1、 WORLDWIDE ENGINEERING STANDARDS Test Procedure GMW15635 Determination of Aldehyde and Ketone Emissions from Interior Materials Copyright 2012 General Motors Company All Rights Reserved August 2012 Originating Department: North American Engineering Standards Page 1 of 10 1 Scope Note: Nothing in thi
2、s standard supercedes applicable laws and regulations. Note: In the event of conflict between the English and domestic language, the English language shall take precedence. 1.1 Purpose. This test procedure describes a measuring process for determining the aldehyde and ketone emissions from vehicle i
3、nterior materials. 1.1.1 For this test, test pieces are fastened above deionized water in a sealed bottle and stored in an oven for a specific period. Afterwards, the bottles are cooled and the aldehydes and ketones absorbed in the demineralized water are determined. 1.1.2 The concentrations of alde
4、hydes and ketones are determined by 2,4-dinitrophenylhydrazine (DNPH) derivatization followed by high performance liquid chromatography (HPLC) with ultraviolet (UV) detection. 1.1.3 The quantity of aldehydes and ketones are ascertained as a proportion of the dry weight in micrograms per gram (g/g) o
5、f the test piece. 1.2 Foreword. The determination of aldehydes and ketones in vehicle materials and components is essential to meet customer requirements and regulatory requirements in some global markets. 1.3 Applicability. This test procedure is applicable to materials and components used in vehic
6、le interiors that may contain carbonyls (e.g., polyoxymethylene, parts containing wood, natural or laminated fibers, leather, artificial leather, adhesives, sealants, polyurethane, cotton fleece, joint fabric fleece, phenol/formaldehyde resins, etc.) The results will provide complementary informatio
7、n to GMW14444. 2 References Note: Only the latest approved standards are applicable unless otherwise specified. 2.1 External Standards/Specifications. DIN 55531 ISO 16979 ISO/IEC 17025 2.2 GM Standards/Specifications. GMW3059 GMW14444 2.3 Additional References. 3 Resources 3.1 Facilities. Not appli
8、cable. 3.2 Equipment. This test procedure utilizes commonly available equipment and instrumentation. Specific instrumentation and test conditions are noted in the Appendix. 3.2.1 Test Apparatus. 3.2.1.1 Precision weighing device with scale graduation 1 mg. 3.2.1.2 Air circulating oven capable of mai
9、ntaining the required temperature within 3 C. 3.2.1.3 One liter (1 L) polyethylene bottle with an integrated hook implemented within the lid (see Figure 1). 3.2.1.4 High performance liquid chromatograph with binary pump, solvent degasser, heated column compartment, autosampler (optional), variable w
10、avelength or diode array detector (DAD), and personal Copyright General Motors Company Provided by IHS under license with General Motors CompanyNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-GM WORLDWIDE ENGINEERING STANDARDS GMW15635 Copyright 2012 General Motors
11、 Company All Rights Reserved August 2012 Page 2 of 10 computer (PC)-based controller and data evaluation. System must be capable of gradient operation to 3.5 mL/minute and 350 bar (maximum ceiling pressure capacity), and UV detection at 360 nm to 365 nm (e.g., Agilent 1100 Series and Agilent ChemSta
12、tion for system control and data evaluation, or comparable equipment). 3.2.1.5 HPLC column capable of separating and resolving the 2,4-dinitrophenylhydrazine derivatives of the specified aldehydes/ketones using gradient elution conditions. The separation of the DNPH derivatives depends on the HPLC c
13、olumn used. See Appendices A, B and C for conditions. 3.2.2 Reagents. 3.2.2.1 Acetonitrile. HPLC grade. 3.2.2.2 Tetrahydrofuran. HPLC grade containing no antioxidant additive. 3.2.2.3 Water. HPLC grade. 3.2.2.4 Phosphoric Acid. Concentrated, reagent grade. 3.2.2.5 Derivatizing Reagent. 3.2.2.5.1 DNP
14、H Solution. Approximately 250 mg of 2,4-dinitrophenylhydrazine dissolved in 50 mL of acetonitrile. 3.2.2.6 Calibration standards containing the components of interest already derivatized in appropriate concentration range, typically 0.1 g/mL to 15 g/mL in acetonitrile. 3.2.2.6.1 Calibration standard
