.983 Btuilb mol O F Moles of water per 100 gal = 46.365 ib mol

Uw and dissemination ol the inlormalicn cmlained in this 5-31 dwment are SublSn 10 RSltidIQnS On the mpytighl page.


Step


e) Solid Waste Generation, Potential for Airborne Contamfnants, and Wastewater Generation

Chemical Solid Possfble Wastewater Name Waste Generated Airborne NeutraIIzalion I Compounds Requiring

I II 11 Contaminant? 11 Required? 1 IAicoat3000C unknown yes yes 3 I Alcoat 30M)B unknown yes yes

Treatment . unknown unknown

Chemical Name

Alcoat3ooOC Alcoat3OOOB


HMlS Health Total Number of Etfects Protective Gear Carcinogens? Hazard Ranking Acute Chronic Required ?

unknown 3 unknown yes no unknown unknown unknown yes no

'

Alcost 3WOB

Acute Effects: I Unknown HMlS ha rd ranking = Unknown

Alcoat3WOC

Acute Effects:

Chronic Effects: Unknown Personal Protection:

HMlS hazard ranking Unknown

Can cause irritation to the skin, eyes, and respiratory system.

Chemical goggles and neoprene rubber gloves are required. Chemical boots and other protective clothing (aprons) required. Approved filter mask or respirator required. Ventilation is necessary to keep concentrations below threshold limit values.

I Chronic EHects: I Unknown Personal Protection: Chemical goggles and industrial rubber apron and gloves are required. Chemical boots required. Approved filter

mask or respirator required. Full face shield should be used. Ventilation is necessary to keep concentrations below threshold limit values.

5-32 Us and disssmination ol the inlonation wnminnd in this documenlaresubinn loresldnimson lha mprighl paw.


Step ODSs HAPs 1 None detected None detected 2 None detected None detected

Table 5-16. Alcoat 4000 Environmental Impact Data Sheet

Process Type: Alternative Chrome Conversion Coaling Company: Circle-Prosco inc.


Carcinogens None present None present

I step I Description

Total: I 0

Alcoat 4OoOC

Water rinsin

4 0

Water rinsin

3 I None oefecteo 2 oeiecteo I hone present 4 I None aeiected I None oetecteo I hone present

I 5 I Nonedetected I2detected I None present I 6 I None aeiecteo I None oetecteo I hone present 7 I None aeiecteo I None oetecteo I hone present I

Use and disseminalion of Ihe information conlained in this document are subject Io restfinions an lhe capyrighl page.

5-33


Acute Effects: Chronic Elfects: Personal Protection:



Can cause irritation to the skin and eyes. Unknown - Splash-proof goggles and rubber gloves required. Rubber boots and aDmn are also required. Ventilate as

' It the manufacturer specified a range lor the chemical concentration. the largest value was used. " Reference temperature = 6B"F Specjfic heat capacity 01 water = 8.983 Btu/lb mol O F Moles of water per 100 gal = 46.365 Ib mol


9 Worker Health


AlCoat 4000C HMlS hazard ranking E Unknown

. . .. necessary to keep concentrationsbelow the threshold limit value. Approved filter maskor respirator required if vapor mist is present. -

?-

5-34 Use and diss8minalion of lhe inlomalon conlainsd in this d c w " are subiecl to resttidims on lhe cowtight pags.


Acute Ellects: Chronic Effects: Personal Protedion:

Unknown Unknown Chemical goggles and neoprene rubber gloves are required. Chemical boots and other protective clothing (aprons) required. Approved lilter mask or respirator required. Ventilation is necessary to keep concentrations below threshold limit value.

Alcoat 4000s Acute Ellects:


I Can cause severe burns to the eyes, skin, and mucous membranes.

Chronic Effects: Personal Protedion:

Unknown Chemical goggles and neoprene rubber gloves are required. Chemical boots and other protective clothing (aprons) required. Approved fiiter mask or respirator required. Ventilation is necessary to keep concentrations below threshold limit values.

5-35

i


Table 5-17. Alcoat 5000 Environmental lmpact Data Sheet



5 I Alcoat 50005 6 I Oven dry at 250'F lor 10 min



1 I sodium tripolyphosphate I Alwat 5OOOC I 7758-29-4 I none 3 zirconium salt I Alwat5000B I unknown I unknown I unknown q

d) Resource Usage - Process Chemicals, Water, and Energy .

' I1 the manulacturer specilied a range lor the chemical concentration, the largest value was used. ' Relerence temperature = 68'F Specilic heat capacity of water = 8.983 Btullb mol OF Moles of water per 100 gal = 46.365 Ib mol

Use and dissemination of the information conlained in lhis document are subjea to mstnoUons on the mpynght page.

5-37

National Center for Manufacturing Sdences

Step

1 3 5

Possible Wastewater Chemical Solid

Waste Generated Airborne Neutralization Compounds Requiring -~ Name Contaminant? Required? Treatment

Alcoat5WOC unknown yes yes unknown Alcoat50M)B unknown yes yes unknown Alcoat5000S unknown yes yes , unknown

~~

~

f) Worker Health



Can cause eye, skin, and respiratory irritation. Unknown

Splash-prool goggles and rubber gloves required. Rubber boots and apron are also requried. Ventilate as necessary to keep concentrations below the threshold limit vaiue. Approved filter mask or respirator required if vaDor mist is Dresent.

Acute Effects:


Unknown Unknown

Chemical goggles and industrial rubber apron and gloves are required. Chemical boots required. Approved filter mask or respirator required. Full face shield should be used. Ventilation is necessary to keep concentrations below threshold limit values.

-

5-38 Use and disseminalion of Ihe inlormalim Mnleinsd in this documenl are subjen lo restnclims on he copyright page.

Alcoat 50005 Acute Effects: Unknown Chronic Effects: Unknown Personal Protection:


Chemical goggles and neoprene rubber gloves are required. Chemical boots and other protective clothing (aprons) required. Approved filter mask or respirator required. Ventilation is necessary to keep concentrations below threshold iimil VaIIIA


1 2 3 4 5

Table 5-18. GM 1 Envimnmental Impact Data Sheet

Process Type: Alternative Chrome Conversion Coating Company: General Motors, Delphi Harrison Thermal Systems

Unknown Unknown Unknown None detected None detected None present None detected None detected None present None detected Nom detected None present None detected , None detected None present ~

