1、Designation: D 6442 06Standard Test Method forDetermination of Copper Release Rate From AntifoulingCoatings in Substitute Ocean Water1This standard is issued under the fixed designation D 6442; the number immediately following the designation indicates the year oforiginal adoption or, in the case of
2、 revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope*1.1 This test method covers the laboratory determination ofthe rate at which copper is released f
3、rom an antifouling (AF)coating in substitute ocean water. The practical limits forquantifying copper release rates by this method are from 1.8 to500 g cm-2d-1. This range may be extended to 0.2 to 500 gcm-2d-1if the analytical procedure described inAppendix X1 isfollowed.NOTE 1The term “substitute o
4、cean water” is used throughout thisstandard to refer to artificial or synthetic seawater prepared in accordancewith Practice D 1141.1.2 The procedure contains the preparation steps for therelease rate determination of copper from antifouling paintsincluding apparatus, reagents, holding tank conditio
5、ns, andsampling point details.Analysis for the concentration of copperin substitute ocean water requires the accurate determination ofcopper at the low parts g L-1(parts per billion, ppb) level. Todetect and correct for reagent impurities, acceptable analyticalprecision standards are necessary. Ther
6、efore, the limit ofquantitation (LOQ) for copper in substitute ocean water for theanalytical method shall be 10 g L-1(10 ppb) or less. Theprocedure for determining the LOQ for copper in substituteocean water for the analytical method is found in Annex A2.1.3 A suitable method is described in Appendi
7、x X1 (graph-ite furnace atomic absorption spectroscopy, GF-AAS). Otheranalytical methods may be utilized with relevant proceduralchanges, as needed, to accommodate selected specific methods.Such methods must meet the limit of quantitation for copper insubstitute ocean water of 10 g L-1(10 ppb) or le
8、ss. See 1.2.1.4 This results of this test method do not reflect environ-mental copper release rates for antifouling products, and arenot suitable for direct use in the process of generatingenvironmental risk assessments, environmental loading esti-mates, or for establishing release rate limits for r
9、egulatorypurposes. See also Section 4 on Significance and Use.1.5 The values stated in SI units are to be regarded as thestandard. The values given in parentheses are for informationonly.1.6 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is t
10、heresponsibility of the user of this standard to establish appro-priate safety practices and to determine the applicability ofregulatory limits prior to use. For specific hazard statements,see Section 7.2. Referenced Documents2.1 ASTM Standards:2D 1005 Test Method for Measurement of Dry-Film Thick-n
11、ess of Organic Coatings Using MicrometersD 1141 Practice for the Preparation of Substitute OceanWaterD 1193 Specification for Reagent Water3. Summary of Test Method3.1 The candidate paint is applied to cylindrical test speci-mens. The coated specimens are placed in a tank of substituteocean water wh
12、ere the copper levels are kept below 100 g L-1by circulating the substitute ocean water through a suitablefiltration system (see 5.3). At specified intervals, each speci-men is placed in 1500 mL of substitute ocean water (seeSection 9 for details) and rotated at 60 revolutions per minute(rpm) for 1
13、h (or less, see 9.8 for further explanation andinstruction). The rate of copper release from the paint isdetermined by measuring copper concentrations of the substi-tute ocean water in the individual measuring containers.3.2 Appendix X1 provides an analytical procedure formeasuring copper concentrat
14、ions in substitute ocean water.4. Significance and Use4.1 This test method is designed to provide a laboratoryprocedure to quantify and characterize the release rates ofcopper from antifouling coatings in substitute ocean water over1This test method is under the jurisdiction of ASTM Committee D01 on
15、 Paintand Related Coatings, Materials, and Applications and is the direct responsibility ofSubcommittee D01.45 on Marine Coatings.Current edition approved June 1, 2006. Published August 2006. Originallyapproved in 1999. Last previous edition approved in 2005 as D 6442 - 05.2For referenced ASTM stand
16、ards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.1*A Summary of Changes section appears at the end of this standard.Copyright ASTM Inter
17、national, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.a period of immersion under specified laboratory conditions ofconstant temperature, pH, salinity, and low copper concentra-tion. Quantitative measurement of the release rate is necessaryto help in selection