15、s, among others, are available from: Cerilliant: ERA-037, ERA-13K, ERA-028, 13 components in acetonitrile, 1 g/mL to 15 g/mL of each component as aldehyde/ketone, (). Supelco: TO11/IP-6-A Carbonyl-DNPH-Mix, 15 components in acetonitrile, 15 g/mL of each component (aldehyde equivalent), Sigma-Aldrich
16、 (Supelco), 47285-U. 3.3 Test Vehicle/Test Piece. 3.3.1 Test Sample Handling and Preparation. If possible, the test sample shall be taken out of the finished part of the material or the component. 3.3.1.1 In exceptional cases (e.g., if only one material of a component is to be tested, or if the comp
17、lete component is not available), tests can be conducted on specially prepared parts. 3.3.1.2 The sample should be taken within 7 days after production. The production date and sampling should be documented. Care should be taken to prevent material from thermal desorption before analysis (package, r
18、efrigerate). 3.3.1.3 A representative material sample (smaller samples) have to cut out from large components to a size of 10 cm x 15 cm. The sample shall be handled with protective gloves and the cutting shall be done with an oil-free tool such as a disposable razor blade. The sample should be pack
19、ed by aluminum composite films (e.g., VACUPAC or any other material according to DIN 55531) prior to shipping. In the exceptional case, the sample can be packed twice into thick silicone-free aluminum foil (pre-cleaned with n-pentane). The edges should be folded multiple times to prevent contaminati
20、on from outside and to ensure an air-tight packing. The aluminum foil packed sample should then be packed additionally and placed in a polyethylene bag. The bag shall be labeled with sample identification (ID) number; final sample name (cannot be changed or altered afterwards), production date and s
21、ampling date shall be recorded in Appendix D, Data Sheet D1. If this information is missing, the sample should not be analyzed. 3.3.2 Removing Test Pieces. The test pieces shall be removed from suitable and representative areas spread evenly across the width of the part. They must be taken 50 mm fro
22、m the edge of the part. 3.3.3 The size of each test piece is nominally 40 mm x 100 mm x thickness. If the size of the molded part is smaller or the distance of 50 mm to the edge of the part is not possible, this test may also be performed using smaller test pieces. Here, care must be taken to ensure
23、 that all the edges of test pieces are freshly cut. To fasten the test piece, a hole corresponding to the diameter of the hook is drilled near its center, 10 mm from the upper edge. 3.3.3.1 For small parts, at least 3 samples must be taken from each part. Two (2) parts are used for determining aldeh
24、ydes/ketones and 1 part is used to determine the moisture content. 3.3.4 If the testing of the samples cannot take place immediately, they must be stored in cool, air-tight conditions with a minimal air volume. Storage time should not exceed 5 days. Copyright General Motors Company Provided by IHS u
25、nder license with General Motors CompanyNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-GM WORLDWIDE ENGINEERING STANDARDS GMW15635 Copyright 2012 General Motors Company All Rights Reserved August 2012 Page 3 of 10 3.4 Test Time. Sampling of the test pieces require
26、s 3 h in the oven and 1 h of cool down. Sampling is best conducted for several materials in parallel in individual bottles in the oven. The determination of aldehydes/ketones by derivatization and HPLC is conducted serially with each sample requiring 30 minutes 5 minutes. 3.5 Test Required Informati
27、on. Material component information such as vendor name, production date, pretreatment, etc., should be recorded in Appendix D, Data Sheet D1. 3.6 Personnel/Skills. Proper training is required to process the samples and operate the HPLC instrument. A professional degree in chemistry, chemical enginee
28、ring or the health sciences, and familiarity with the operation of HPLC instrumentation is required. 4 Procedure 4.1 Preparation. 4.1.1 Determining the Moisture Content. The moisture content is determined in accordance with ISO 16979. 4.1.1.1 The moisture content H% of the part in percent is derived