a) Number of Process Steps step I Description

~

6 1 None detected 7 I None detected

~otal: I 1 unknown

~~~ :: c1e;i;: C~~CWP~OSC;PC~ZZ 4 Water rns n ' continLous overhow assLmeo Sudace lreatin ; trietnanolam ne Water nns, , continuhs overflow- Non-chrome convers'on coa1.n ; cerods CnlOnOe Water rinsin : ContinuoJs overflow assmeo

7 D in : 10minar250'F

None detected None present None detected None present

1 unknown 1 unknown

bl Ozone DeDletina Substances (ODSs), Hazardous Air Pollutants (HAPs), and Carcinogens -, ~ - 1 step I ODSs I HAPs I Carcinogens

C) Regulated and Hazardous Chemicals

d) Rei~urce Usage- Process Chemicals, Water, and Energy

' II the manulacturer specilied a range lor the chemical concentration, the largest value was used. * Relersnce temperature = W F Specilic heat capacity of water = 8.983 Btu/lb mol OF Moles 01 water per 100 gal = 46.365 ib mol


step

1 3 5

Chemical Solld Posslble Wastewater Name Waste Generated Airborne Neutralhatton Compounds Requlrlng

Contamlnant? Required? Treatment PC522 unknown unknown unknown unknown triethanolamine unknown yes no no

,cerowchloride unknown unknown unknown unknown

9 Worker Health

Chemical Name

PC522 triethanolamine cercus chloride

HMlS Health Total Number of Elfecto Protective Gear Carcinogens? Acub

unknown unknown unknown 1 5 4 yes no

unknown unknown unknown unknown no


:necrs: I rermna Protection:

Pc522 Acute Eflects: I Unknown

HMlS hazard ranking Unknown

Unknown

Unknown Unknown

Chmnic Eflecls: I Unknown Pemnat Protectmn: I Unknown

~

I Personal Protadion: I Local exhaust, respirator with organic vapor carlridge. Splashproof goggles, appropriate clothing.


In CAS Threshold Llmlt Number Value (ACGIH)

Step Chemical

Table 5-19, GM2 Environmental hpact Data Sheet

Process Type: Alternative Chrome Conversion Coating Company: General Motors, Delphi Harrison Thermal Systems


Permissible Expo- Source Code sure Limit (OSHA) (see Tab e 5.2)


9 I None detected I None detected I None present Total: I Zunknown 1 2unknown I 2 unknown


~~

Use and dissemination 01 Ihe informalion contained in lhis document 84 subjsd lo reslricliOnr an lhe mpyrighl page.

5-41


Chemical Name

Table 5-19. GM2 (continued)


HMIS Health Total Number of Effects Protective Gear Carcinogens? Hazard Ranking Acute 1 Chronlc Required?

Name Usage? PC522 27,905

PC522 AC8 Triethanolamine Cerous Chloride

' if the manufacturer specilied a range for the chemical concentration, the largest value was used. ' Relerence temperature = 68°F Specilic heat capacity of water = 8.983 Btullb mol OF Moles of water per 100 gal = 46.365 ib mol

unknown unknown unknown unknown unknown unknown unknown unknown unknown unknown

1 5 4 yes no unknown unknown unknown unknown no


Acute Eflects: Chronic Eflects: Personal Protection:

9 Worker Health


Acute Eflects: Chronic Effects: Personal Protection:



5-42 Use and dissemination ot the iniormatim Wnlained in vlis dmumsnt are subject to reslric~ions on he copyright page.


Acute Effects: Chronic Eflects: Personal Protection:

Skin and eye irritation, poisonous to system, causes respiratory irritation. If ingested, will burn gastrointestinal tract May cause dermatitis and eczema. Also causes conjunclivitis and central nervous system depression. Local exhaust, respirator with organic vapor canridge. Splashproof goggles, appropdate clothing.

Acute Ellects: Chronic Effects:

Personal Protection

U s and dissminabn ol the inlormaAoo wnlained in Ihis dDNment are subim lo resmons M the mpydghl page.

5-43


L


1 2 3

4

Surface cleaning; Ridoiine 53 recommended Water rinsing; continuous overflow required Deoxidizing; Deoxidizer 6 with Deoxidizer 16 as replenisher recommended (Deoxodizer 6 and Replenisher 16 may be replaced by Deoxidizer 7 and Replenisher 17 depending on amounl of oxidation present.) Water rinsing; continuous overllow required

-~

Table 5-20. Alodine 1200s Environmental Impact Data Sheet

Process Type: Chrome Conversion Coating-Baseline Reference Company: Parker Amchem

a) Number of Steps (Vendor has several treatment options available depending on the condition of the panel to be treated.)

I step I Description

3 5

potassium ferricyanide Replenisher 17 13746-66-2 I none none q - potassium ferricyanide Alodine 1200s 13746-66-2 I none none 9 potassium fluoborate 14075.53-7 I 2.5 mglm’ 2.5 mglm’ 9

5 6

I Dying; air dry or heal cure; clean uncontaminated heat sources 7

I Chrome conversion coaling; Alodine 1200s I Water rinsing; continuous overflow required


c) Regulated and Hazardous Chemicals (Only Deoxidizer 6 with Replenisher 16 was evaluated in this assessmenl.)

Use and dissemination of the information contained in this dccument are subjet4 to reStrictionS on the mpytisht page

5-45


Chemical Step Name

1 Ridoline53 3 Deoxidizer 6

5 Alodine 1200s Replenisher 16 ~~~~~~ ~

Table 5-20. Alodine 1200s (continued)

d) Resource Usage- Process Chemicals, Water, and Energy

Solld Posolble Wastewater Waste Generated Airborne Neutralization Compounds Requiring

Contaminant? Required? Treatment aluminum silicate yes yes phosphates aluminum fluoride yes yes none aluminum fluoride yes yes none aluminum fluoride; yes yes chromium compounds; copper ferricyanide fluoride compounds;

potassium ferricyanide

- ~~

- ~~

~

' II the manufacturer specified a range lor the chemical concentration, the largest value was used. ~~

' Reference temperature = 68°F Specific heat capacity of water = 8.983 Btu/lb mol "F Moles of water per 100 gal = 46.365 ib mol

Ridoline 53

Acute Elleds:


NFPA hazard ranking = 2

May cause burns or damage to eyes. Can cause irritation or dermatitis to skin. Inhalation of dust can be an irritant to the respiratory tract. Ingestion can result in gastrointestinal damage. There are no known medical conditions aggravated by prolonged exposure.

required. MSHANIOSH dust filter mask or respirator required il dusting occurs. Eye wash station and emergency Chemical goggles or lace shield required. Neoprene or polyvinyl gloves and appropriate protective clothing

-

-

f) Worker Health


5-46 Use and dissemination of the information contarned in this document are SubiSn to restriclims on the mpyrighl pap.


&cute Effects:

Table 5-20. Alodlne 12Mls (continued)


Contact with eyes, skin, or mucous membranes can cause severe burns, which may not be immediately painful or visible. Material causes acid bums. Large burns may also cause hypocalcemia and other systemic ellects which may be FATAL. Inhalation of vapors can cause extreme irritation of the respiratory tract, pulmonary edema, congestion, and fluorosis. Ingestion could result in tissue destruction of the digestive tract, and even small amounts can cause potentially FATAL hypocalcemia and systemic toxicity. This product contains chromic acid which may


. .- 1 be absomed throLgn !he sk n Chromic ac'd is considereo very 1ox.c I Contains I uorioes. Exposure 10 fluor des over years may cause I Loros s Conla ns cnrom c ac d Prolonged or Chronic Effects

repeated skin contact may cause "chrome sores.'' Longterm exposure can cause liver damage, kidney damage, and dermatitis. Prolonged or repeated inhalation 01 mist may cause ulceration and perforation of nasal septum. POSSiBLE CANCER HAZARD. May aggravate respiratory diseases. Chemical face shield or goggles required. Neoprene or polyvinyl gloves and appropriate protective clothing required. MSHAINIOSH approved respirator required lor misting operations. Eye wash facility and emergency shower should be in close proximity.


Same as Deoxidizer 6.

Same as Deoxidizer 6. Same as Deoxidizer 6.

Acute Effects:

Chronic Elfects:

