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现行 ASTM D6903-07(2020)
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Standard Test Method for Determination of Organic Biocide Release Rate From Antifouling Coatings in Substitute Ocean Water 用于替代海水中防污涂料的有机杀菌剂释放速率的标准测试方法
发布日期: 2020-08-01
1.1 本试验方法涵盖实验室测定暴露在替代海水中的防污涂层释放有机杀生物剂的速率。该测试完全在pH、温度、盐度和流体动力学的受控条件下在实验室中进行。提供了用于测定4,5-二氯-2-n-辛基异噻唑啉-3-酮(DCOIT)、锌和铜硫腙(ZPT和CuPT)的释放速率的分析程序,以及 N -环丙基- N ′ -(1,1-二甲基乙基)-6-(甲硫基)-1,3,5-三嗪-2,4-二胺(CDMTD)。 在预定的时间间隔内,使用合适的分析技术分析替代海水样品中的浸出杀生物剂。 1.2 在防污涂层同时包含有机杀生物剂和铜基杀生物剂的情况下,可以根据试验方法中的程序选择性地同时测定铜的释放速率 D6442 . 1.3 该程序包含用于测定防污涂料替代海水中杀生物剂释放速率的准备步骤,包括仪器、试剂、储罐条件和采样点细节。 该程序要求在较低温度下准确测定替代海水中的有机杀生物剂浓度 μ g L -1 (十亿分之一,ppb)水平。为了检测和校正试剂杂质,并达到适当的分析精度,用于测定替代海水中有机杀生物剂浓度的分析方法必须满足中给出的可接受标准 附件A2 . 哪里 附件A2 规定了定量限(LOQ),即通过中提出的分析方法测定替代海水中有机杀生物剂的LOQ的程序 附件A3 必须遵循。 1.4 中给出了使用高效液相色谱法(HPLC)测定替代海水中DCOIT、ZPT和CuPT以及CDMTD浓度的合适分析方法 附录X1– 附录X3 分别地可以使用其他方法,前提是它们满足中给出的适当标准 附件A2 . 1.5 当测定高度光敏性有机杀生物剂的释放速率时,必须采取措施保护仪器和样品免受自然和人工可见光源的照射。 对特定杀生物剂采取这些步骤的任何此类要求如 附件A2 . 1.6 通过该方法量化杀生物剂释放率的实际极限为4.5到500 μ g厘米 -2 d -1 对于DCOIT,0.36到500 μ g厘米 -2 d -1 对于CuPT,0.36至500 μ g厘米 -2 d -1 对于ZPT,和2.7至500 μ g厘米 -2 d -1 用于CDMTD。这些范围可以扩展到3.8到500 μ g厘米 -2 d -1 对于DCOIT,0.16到500 μ g厘米 -2 d -1 对于CuPT,0.2至500 μ g厘米 -2 d -1 对于ZPT,和2.2至500 μ g厘米 -2 d -1 对于CDMTD,如果按照 附录X1– 附录X3 (视情况而定)。低于这些范围的释放率定量将需要使用定量限低于中规定的分析方法 附件A2 . 1.7 本试验方法的结果不反映防污产品的环境杀生物剂释放速率,不适合直接用于生成环境风险评估、环境负荷估计或出于监管目的确定释放速率限值的过程。另请参见第节 4. . 1.8 以国际单位制表示的数值应视为标准。 括号中给出的值仅供参考。 1.9 本标准并非旨在解决与其使用相关的所有安全问题(如有)。本标准的用户有责任在使用前制定适当的安全、健康和环境实践,并确定监管限制的适用性。 1.10 本国际标准是根据世界贸易组织技术性贸易壁垒(TBT)委员会发布的《关于制定国际标准、指南和建议的原则的决定》中确立的国际公认标准化原则制定的。 ====意义和用途====== 4.1 本试验方法旨在提供一种实验室程序,以量化和表征在恒温、pH值、盐度和流体动力学的特定实验室条件下浸泡期间防污涂层中有机杀生物剂释放速率的变化。定量测量杀生物剂释放速率有助于选择材料、提供质量控制和了解性能机制。 4.2 本试验方法的结果确定了在受控实验室条件下至少45天暴露时间内,防污涂层中的杀生物剂释放模式。 在用防污涂料的杀生物剂释放率在涂层系统的整个使用寿命内有所不同,这取决于配方和环境的物理和化学性质。停泊位置、操作时间表、服务时间、漆膜表面状况、温度、pH值和盐度等因素的差异会影响环境条件下的实际释放速率。使用本试验方法获得的结果并不反映在使用中发生的实际杀生物剂释放率,但提供了在规定实验室条件下替代海水中不同防污配方释放率特性的比较。 4.3 通过与已发布的铜和有机锡释放率数据进行比较 4. , 5. 通过直接测量船体或港口暴露面板的释放率获得的所有数据表明,与在役条件下的释放率相比,这种通用旋转圆柱体试验方法的结果明显高估了杀生物剂的释放率。例如,已公布的结果表明,这种通用测试方法对铜和有机锡释放率的测量值高于对同一涂层的直接原位测量值- 服务船船体和港口外露面板。基于几种商用防污涂料的铜释放速率数据,该测试方法的结果与面板和船舶研究的结果之间的差异高达约30倍。 4. 6. 迄今为止,尚未从船体或港口暴露面板中生成该方法涵盖的杀生物剂的直接释放率数据。然而,当与从船体和港口暴露面板直接测量的结果进行比较时,预期该测试方法的结果可能遵循相同的趋势。 只有在考虑了通过本试验方法获得的结果与在役防污涂层释放速率之间的差异的情况下,才能从本试验方法中获得在役条件下船体释放的杀生物剂的实际估计值。 4.4 如果本试验方法的结果用于生成环境风险评估、环境负荷估计或监管目的,强烈建议考虑实验室释放率和实际环境输入之间的关系,以便更准确地近似真实环境下防污涂料中的杀生物剂释放率- 生活条件。这可以通过应用适当的校正因子来实现。 6.
1.1 This test method covers the laboratory determination of the rate at which organic biocide is released from an antifouling coating exposed in substitute ocean water. The test is run entirely in the laboratory under controlled conditions of pH, temperature, salinity, and hydrodynamics. Analytical procedures are provided for the determination of the release rate of 4,5-dichloro-2-n-octylisothiazolin-3-one (DCOIT), zinc and copper pyrithione (ZPT and CuPT), and N -cyclopropyl- N ′ -(1,1-dimethylethyl)-6-(methylthio)-1,3,5-triazine-2,4-diamine (CDMTD). At predetermined intervals, substitute ocean water samples are analyzed for leached biocide using a suitable analytical technique. 