18、 of materials, in providing quality control,and in understanding the performance mechanism.4.2 Results from this test method establish a pattern ofcopper release from an antifouling coating over a minimum of45 days exposure under controlled laboratory conditions.Copper release rates from antifouling
19、 paints in-service varyover the life of the coating system depending on the formula-tion and on the physical and chemical properties of theenvironment. Factors such as differences in berthing locations,operating schedules, length of service, condition of paint filmsurface, temperature, pH, and salin
20、ity influence the actualrelease rate under environmental conditions. Results obtainedusing this test method do not reflect actual copper release ratesthat will occur in-service, but provide comparisons of therelease rate of different antifouling formulations in substituteocean water under the prescr
21、ibed laboratory conditions.4.3 By comparison with copper release rate measurementsobtained either by direct measurements of copper release ratefrom AF coating systems on ship hulls, or copper release ratemeasurements from AF coating systems from harbor exposedpanels, all available data indicate that
22、 the results of this testmethod (Test Method D 6442) significantly overestimate therelease rate of copper when compared to release rates underin-service conditions. Published results demonstrate that thistest method produces higher measurements of copper releaserate than from direct in-situ measurem
23、ents for the same coatingon in-service ship hulls and harbor-exposed panels. Thedifference between the results of this test method and the paneland ship studies was up to a factor of about 30 based on datafor several commercial antifouling coatings.3,4Realistic esti-mates of the copper release from
24、a ships hull under in-serviceconditions can only be obtained from this test method wherethe difference between the results obtained by this test methodand the release rate from an AF coating in-service is taken intoaccount.4.4 Where the results of this test method are used in theprocess of generatin
25、g environmental risk assessments, forenvironmental loading estimates, or for regulatory purposes, itis most strongly recommended that the relationship betweenlaboratory release rates and actual environment inputs is takeninto account to allow a more accurate approximation of thecopper release rate f
26、rom antifouling coatings under real-lifeconditions. This can be accomplished through the applicationof appropriate correction factors.45. Apparatus5.1 Release Rate Measuring ContainerA nominal 2 L (12gal.) polycarbonate container, approximately 13.5 cm (5.3 in.)in diameter and 19 cm (7.5 in.) high,
27、fitted with threepolycarbonate rods approximately 6 mm (nominal14 in.) indiameter to serve as baffles. Rods shall be evenly spaced on theinside circumference of the container to prevent swirling of thewater with the test cylinder during rotation. The rods will besecured to the container walls using
28、acetone or methylenechloride (see Annex A1).5.2 Constant Temperature ControlA means of maintain-ing the release rate measuring test containers at a temperatureof 25 6 1C during the rotation period (see 9.8).5.3 Holding TankAn inert plastic container of such di-mensions so as to permit immersion of f
29、our or more testcylinders; must be equipped with a system to continuouslycirculate the substitute ocean water in the tank through anactivated carbon filter and optionally an absorbent filter.5If anabsorbent filter is used, regenerate the ion-exchange resinfollowing the manufacturers instructions and
30、 wash the resinwith substitute ocean water prior to use. The rate of water flowand the size of the filter(s) shall be selected to maintain copperconcentrations below 100 g L-1. Flow rates should be set toobtain 2 to 8 turnovers per hour.5.4 The size and geometry of the tanks as well as thepositionin
31、g of the inflow and outflow ports for the watercirculation system shall be selected to obtain a slow, relativelyuniform flow of substitute ocean water past all test cylinders inthe tank. Maintain the pH of the substitute ocean waterbetween 7.9 and 8.1, the salinity between 33 and 34 parts perthousan
32、d (ppt), and temperature at 25 6 1C (77 6 2F).5.5 Test CylindersApproximately 6.4 cm (nominal 212in.) outside diameter by 17.8 cm (nominal 7 in.) long polycar-bonate pipe or equivalent polycarbonate cylindrical shapescoated with a 10 cm (3.94 in.) band of antifouling paint aroundthe exterior circumf
33、erence of the test cylinder to provide 200cm2of paint film that can be immersed and freely rotated in therelease rate measuring container (see Note 2). A top disc, fittedwith a shaft of proper diameter for the rotating device, shouldbe sealed to the cylinder. Seal the bottom of the test cylinderwith
34、 a polycarbonate disc using acetone, methylene chloride ora polycarbonate cement so as to form a watertight joint. Do notcoat the lower 1 to 2 cm (0.39 to 0.79 in.) of the test cylinder.The test cylinder shall be of such height so that a rotatingdevice can be attached to rotate the cylinder with the