Contact with eyes may result in loss 01 vision or severe burns. Product is corrosive to skin tissues. Inhalation of dust can irritate the respiratory tract. Ingestion could result in tissue deStNCtiOn of the digestive tract and severe imitation 01 the respiratory tract.

Prolonged or repeated exposure to skin may cause "chrome sores." Long-term exposure may cause liver damage,

Use and dissemination c4 Ihe inlmlim wnlained in this drmmenl are subiea lo restridons ~1 lh mwrighl page.


5-47

kidney damage, and dermatitis. Prolonged or repeated inhalation may cause ulceration and perforation of the nasal septum. Contains fluorides. Exposure to fiuoriis over years may cause fluorosis. POSSIBLE CANCER HAZARD. Local exhaust required. Chemical faw, shield or goggles required. Neoprene or polyvinyl gloves and appropriate protective clothing required. Eye wash station and emergency shower should be in close proximity.


CAS Threshold Limit Number Value (ACGIH)

Contained In Chemical (carcinogens indicated in bold)

Step

1 tetrasodium pyrophosphate Ridoiine 53 7722-88-5 5 m g / d 3 hydrogen fluoride Deoxidizer 6 7664-39-3 3 ppm as F

Table 5-21. Alodine ZOO0 Environmental Impact Data Sheet

Process Type: Alternative Chrome Conversion Coating Company: Parker Amchem


Permissible Expo- Source Code sure Limit (OSHA) (see Table 5.2)

5 mg/ma m, n 3 ppm as F d-g, i, j, m o

8 9

I Water rinsing; continuous overfiow required 1 Dtying; air dry or heal cure


ODSs I HAPs I Carcinogens

I Total: 1 unknown I 3 t 1 unknown I 1 t 1 unknown

Use and dissemination dlhe inlarmalim mlained in lhis document are subject Io mlrictions MI lhs copyright Page.

5-49


step

1 3

5

7

Table 5-21. Alodine 2000 (continued)


Chemical Solid Posslble Wastewater Name Waste Generated Airborne Neutralization Compounds Requiring

Contaminant? Required? Treatment Ridoline 53 aluminum silicate yes yes phosphates Deoxidizer 6 aluminum fluoride yes yes none Replenisher 16 aluminum fluoride yes yes none TD2WOH unknown yes no none

no no none TD Zoo01 - yes no none TD 30578 -

TD3095Y unknown unknown unknown unknown

Chemical I Amount 11 Continuous Name Il*ana?

Process Chemicals' Water Energ4

..-...- ---~". ("F) (Btu) i Gallons Tfin Q,," T,, Q,,,

(Btu) 1 Ridoline 53 12.5 Ib no 100 140 29,986 160 36,318

9,163

Step

- - yes 200 ambient NIA ambient

NIA 21,658

5 gal no 100 50 With Nitric Acid 10 gal

- yes 200 ambient 10 gal no 100 120

1.75 gal

' If the manufacturer specilied a range for the chemical mncentration, the largest value was used. Reference temperature = 68'F Specific heat capacity of water = 8.983 Btdb mol "F Moles of water per 100 gal = 46.365 Ib mol

f) Worker Health

5-50 Usa and disseminalion ol the inlormalim mtained in his documen1 are subjen lo realfinions on the Wpyrighl page.


Acute Ellecls:

Chronic EHects: Personal Protection:

May cause burns or damage to eyes. Can cause irritation or dermatitis to skin. inhalation 01 dust can be an irritant to the respiratory tract. ingestion can resuit in gastrointestinal damage. There are no known medical conditions aggravated by prolonged exposure.

Chemical goggles or face shield required. Neoprene or polyvinyl gloves and appropriate protective clothing required. MSHAlNiOSH dust filter mask or respirator required if dusting occurs. Eye wash station and emergency I shower should be in close proximity. Local exhaust required.

Acute Eflects:

Chronic EHects:

Contact with eyes, skin, or mucous membranes can cause severe burns, which may not be immediately painful or visible. Material causes acid bums. Large bums may aim cause hypocalcemia and other systemic effects which may be FATAL. inhalation of vapors can cause extreme irritation 01 the respiratory tract, pulmonary edema, congestion. and Iluorosis. Ingestion could result in tissue destruction 01 the digestive tract, and even small amounts can cause potentially FATAL hypocalcemia and systemic toxicity. This product contains chromic acid which may be absorbed through the skin. Chromic acid is considered very toxic. Contains Iluorides. Exposure to lluorides over years may cause fluorosis. Contains chromic acid. Prolonged or repeated skin contact may cause 'chrome sores.'' Long-term exposure can cause liver damage, kidney damage, and dermatitis. Prolonged or repeated inhalation of mist may cause ulceration and perforation of nasal septum, POSSIBLE CANCER HAZARD. May aggravate respiratory diseases. Chemical lace shield or goggles required. Neoprene or polyvinyl gloves and appropriate protective clothing required. MSHAlNiOSH approved respirator required for misting operations. Eye wash laciiity and emergency shower should be in close proximity.

- Personal Protection:

Acute Effects: Chronic EHects: Personal Protection:

TD 2000H Acute Elleds:

NFPA hazard ranking 1

I Contact with eyes causes irritation. Contact with skin can cause allergic skin reactions to occur. Inhalation 01 dust





I I gloves and appropriate protective clothing required. Eye wash station and emergency shower should be in close 1

can cause respiratory iiiness and lung disease. Ingestion could resuit in blood, heart, and pancreas damage.

None Local exhaust required. NlOSH approved respirator recommended. Chemical goggles required. Chemical-resistant

Uw and dissemination ol h e inlomum rmtained in (his dOEUment ale subled to restncfions M (he copyright page

5-51


TD 20001

Acute Effects: NFPA hazard ranklng = 1

Can cause eye and skin irritation. inhalation causes nose, throat, and respiratory tract irritation. Ingestion is moderatelv toxic.

- I . . . . . . . -. . .

Chronic Effects:

Personal Protection: I Lccal exhaust required. NlOSH approved respirator not normally required. Chemical aoaales rewired. Chemical-

I Could result in kidney damage.

I . . - -- I resistant gloves and appropriate pmtective clothing required. Eye wash station and emergency shower should be

in close oroximitv.

~~

~

Acute Effects: Contact with eyes wuld result in bums and damage. Contact with skin can cause burns. inhalation of mist can cause nose, throat, and respiratory tract irritation. Ingestion could result in gastrointestinal damage and digestive tract burns.

TO 309W

Acute Effects: I Unknown

NFPA hazard ranking Unknown


Chronic Effects: I Unknown Personal Protection: I Unknown Acwrding to information received from Parker Amchem after completion of the assessment, TD 3095Y is a proprietary tungstenhanadium seal. The technology has been changed since the coatings were provided. The current version has a hazard ranking = 1.

None.

Local exhaust required. NlOSH approved respirator recommended. Chemical resistant gloves and appropriate protective clothing required. Eye wash station and emergency shower should be in close proximity. Ventilate to keep below threshold limit values.

5-52 Useand dissemination of he.in1om~mmlBinedinlhis document are subjet3 lo rsstridons On tha d e h l Page.


Step ODSs HAPs 1 None detected None detected 2 None detected None detected 3 None detected 1 detected

Table 5-22. Patclin 7970 A, 6, C Environmental lmpact Data Sheet

Process Type: Alternative Chrome Conversion Coating Company: Patclin Chemical Co., Inc.


Carcinogens None present None present None present

6 7 8 9

Total:

4 I None detected I None detected I None present 5 I None detected I 1 detected 1 None present

None aetected None detectea None present None aetefled 1 aetectea (manganese) None present Noneaetefled Nonedetedea None present None aetected None aetected None present

0 3 0

c\ Reauiated and Hazardous Chemicals

5-53 Use and diSwmination d the information contained in lhis document are rubjecf to restrictions on h e copyright page.


1 8 )

I