1.2 In cases in which the antifouling coating contains both an organic biocide and a copper-based biocide, the release rate of copper may optionally be concurrently determined according to the procedure found in Test Method D6442 . 1.3 The procedure contains the preparation steps for the determination of the release rate of biocide in substitute ocean water from antifouling paints including apparatus, reagents, holding tank conditions, and sampling point details. The procedure calls for the accurate determination of organic biocide concentrations in substitute ocean water at the low μ g L -1 (parts per billion, ppb) level. To detect and correct for reagent impurities and allow a suitable level of analytical precision to be achieved, the analytical method to be used for the determination of the concentration of organic biocide in substitute ocean water must meet the acceptability criteria given in Annex A2 . Where Annex A2 specifies a limit of quantitation (LOQ), the procedure for determining the LOQ for the organic biocide in substitute ocean water by the analytical method presented in Annex A3 is to be followed. 1.4 Suitable analytical methods that use high-performance liquid chromatography (HPLC) for determining the concentration of DCOIT, ZPT and CuPT, and CDMTD in substitute ocean water are given in Appendix X1 – Appendix X3 , respectively. Other methods may be used provided that they meet the appropriate criteria given in Annex A2 . 1.5 When the release rate of a highly photosensitive organic biocide is being determined, steps must be taken to protect the apparatus and samples from exposure to natural and artificial visible light sources. Any such requirement for these steps to be taken for a particular biocide is indicated in Annex A2 . 1.6 The practical limits for quantifying biocide release rates by this method are from 4.5 to 500 μ g cm -2 d -1 for DCOIT, 0.36 to 500 μ g cm -2 d -1 for CuPT, 0.36 to 500 μ g cm -2 d -1 for ZPT, and 2.7 to 500 μ g cm -2 d -1 for CDMTD. These ranges may be extended to 3.8 to 500 μ g cm -2 d -1 for DCOIT, 0.16 to 500 μ g cm -2 d -1 for CuPT, 0.2 to 500 μ g cm -2 d -1 for ZPT, and 2.2 to 500 μ g cm -2 d -1 for CDMTD if the procedures described in Appendix X1 – Appendix X3 (as appropriate) are followed. The quantitation of release rates lower than these ranges will require the use of analytical methods with lower limits of quantitation than those specified in Annex A2 . 1.7 The results of this test method do not reflect environmental biocide release rates for antifouling products, and are not suitable for direct use in the process of generating environmental risk assessments, environmental loading estimates, or for establishing release rate limits for regulatory purposes. See also Section 4 . 1.8 The values stated in SI units are to be regarded as the standard. The values given in parentheses are for information only. 1.9 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use. 1.10 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee. ====== Significance And Use ====== 4.1 This test method is designed to provide a laboratory procedure to quantify and characterize changes in the release rate of organic biocide from antifouling coatings that occur during a period of immersion under specified laboratory conditions of constant temperature, pH, salinity, and hydrodynamics. Quantitative measurement of biocide release rate is necessary to help in selection of materials, providing quality control, and understanding the performance mechanism. 