35、 upper endof the cylinder above the level of the test container immersionliquid to prevent entry of the immersion liquid into the testcylinder (see Annex A1). It is advisable to weight the cylinderby filling with water so that the unit does not have buoyancy.NOTE 2When coating release rates are very
36、 high, it may be desirabletousea5cmband (100 cm2) paint area to avoid exceeding 200 g L-1ofcopper in the measuring containers (see 9.8.1).5.6 Test Cylinder Rotating DeviceThe device shall becapable of rotating the test cylinder in the release rate measur-ing container at 60 6 5 rpm (0.2 6 0.02 ms-1,
37、 velocity of testcylinder surface). No part of the device shall be immersed insubstitute ocean water.3Valkirs, A. O, Seligman, P. F., Haslbeck, E., and Caso, J. S., Marine PollutionBulletin, Vol 46 (2003), pp 763779.4Finnie, A. A., Improved Estimates of Environmental Copper Release Ratesfrom Antifou
38、ling Products, Biofouling, Vol. 22 (2006). In press.5A filter cartridge, containing a chelating iminodiacetic (alternative spelling imminodiacetic) acid ion-exchange resin on a styrene support (nominal particle sizerange approximately 0.300 to 0.850 mm (20 to 50 mesh) of sufficient capacity torequir
39、e regeneration only once a month or less frequently, has been found suitable.D64420625.7 Sample Tubes60 mL capacity with screw closures (ordisposable bottles, culture tubes, etc.) made of polycarbonate,polypropylene or borosilicate glass.5.8 DispensersAutomatic or repeating for reagents.5.9 pH Meter
40、, with a suitable electrode.5.10 Appropriate Hydrometer or Salinometer.5.11 Appropriate Volumetric Flasks.5.12 Disposable Polypropylene Syringes,60mL.5.13 Syringe Filters, 0.45 m.6. Reagents and Materials6.1 Purity of ReagentsAll reagents and cleaning agentsare to be reagent grade or better.6.2 Puri
41、ty of WaterDistilled water conforming to Type IIof Specification D 1193.6.3 Substitute Ocean WaterArtificial ocean water in ac-cordance with Practice D 1141, section on Preparation ofSubstitute Ocean Water, or a proprietary equivalent with asalinity of 33 to 34 ppt and pH 7.9 to 8.1.6.4 Extraction M
42、ediaActivated carbon and, optionally, achelating ion-exchange resin,5iminodiacetic (imminodiacetic)acid exchange resin on a styrene support, nominal particle sizerange approximately 0.300 to 0.850 mm (20 to 50 mesh) (see5.3).6.5 Copper StandardsPrepare standards using a stocksolution of copper, 1000
43、 mg L-1(1000 ppm), or other concen-tration suitable to the selected analytical technique (see Section8).6.6 Nitric Acid (HNO3)Concentrated, high purity grade.6.7 Hydrochloric Acid (HCl), 10 %, v/v, aqueous solution.6.8 Sodium Hydroxide (NaOH),1N, aqueous solution.6.9 Deionized Water.6.10 Sodium Chlo
44、ride (NaCl), 5 M, aqueous solution.7. Hazards7.1 WarningAntifouling paints may contain toxic mate-rials that could cause skin and eye irritation on contact andadverse physiological effects if ingested or inhaled. See anti-fouling coating suppliers Material Safety Data Sheet.7.2 In the preparation of
45、 test specimens and the applicationof various types of paints, the use of appropriate protectiveclothing and equipment is required consistent with local, state,and federal government regulations, and recognized industrialand technical standards. Spills, overspray, and unused materialshould not be fl
46、ushed down the drain, but should be disposedof as hazardous waste.8. Calibration and Standardization8.1 Prepare five suitable standards from the copper stocksolution (see 6.5) in a medium appropriate to the analyticalmethod.8.2 Prepare spikes in substitute ocean water at 10, 50 and200 g L-1to cover
47、the working range of the method.Additional spikes may be prepared at appropriate levels andappropriate to the analytical technique being used.8.3 At the beginning of each instrument run, analyze asuitable blank and standards in order to establish that theresponse of the instrument is linear. Plot se
48、parate calibrationcurves for each analysis of the standards (instrument responseversus copper concentration) and calculate the slope, intercept,and correlation coefficient for each curve using least squares fitor another appropriate procedure.8.4 Analyze the following:8.4.1 Substitute Ocean Water Bl
49、ank: Acidify, extract andanalyze as specified (see 9.10 and 9.11) for test samples, toestablish baseline.8.4.2 Spiked Substitute Ocean Water Samples: Acidify, ex-tract and analyze as specified (see 9.10 and 9.11) for the testsamples to determine extraction efficiency. Recovery must be100 % 6 10 % for the 50 g L-1spike and spikes of higherconcentration. Recovery must be 100 % 6 15 % for spikeswith a concentration below 50 g L-1.9. Procedure9.1 Clean polycarbonate ware with tap water then rinse withdeionized water. All glass laboratory ware used fo