Table 5-22, Patclh 1910 A, 6, C (continued)


I yes I 200 11 ambient 1 NIA I ambient I NIA - - Dry Totail 90.5 ib Totail 1,100 I/ Totall 110,789 1 Totall 110,789 Wet Totail unknown

Chemical Solid Possible Step Name Waste Generated Airborne

Wastewater Neutralization I Compounds Requiring

1 Patdin 342 3 Patclin 366G 5 De-smutter 7 Patciin 1910

9 Worker Health

For those chemicals with more than one component, the number given is lor the component with the highest hazard ranking.


.~ Contaminant? Required? Treatment

unknown yes no unknown

unknown yes yes unknown unknown yes yes unknown

unknown yes I yes unknown

Acute Eflects:


I Pstclin 842 -Sodium Triaolvohosohate NFPA hazard rankina = 1 I

Upper respiratory irritation, coughing, shortness of breath. Skin and eye irritation. Corneal bums. Abdominal pain, vomiting, nausea. Oral bums. Burns to alimentary canal. May cause dermatitis and conjunctivitis. Ulcerations of mouth and gastrointestinal disturbances. Chemical goggles or face shield required. Rubber gloves and appropriate pmtective clothing (aprons) required. Respirator required. Eye wash station and emergency shower should be in close proximity. Normal ventilation.

. ___r..,r ... . ... ~~~

Acute Ellens: Chronic Effects:

I lrntaton to 00th eyes ana sk n. Sore throat, cmgning, snorlness 01 breath. Abdom na pain. t Caused arowth retardation. e evated ddnevmdv we aht rat os. an0 1.b- ar neohrooalhv in rats "~ ~ ~~ , , " , . . ~ ~ ~~. ~ I Personal Protection: I Chemical goggles or face shield required. Rubber gloves and appropriate protective clothing (aprons) required. I

I I ResDiratorreiuired. Eve wash station and emeroencv shower should be in close omximitv. Normal ventilation. I

5-54 Use and disseminalon of the informalon contained in lhiS dacument are subject lo resttinions bn the mpytight page.


Acute Effects:


Nasal irritation. Pneumonitis at high concentrations. Skin irritation and damage. May cause disintegration or damage to eyes. lntemal burns if ingested. Nasal passage ulceration. Skin dermatitis. May cause conjunctivitis. Ventilate to keep below exposure limits. NIOSHA approved respirator required. Safety goggles and face shield required. Chemical-resistant gloves and protective clothing required. Eye wash lacility and emergency shower should be in close proximity.

rPatclin366G -Sodium Gluconate NFPA hazard ranking Unknown (assuming 3 or less)

on: Chronic Ellects:


Acute Ellects:

Chronic Ellects: Personal Protection:

Nausea, vomiting, iightheadedness. Respiratory Irritation. Irritation or burns to skin or eyes. Internal burns if ingested. Adverse effect on kidneys, possibly latal. Safety goggles and face shield required. Acid-resistant gloves and appropriate protective clothing (aprons) required. Respirator required. Eye wash station and emergency shower should be in close proximity. Ventilate to keep below exposure limits. Acid cartridge (recommended) respirator required.

Desmutter - Ammonium Bifiuoride Acute Ellects:

NFPA hazard ranking = 3 I lrritat on to respiratory system, co,gh ng. shortness of oreatn. Irrtation 01 b,ms to sltin and eyes. intema


ingested. May cause or aggravate asthma. Dermatitis, conjunctivitis, fluorosis. Splash-praol goggles and face shield required. Protective gloves and appropriate protective clothing (aprons) required. Acid cartridge (recommended) respirator required. Eye wash station and emergency shower should be in close pmximity. Ventilate to keep below exposure limits.

Patciin 1910 - Potassium Permanganate Acute Ellects: Chronic Effects: Personal Protection:

NFPA hazard ranking 1 Severe irritation to respiratory tract. irritation and burns to skin and eyes. Internal burns if ingested. Causes tooth erosion and mouth damage. Dermatitis. May cause mariganism. Splash-prool goggles and face shield required. Rubber gloves and appropriate protective clothing (aprons) required. DusWmist respirator recommended. Eye wash station and emergency shower should be in close proximity. Ventilate to keep below exposure limits. -

Acute Effects: Chronic Ellects: Personal Protection:

USB and dismminalion of the information conuined in this drmmnl are subjed lo rastncbns on me copylight page

May cause mucous membrane irritation, coughing. irritation to skin and eyes. May cause dermatitis and increase bone density. Splash-proof goggles and face shield required. Rubber gloves and appropriate protective clothing (aprons) required. DusWmist respirator recommended. Eye wash station and emergency shower should be in close proximity. Ventilate to keep below exposure limits.

5-55


Table 5-23. Patclin 19118 Environmental lmpact Data Sheet

Process Type: Alternative Chrome Conversion Coating Company: Patclin Chemical Co., Inc,


Total:


Use and dissemination of the information conlained in this dwumsnl are subject to resttinions on the mpyright pug0

5-57


Step

1 3 5 7

Table 5-23. Pafclin 191 16 (continued)


Chemical Solid Possible Wastewater Name Waste Generated Airbome Neutralization Compounds Requiring

Contaminant? Required? Treatment Patciin 342 unknown yes no unknown Patciin 366G unknown yes yes unknown Desmutter unknown yes yes unknown Patdin 1911 unknown yes yes unknown

' it the manufacturer specilied a range for the chemical concentration, the largest value was used. Relerence temperature = 68°F Specific heat capacity 01 water = 8.983 Btullb mol "F Moles of water per 1W gal = 46.365 ib mol

Chemical Name

Patciin 342 Patciin 3666

NFPA Health Total Number of Effects Protective Gear Carcinogens? ' Hazard Ranking' Acute I Chronic Required 1

3 11 I 7 yes no 3 unknown I unknown yes no

9 Worker Health

Acute Effects: Upper respiratory irritation, coughing, shortness 01 breath. Skin and eye irritation. Corneal burns. Abdominal pain, vomitino. nausea. Oral burns. Burns to aiimentarv canal.

Chronic Ellects. Persona Protect:on,

~ ~,~~ ~ ~~ ~~~ ".

May cause dermatitis and con.unn vlt s. Licerat ons 01 m o n ana gastroinleslinai a StJrbanCas. Cnem ca goggles or lace shieia requ red. Ruboer gloves ana appropr ate protective c 0th ng (aprons) requ.rea Respirator requ red. Eye wash s1at;on ana emergency snower sno.ld be in c ose prox m ty. hormai ventiation. -_

.. ._ -_-_ Eye wasn station and emergeny Shower snouia ne in c ose prox mity. horma vent la1 on

I Pa tch 342 -Sodium TliDOlVDhOSDhate NFPA hazard rankina 1 I . ,. . " A w e Ellects Chronic Ellects

I irntat on to Dotn eyes ana SI( n Sore throat, cough ng shonness 01 Dreath Aooom na pan I Cause0 arowtn retardat on. e evateo I( dnevloodv weight ratios and tuo.iar neohronathv in rats

5-58 Uss and dissemination of the inlormasoo cantained in his document 818 subject to restriaions on h e mpyrighl page.


-. - . Patclln 3660 -Sodium Hydroxide

Acute Effects:

Chronic Eflects: personal Protection:

NFPA hazard ranking = 3 Nasal irritalion. Pneumonitis at high concentrations. Skin irritation and damage. May cause disintegration or damage to eyes. Internal bums if ingested. Nasal passage ulceration. Skin dermatitis. May cause conjunctivitis. Ventilate to keep below exposure limits. NIOSHA approved respirator required. Safety goggles and face shield required. Chemical-resistant gloves and protective clothing required. Eye wash facility and emergency shower

Table 5-23. Patclin 191 fB (continued)

a) Raw Material Toxicity and Personal Protection Data (continued)




Desmutter - Nitric Acid Acute Effects:

NFPA hazard ranking = 3 I Nausea, vomiting, lightheadedness. Respiratory irritation. irritation or burns to skin or eyes. internal bums if