4.2 Results from this test method establish a pattern of biocide release from an antifouling coating over a minimum of 45 days exposure under controlled laboratory conditions. Biocide release rates of antifouling paints in-service vary over the life of the coating system depending on the formulation and on the physical and chemical properties of the environment. Factors such as differences in berthing locations, operating schedules, length of service, condition of paint film surface, temperature, pH, and salinity influence the actual release rate under environmental conditions. Results obtained using this test method do not reflect actual biocide release rates that will occur in service, but provide comparisons of the release rate characteristics of different antifouling formulations in substitute ocean water under the prescribed laboratory conditions. 4.3 By comparison with published copper and organotin release rate data 4 , 5 obtained either by direct measurements from ship hulls or release rate measurements from harbor exposed panels, all data indicate that the results of this generic rotating-cylinder test method significantly overestimate the release rate of biocide when compared to release rates under in-service conditions. For example, published results demonstrate that this generic test method produces higher measurements of copper and organotin release rates than from direct in situ measurements for the same coating on in-service ship hulls and harbor-exposed panels. The difference between the results of this test method and the panel and ship studies was up to a factor of about 30 based on copper release rate data for several commercial antifouling coatings. 4, 6 No direct release rate data from ship hulls or harbor-exposed panels have been generated to-date for the biocides covered by this method. However, the expectation is that the results of this test method, when compared with the direct measurements from ship hulls and harbor-exposed panels, could follow the same trend. Realistic estimates of the biocide release from a ship’s hull under in-service conditions can only be obtained from this test method where the difference between the results obtained by this test method and the release rate of an antifouling coating in service is taken into account. 4.4 Where the results of this test method are used in the process of generating environmental risk assessments, for environmental loading estimates, or for regulatory purposes, it is most strongly recommended that the relationship between laboratory release rates and actual environment inputs is taken into account to allow a more accurate approximation of the biocide release rate from antifouling coatings under real-life conditions. This can be accomplished through the application of appropriate correction factors. 6
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