ingested. Adverse effect on kidneys, possibly fatai. Safety goggles and lace shield required. Acid-resistant gloves and appropriate protective clothing (aprons) required. Respirator required. Eye wash station and emergency shower should be in close proximity. Ventilate to keep below exposure limits. Acid cartridge (recommended) respirator required.


~ ~~~

Desmuner - Ammonium Bifluorlde Acute Ellects:

NFPA hazard ranking = 3 I Irritation to respiratory system, coughing, shortness of breath. Irritation or bums to sMn and eyes. internal burns if ingested. May cause or aggravate asthma. Dermatitis, conjunctivitis, fluorosis. Splash-proof goggles and face shield required. Protective gloves and appropriate protective clothing (aprons) required. Acid cartridge (recommended) respirator required. Eye wash station and emergency shower should be in close proximity. Ventilate to keep below exposure limits.

Acute Ellects: Chronic Efiects: Personal Protection:

Severe irritation to respiratory tract. Irritation and burnsto skin and eyes. Internal burns if ingested. Causes tooth erosion and mouth damage. Dermatitis. May cause manganism. Splash-prool goggles and face shield required. Rubber gloves and appropriate protective clothing (aprons) required. DusVmist respirator recommended. Eye wash station and emergency shower should be in close proximily. Ventilate to keep below exposure limits.

_ _ _ _ Chron c Ellects Personal Proten on

[ May cause oermatit s ana ncrease Done density I Solash-orool aoooes and face shied reau red RuoDer gtoves ana appropriate protect ve ciotnlng (aprons)

I - "" I 1 reh ied DusVmisl respirator recommended. Eye wash station and emergency shower should be in ciose

I 1 proximity. Ventilate to keep below exposure limits.

Use and disseminahn d the inlomtion cmlained in this document 818 wbiw lo restridnns M Iha wpylight paw

5-59

i

-

!


Step t 2

Table 5-24. Sandia 1 and Sandia 2 Environmental lmpact Data Sheer

Process Type: Alternative Chrome Conversion Coating Company: Sandia National Laboratories

ODSs HAPs I Carcinogens None detected None detected I None present None detected None detected I None present




U s e and dissemination of the inlormalion mtained in this document are subjecl lo resttictiom on the copytighl page

5-61


Step

1 3

5 7

Table 5-24. Sandia 1 and Sandia 2 (continued)


Possible Wastewater Chemical Solid Name Waste Generated Airborne Neutrallzatlon Compounds Requiring

Contaminant? Required? Treatment Alconox unknown yes no Aimnox sodium metasilicate unknown yes no unknown - sodium carbonate unknown yes no unknown Sanchem 1000 unknown no no unknown sodium aluminate unknown no no unknown lithium carbonate unknown yes no unknown

' If the manufacturer specified a range lor the chemical concentration, the largest value was used. Reference temperature = 68°F Specific heat capacity 01 water = 8.983 Btdib mol "F Moles of water per 100 gal = 46.365 Ib mol

sodium aluminate unknown 4 I unknown I yes no

t) Worker Health

lithium carbonate 1 7 4 yes no

5-62


Acute Elfects: Chronic Effects: Personal Protection:

Irritation to the skin and eyes. Unknown. Chemical lace shield or aoaales required. Proper doves and appropriate protective clothinq reauired. Eve wash - _ _ . - . . . . . facility and emergency shower should be in close proximity. Local exhaust required. If airborne concentrations are hiah. use a resoirator.

Acute Effects:


Upper respiratory irritation, coughing, shortness of breath. Skin and eye irritation. Corneal burns. Abdominal pain, vomiting, nausea. Oral bums. Burns to alimentary canal. May cause dermatitis and conjunctivitis. Ulcerations 01 mouth and gastrointestinal disturbances.

Chemical goggles or face shield required. Rubber gloves and appropriate protective clothing (aprons) required. Respirator required. Eye wash station and emergency shower should be in close proximity. Normal ventilation.

Sodium Carbonate Acute Eflects:


I Mav cause couohina. shortness of breathe. oastrointestinal chanaes. and mucus membrane irritation.


Decrease in weight gain and perforation of nasal septum. May cause internal damage.

Splash-prool goggles required. Proper gloves and appropriate protective clothing required. Eye wash lacility and emergency shower should be in dose proximity. Local exhaust required. Use an approved respirator or selfcontained breathing apparatus, depending on airborne concentration.

Sanchem 1000 NFPA hazard ranklng = 1 1


Acute Eflects: I None. Chmnic Effects: 1 None.

Unknown. Proper goggles and lace shield required. Rubber gloves and appropriate protective clothing required. Eye wash lacility and emergency shower should be in close proximity. Local exhaust required. Respirator or selfcontained breathing apparatus are not normally required.

I Personal Protection: I Rubber gloves and local exhaust required. J


Sodium Aluminate

Acute Ellects:

NFPA hazard ranking Unknown

I May cause bums to the skin and eyes, blindness, and irdtation and burns to the respiratory tract.

" - . . Affects skin, eyes, gastrointestinal tract, and central nervous system. Splash-proof goggles or lace shield required. Rubber gloves and appropriate protective clothing (aprons) required. Use an appmved respirator or self-contained breathing apparatus, depending on airborne concentration. Eye wash station and emergency shower should be in close proximity. Local ventilation.


I Mav cause couoh na, sore throat and in'tat on. Allens win eves. gastro nlestinal tract. an0 centra neN0t.s system.

5-63


1 2 3 4 5

Table 5-25. Alumicoat 6788 Environmental Impact Data Sheet

Process Type: Alternative Chrome Conversion Coating Company: Elf Atochem - Turco Products Division


Surface cieaninudegreasing Water rinsing; continuous overliow assumed Deoxidizeldesmutler Water rinsing; continuous overllow assumed Nonchrome conversion waling

step I Description

Step ODSs 1 Unknown 2 None detected

HAPs Carcinogens Unknown Unknown None detected None present

6 7

I Dry ng; arip dry I Post-dry cxe 30 min al I8O'F

5 6 7

Unknown Unknown I Unknown None detected None detected 1 None present None detected None detected I None present

3 1 Unnnown I Un<nown I h n o w n 4 I None oelecied I None oelecled I None presenl

' Con,ained In CAS Threshold Limit Number Value (ACGIH)

Chemical Step Permissible Expo- Source Code sure Llmlt (OSHA) (see Taole 5-21

I Total: I 3unknown I 3unknown I 3unknown I * Turco has stated that there are no carcinogens in this process. No MSDS was provided. In such cases, RPI preters to apply the "unknown" designation for the purposes of this assessment, in order to treat inlormation from all suppliers on a consistent basis.


Use and direemination 01 be information mntained in this document are subleet to resttidons on the mpyright page.

5-65


Chemical Solid Possible Wastewater Step Name Waste Generated Alrborne Neutralization Compounds Requiring

Contaminant? Required? Treatment 1 Cleanerldegreaser unknown unknown unknown unknown 3 Deoxidizer unknown unknown unknown unknown

, 5 .Alumicoat6788 unknown unknown .. unknown ,unknown

Table 5-25. Alumicoat 6788 (continued)


Chemical HMlS Health Name Hazard Ranking

Degreaser unknown Deoxidizer unknown Alumicoat 6788 unknown

' If the manufacturer specified a range for the chemical concentration, the largest value was used. Reference temperature = 68'F Specilic heat capacity 01 water = 8.983 Btu/lb mol "F Moles of water per 100 gal = 46.365 Ib mol

Total Number of Effecto Protective Gear Carcinogens?

unknown unknown unknown unknown unknown unknown unknown unknown unknown unknown unknown unknown

Acute Chronlc Required ?

Acute Etlects: Chronic Effects: Personal Protection:

Unknown tor all three chemicals Unknown tor all three chemicals Unknown for all three chemicals'

~~~~~ ~ ~

5-66 Uss and disseminaabn of the inlormalion contained in ais document 818 subjen to reittictiom on the mpydght page.


3 4 5 6

Total:

Table 5-26.2438-280 Environmental Impact Data Sheet

Process Type: Alternative Chrome Conversion Coating Company: Elf Atochem - Turco Products Division


Unknown Unknown Unknown None detected None detected None present Unknown Unknown Unknown None detected None detected None present .

3 unknown 3 unknown 3 unknown

b) Ozone Depleting Substances i (ODSs), Hazardous Air Pollutants (HAPs), and Carcinogens*

Step I ODSS I HAPs I Carcinogens 1 1 Unknown I Unknown I Unknown 2 1 None detected I None detected I None present



I II 11 NIA 1 N/A 11 NIA I NIA - - - - DryTotalI unknown 11 Total I unknown 1 Total I 25,823 11 Total I 25,623 WetTotal I unknown 1

' II the manufacturer specilied a range for the chemical cancentration, the largest value was used. * Reference temperature = 68°F Spedlic heat capacity of water = 6.983 Btdb mol "F Moles 01 water per 1M) gal = 46.365 Ib mol

Use and dissemination d me InIomUon contained in h is d r m m s n t a r e s u b j e n l o m ~ ~ o n l h e mpyrighlpage.

5-67


Step

1 3 5

Table 5-26.2438-28D (continued)

Chemical Solid Possible Wastewater Name Waste Generated Airborne Neutralization Compounds Requiring

Contaminant? Required? Treatment - Cleanerldegreaser unknown unknown unknown unknown Deoxidizer unknown unknown unknown unknown 243828D unknown unknown unknown unknown


Chemical Name

Cleanerldegreaser Deoxidizer 2438-28D

Health . Total Number oi Effects Protective Gear Carcinogens?

unknown unknown unknown unknown unknown unknown unknown unknown unknown unknown unknown unknown unknown unknown unknown

Hazard Ranking Acute Chronic Required 1

f) Worker Health


I Dwreaser HMlS hazard rankina = Unknown I I Deoxidizer HMlS hazard rankina i: Unknown I

I Chronic Effects: I Unknown for all three chemicals I I Personal Protection: I Unknown for all three chemicals* I ' Turco recommends gloves, respirator, Nbber aprons, and goggles as personal protection for the degreaser and deoxidizer steps only. No

MSDS was provided. In such cases, RPI prelers to apply the "unknown" designation for the purposes 01 this assessment, in order to treat information from all suppliers on a consistent basis.


step ODSs HAPs 1 None detected 1 detected 2 None detected None detected

Table 5-27. Ce-Mo 2024 Environmental lmpact Data Sheet

Process Type: Alternative Chrome Conversion Coating Company: University of Southern California


Carcinogens None present None present

3 IUnknown I Unknown I Unknown 4 1 None detected I None detected I None present

5-69 Use anddisseminatianol the inlamalion conlainsd in this dmmenl8re subject to restdclions On the copyright page.


9 Ce(CH,CO$ Ce (CH,CO$ unknown unknown unknown 9

- 13 Ce(NOJ3 cerium nitrate unknown unknown unknown 9 11 sodium molybdate sodium molybdate unknown unknown unknown 9


I II the manufacturer specified a range for the chemical omcentration, the largest value was used. ' Reference temperature = 68°F Specilic heat capacity 01 water = 8.983 Btuhb mol "F Moles of water per 100 gal = 46.365 ib mol

5-70 U s and disseminaflon of h e inlormalm contained in this dmumenl are subied lo restrictions on h s copyright page.


Solid Possible Waste Generated Airborne

Contaminant?

Table 5-27. Ce-Mo 2024 (continued)


Wastewater Neutralization Compounds Requiring

. Required? Treatment S@P

1

3 5

7 9

11 13

f) Worker Health

Chemical Name

hexane Alconox Diversey 560 Deoxidizer 7

phosphoric acid nitric acid Ce(CH,CO$ sodium molybdate cerium nitrate

. . . ~ ~


, - ~ " " ~~~ ~

sure limits are ab&e the threbhold k i t value: if &centration is below 1000 ppm, use organic vapor cartridge; and if concentration is above loo0 ppm, use sell-contained breathing apparatus. Eye wash Station and emergency shower should be in close proximity. Ventilate to keep below exposure limits. Local exhaust required.

~~

Hexane Acute Ellects:


I Can cause irritation to skin or eves. Headache, nausea, vomiting, dizziness, and drowsiness may occur. irritation

Acute Ellects: Chronic Effects: Personal Protection:

to the respiratory tract, loss of consciousness, and narcosis may also result. ingestion can resuit in gastrointestinal I inilltin"

Irritation to the skin and eyes. Unknown Chemical face shield or goggles required. Proper gloves and appropriate protective clothing required. Eye wash lacilib and emergency shower should be in close proximity. Local exhaust required. If airborne concentrations are high, use a respirator.

.. .."..".. Chronic Elfects Personal Ploted on

I Central nervous system depress on I SaleN 0000 es readreo NeoDrene uioves an0 aDprOpr ate protectlve clothlng requ red Resplrator reqL red 11 expo


Acute Eflects:



Diversey 560 Acute Ellects: 1 Unknown Chronic Elfects: I Unknown Personal Protection: I Unknown

hazard ranking Unknown

-

Eye burns and skin irritation may occur. May causa bums to the respiratory tract and digestive tract. May cause damage to the gastrointestinal tract.

- 1 Deoxidizer 7 NFPA hazard rankina = 3 I

~ ~~


I

.. -. . . , .. ~~ ~~~ , ~~~~~~ ~~~~~ ~~.

None Chemical lace shield or goggles required. Polyvinyl alcohol gloves and appropriate protective clothing required. Respirator required if exposure limits are above the threshold limit value: if concentration is below 12 ppm, use a high.particulate cartridge; and if the concentration is above 12 ppm, use self-contained breathing apparatus. Eye wash laciiity and emergency shower should be in close proximity. Local exhaust required. Ventilate to keep below exuosure limits.

Persona Protea;on: Chemical face snield or goggles reqLiren. Neoprene or polyv nyi g oves ann appropr ale protect,ve cloth ng requiren. Approved resp ralor recommendw. Eye wasn lacility and emergency shower shou,d be in close

Acute Elfects:


I I oroximitv. Local exhaust reauired. Ventilate to keeo below exoosure limits. I

Nausea, vomiting, lightheadedness. Respiratory irritation. irritation or burns to skin or eyes. Internal burns il ingested. Adverse eltect on kidneys, possibly fatai. Safety goggles and lace shield required. Acid-resistant gloves and appropriate protective clothing (aprons) required. Respirator required. Eye wash station and emergency shower should be in close proximity. Ventilate to keep below exposure limits. Acid cartridge (recommended) respirator required.

Phosphoric Acid Acute Effects:

NFPA hazard ranking = 2 I Eve burns and skin irritation mavoccur. Mav cause initation to the res~lratow trad

Sodium Molybdate Acute Effects: 1 Unknown Chronic Elfects: I Unknown

hazard ranking = Unknown

- Cerium Nitrate Acute Elfects: \ Unknown Chronic Eflects: I Unknown


P c r s n n i l Prolortinn. I I inknnwn

5-72 Use and diaminalion d the inbrmalion wnlained in lhis document 818 subject lo r e s t i c h s on ne mwiaht pap.


2 None detected None detected None present 3 Unknown Unknown Unknown 4 None detected None detected None present

-

Table 5-28. Ce-Mo 6061 Environmental Impact Data Sheet



5 6

9 10 I Surface modilication 1 11

I Oxidizing; baking at 100°C for 2 days

I Water rinsing; continuous overflow unknown (assumed)

None detected 2 detected Potassium dichromate None detected None detected None present

i i; ~ ~ u r f a c e m o ~ 2 pp ~ ~ 1 Water rinsin ;continuous overfiow unknown assumed Surface modification 3; 500 mV a lied for 2 hours Water rinsin ; continuous overfiow unknown assumed

9 10 11 12 13

I 16 I Dying; (assumed) I

None detected None detected None present None detected None detected None present None detected None detected None present None detected None detected None present None detected None detected None present


14 15 16

Step I ODSs I HAPs I Carcinogens 1 I None detected I 1 detected I None present

None detected None detected I None present None detected None detected I None present None detected None detected 1 None present

7 I None aetened 1 1 oetectea I hone present a I None detened I None aetecled I None present 1

1 Total: I 1 unknown I 4 + 1 unknown I 1 + 1 unknown j

Use and dissemination of the inlormalion contained in this dpcumenl are subjsa to restrictions on the cowright page.

5-73


3 10 12 14


unknown Diversey 560 unknown unknown unknown 9 CeCI, CeCI, unknown unknown unknown q

Ce(N0$ cerium nitrate unknown unknown unknown q sodium molybdate sodium molybdate unknown unknown unknown I


Process Chemicals' Water Energy'

Step Chemical Amount Gallons Tdn 9," T,. Q,, Name Usage? ("F) (Btu) ("F) (Btu)

1 hexane unknown no 100 ambient N/A ambient NIA Alconox unknown

U Wet Total I unknown 11 ' If the manufacturer specified a range for the chemical concentration, the largest value was used.

Reference temperature = 68°F Specific heat capacity of water = 8.983 Btu/lb mol "F Moles of water per 100 gal = 46.365 Ib mol

5-74 Use and difrsminalian of lhs information wnlainsd in ais dmumenlm subien lo reslriclons on Ihe wpynghl page.


Chemical Solid Step Name Waste Generated

1 hexane none



Possible Wastewater Airborne Neutralization Compounds Requiring

Contaminant? Required? Treatment yes no I hexane

3 5

Aiconox none yes no Alconox DiverseySM) none unknown unknown unknown

chromium compounds; fluoride compounds

Deoxidizer 7 none yes Yes

hydrochloric acid none yes yes none ?

7 10 12 14

9 Worker Health

nitric acid none yes yes none CeCI, none unknown unknown unknown cerium nitrate none unknown unknown unknown sodium molybdate none unknown unknown unknown


Acute Ellects:

Chronic Elfects: Personal Protection:

Can cause irritation to skin or eyes. Headache, nausea, vomiting, dizziness, and drowsiness may occur. irritation to the respiratory tract loss of consciousness, and narcosis may also result. Ingestion can result in gastrointestinal irritation. Central nervous system depression. Salety goggles required. Neoprene gloves and appropriate protective clothing required. Respirator required if exposure limits are above threshold limit value: if concentration is below 1000 ppm, use organic vapor carlridge; and if concentration is above 1000 ppm use, sell-contained breathing apparatus. Eye wash station and emergency shower should be in close Droximitv. Ventilate to keep below exuosure limits. Lcal exhaust required.

I % Alcanax Acute Ellects: Chronic EHects: Personal Proledon:

Irritation to the skin and eyes. Unknown Chemical lace shield or goggles required. Proper gloves and appropriate protective clothing required. Eye wash facility and emergency shower should be in close proximity. Local exhaust required. If airborne concentrations are high, use a respirator.

U s a d disseminabn of Ihe inlormatian mlained in lhis dwment are subject tp mslMons on Ihe mr.yti$l pap .

5-75


Acute Effects:

Chronic Effects:




Diversey 5M) Acute Effects: I Unknown Chronic Effects: I Unknown Personal Protection: I Unknown


Eye burns and skin irritation may occur. May cause burns to the respiratory tract and digestive tract. May cause damage to the gastrointestinal tract. Chrome sores. Liver and kidney damage. Dermatitis and fluorosis may occur. Ulceration and perforation of the nasal septum. Chemical face shield or goggles required. Neoprene or polyvinyl gloves and appropriate protective clothing rewired. Aooroved resoirator recommended. Eve wash lacilitv and emeraencv shower should be in close

Acute Effects:


~ ~ ~~ ~ ~~ ~ I proximity. iocal exhaust required. Ventilate to ieep belowexiosure limit;, ’ I

Burns to skin and eyes. internal bums il ingested. May cause nausea and vomiting. Irritation 01 the respiratory tract. May cause pulmonary edema. Chemical lace shield and goggles required. Acid-resistant gloves and appropriate protective clothing required. Respirator required if exposure limits are above threshold limit value: il concentration is below 100 ppm, use an acid cartridge; and if concentration is above 100 ppm, use sell-cuntained breathing apparatus. Eye wash facility and emergency shower should be in close proximity. Local exhaust required. Ventilate to keep below threshold

Acute Eflects: Nausea, vomiting, lightheadedness. Respiratory irritation. Irritation or bums to skin or eyes. lntemal burns il inoested.


j Personal Protection: I Unknown I

Adverse effect on kidneys, possibly fatal. Safety goggles and lace shield required. Acid-resistant gloves and appropriate protective clothing (aprons) required. Respirator required. Eye wash station and emergency shower should be in close proximity. Ventilate to keeo below exoosure limits. Acid carlridoe (recommended) resoirator reouired.

Cerium Nitrate Acute Eflects: I Unknown Chronic Effects: I Unknown Personal Protection: I Unknown


Sodium Molybdate Acute Effects: 1 Unknown Chronic Effects: I Unknown Personal Protection: I Unknown


5-76


Table 5-29. CeMo 7075 Environmental lmpact Data Sheel




step I ODSs HAPs I Carcinogens 1 1 None detected 1 detected I None present 2 None detected None detected I None present 3 Unknown Unknown I Unknown

Use and dissemination d the informaYon mtained in this dmumsnl are subject to nstriedons ~1 the Cowright Page.

5-77


Step

1 5

CAS Threshold Limit Permissible Expo. Source Code (carcinogens indicated in bold) Number Value (ACGIH) sum Llmlt (OSHA) (see Table 5-2) hexane hexane 11 0-54-3 180 ms/" 1 .E g/m3 I , m, n sodium bifluoride Deoxidizer 7 1333-83-1 2.5 mglm' . 2.5mg/m3 n

Contained In Chemical

otassium nitrate 7757-79-1 I none none P otassium dichromate 7778-50-9 I 0.05 mglm3 I 0.1 mg/m3 n

Step

1


Process Chemicals' Water Energ$ - Amount Continuous Gallons T ~ . QM" T"", Q,

Name Usage? ("F) (mu) ("F) @tu) Chemical

hexane unknown no 100 ambient NIA ambient NIA Alconox unknown

5-70 Use and dissaminalion d he informalion mlained in his dmmenl are subject to reSlriCtims on the copyright page.



Table 5-29. Ce-hfo 7075 (continued)


Waste Generated

to the respiratory tract, loss of consciousness, and narcosis may also resuit. Ingestion can resuit in gastrointestinal irritation. Central nervous system depression. Salety goggles required. Neoprene gloves and appropriate protective clolhing required. Respirator required if exposure limits are above threshold limit value: if concentration is below 1000 ppm, use organic vapor cartridge; and if the concentration is above 1wO ppm use, sell-contained breathing apparatus. Eye wash station and emergency shower should be in close proximity. Ventilate to keep below exposure limits. Lcal exhaust required.

9 Worker Health

Alconox Acute Effects:

Baker system hmrd ranking 1

I Irritation to the skin and eyes. Chronic Elfects: I Unknown Personal Protection: I Chemical face shield or goggles required. Proper gloves and appropriate protective clothing required. Eye wash

I I facility and emergency shower should be in close proximity. Local exhaust required. If airborne concentrations are I I high, use a respirator.

Use and dbaminalbm d the information wntained in his document 818 subien to msIiclons MI h e mpyrigM pap.

5-79


Dlversey 560 Acute Effects: I Unknown Chronic Eflects: I Unknown Personal Protection: I Unknown

hazard ranklng I Unknown

-

Acute Effects:

Chronic Effects:


Eye burns and skin irritation may occur. May cause burns to the respiratory tract and digestive tract. May cause damage to the gastrointestinal tract. Chrome sores. Liver and kidney damage. Dermatitis and fluorosis may occur. Ulceration and perforation of the nasal septum. Chemical face shield or goggles required. Neoprene or polyvinyl gloves and appropriate protective clothing required. Approved respirator recommended. Eye wash facility and emergency shower should be in close proximity. Local exhaust required. Ventilate to keep below exposure limits.

Acute Effects:


Burns to skin and eyes. lntemal bums if ingested. May cause nausea and vomiting. Irritation of the respiratory tract. May cause pulmonaiy edema. Chemical face shield and goggles required. Acid-resistant gloves and appropriate protective clothing required, Respirator required if exposure limits are above threshold limit value: il concentration is below 100 ppm, use an acid cartridge; and il concentration is above 100 ppm, use selfcontained breathing apparatus. Eye wash facility and emergency shower should be in close proximity. Local exhaust required. Ventilate to keep below threshold limit value.

I =

Cnron c Ellects Personal Protecrion

I Adverse effect on I( dneys. poss oay lata I Safetv aoaoles ana lace snield readed Acid-res slant oloves and anomor ate ororective c 0th ng (aprons)

Acute Elfects:

I - _- I I required. Respirator required. Eye'wash station and emergency shower sihouldi

Nausea, vomiting, lightheadedness. Respiratory irritation. Irritation or burns to skin or eyes. Internal burns il inaested.

Ne in close proximity Ventilate to I I I keeo below exoosure limits. Acid cartridoe frecommendedl resoirator rewired. I

e hazard ranking = Unknown I Unknown I I Inknnl","

~~ ~~~~~ ~~~~~~ ~

Sodium Molybdate hazard ranking = Unknown I I Inbnnam

hazard ranking E Unknown I Unknown

Is: I Unknown ection: I Unknown

5-80 Use and dirreminabnallhe inlomascn containedinlhis dmumenl are rubiecl Io reslriclims on Ihe cowrishl page.


6. References 1.

2.

3.

4.

5.

6.

7.

8.

Chalmer, P. and Buchheit, R. “Compa- rative Testing of Precommercial and Commercial Chromate-Free Conversion Coatings for Aluminum Alloys.” Paper 373, 1995 NACE International Annual Confer- ence and Corrosion Show, Houston, TX.

ASTM B117 - 90. “Standard Method of Salt Spray (Fog) Testing.” ASTM, Phila- delphia, PA. May 1990.

MIL-C-5541E. “Chemical Conversion Coatings on Aluminum and Aluminum Alloys.” 30 November 1990.

American Society for Testing and Materi- als. ASTM D-3359. “Standard Test Meth- ods for Measuring Adhesion by Tape Test.” ASTM, Philadelphia, PA. 1987.

MIL-C-8 1706. “Chemical Conversion Materials for Coating Aluminum and Alu- minum Alloys.” 30 June 1970. Including Interim Amendment 5. 13 November 1979.

Federal Test Method Standard No. 141C. “Paint, Varnish, Lacquer and Related Ma- terials, Methods of Inspection, Sampling and Testing.” Method 6301.2 “Adhesion (Wet) Tape Test.” January 24, 1986.

Bailin, L. J., P. Fitzpatrick, and M. J. Joyce. “Evaluation of Unpainted Alodine Chro- mate Conversion Coatings for Corrosion Resistance and Electrical Conductivity.” LMSC-FO35575 Rev. A, Appendix E. Lockheed Missiles and Space Corporation, Inc., Palo Alto, CA. June 1985.

Finch, J. “Procedure for Contact Electrical Resistance Measurements as Developed

for Use at Sandia National Laboratories.” June 1994.

9. Clarizia, M., N. Clesceri, and J. Korngold. “Environmental Impact Assessment for Alternatives to Chrome Project.” February 1995.

10. Felton, L. et al. “An Environmental Appraisal of Alternatives to Chromium Conversion Coatings.” Design and Manufacturing Institute. May 1994.

11. United States Environmental Protection Agency, Stratospheric Protection Division. “Imported and Exported Ozone-Depleting Substances.” June 1994.

12. United States Environmental Protection Agency. “Clean Air Act, Section 602.” 1990.

13. Henry, J. and G. Heinke. Environmental Science and Engineering. Prentice Hall, Englewood Cliffs, NJ. 1989.

14. United States Environmental Protection Agency. “Clean Air Act, Section 112b.” 1990.

15. New York State Department of Environ- mental Conservation, Division of Air Resources. “Proposed 6 NYCRR Part 201.” May 1995.

16. United States Environmental Protection Agency. “EPA/600/8-89/053 Hazard Rank- ing of Potential Carcinogens.” June 1988.

17. California Environmental Protection Agency. “Chemical Cross Index (List of Lists).” November 1992.

U s and dissminaiim of he inlomafin” cmtsined in this documsnlm subjed io reariclions an h e copyright page.

6-1

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Alternatives to Chromium for Metal Finishing

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