29、 from the following formula: H (%) = 100% x (m1/m0 ) - 1) Where: m1 = mass of the test piece (g) before drying m0 = mass of the test piece (g) after drying 4.1.1.2 The mass constancy is obtained if the results of two successive tests dont deviate more than 1% from one another. 4.2 Conditions. 4.2.1
30、Environmental Conditions. 4.2.1.1 Instrument. Set up the HPLC instrument with the conditions given in the Appendices A, B or C. 4.2.2 Test Conditions. Deviations from the requirements of this standard shall have been agreed upon. Such requirements shall be specified on component drawings, test certi
31、ficates, reports, etc. 4.3 Instructions. 4.3.1 Determining the Release of Aldehydes and Ketones from the Test Samples. Prior to the chemical analysis, the samples are weighed on the analytical balance to 0.01 g. Fifty milliliters (50 mL) aliquots of deionized water are pipetted into each of a clean
32、1 L polyethylene bottle. As soon as the test sample has been attached to the hook, the bottle is sealed and stored for 180 minutes 15 minutes in a heated cabinet at +60 C 3 C. Additionally a blank test shall be run without test piece present. 4.3.1.1 When the test time is completed, the containers a
33、re removed from the heating cabinet then left to stand at +23 C 5 C for 60 minutes 10 minutes. The samples are removed from the bottles. Copyright General Motors Company Provided by IHS under license with General Motors CompanyNot for ResaleNo reproduction or networking permitted without license fro
34、m IHS-,-,-GM WORLDWIDE ENGINEERING STANDARDS GMW15635 Copyright 2012 General Motors Company All Rights Reserved August 2012 Page 4 of 10 Figure 1: Drawing of Test Apparatus 4.3.2 HPLC Determination of the Concentration of Aldehydes and Ketones in the Aqueous Solution. 4.3.2.1 Calibration Standards a
35、nd Chromatograms. Calibration standard solutions of the aldehydes and ketones have to be prepared in concentrations from 0.1 g/mL up to 15 g/mL (related to the corresponding carbonyl compound) in water. 4.3.2.2 Calibration curves are created by measuring the calibration solutions by HPLC according t
36、o the test conditions in Appendices A, B or C depending on the HPLC column utilized. 4.3.2.3 Each measuring sequence should start with pure solvent. Afterward calibration standards are measured with increasing carbonyl content (e.g., 0.1, 0.3, 0.5, 1.0, 3.0 and 15) g/mL. 4.3.2.4 Individual peaks in
37、the samples are identified by their retention times and quantified by evaluation of their peak areas. 4.3.2.5 Tetrahydrofuran (THF) usage may cause swelling in HPLC polyetheretherketone (PEEK) tubing. Therefore, mobile phase solvents and corresponding modifiers are plumbed entirely using stainless s
38、teel tubing from the binary pump purge valve assembly and through the DAD outlet. 4.3.3 Derivatizing of the Aldehydes/Ketones. In an HPLC autosampler vial, mix 1 mL of the test water with 1 mL of derivatizing solution and 100 L (2 drops) of concentrated phosphoric acid. Shake gently and allow 30 min
39、utes for the derivatization reaction to occur. 4.3.4 Analysis. Each analytical measurement should begin with a pure solvent followed by a standard solution. Copyright General Motors Company Provided by IHS under license with General Motors CompanyNot for ResaleNo reproduction or networking permitted
40、 without license from IHS-,-,-GM WORLDWIDE ENGINEERING STANDARDS GMW15635 Copyright 2012 General Motors Company All Rights Reserved August 2012 Page 5 of 10 4.3.4.1 Vials containing the derivatized sample test water can be placed after the standard starting with the blank solution. After the analysi
41、s sequence, inject an aliquot from each vial using the HPLC analysis conditions previously developed. 5 Data 5.1 Calculations. 5.1.1 Determination of Aldehyde and Ketone Concentrations in Solution. All individual peaks in the samples are identified by their retention times and quantitated by compari
42、son of their peak areas to the external standard calibration curves constructed by the instrument software. The values are obtained in micrograms per milliliter (g/mL). 5.1.2 Calculating the Release of Aldehydes and Ketones from the Material Test Piece. The released quantity of aldehydes and ketones
43、 referred to the dry corrected weight (M0) are calculated as follows. C1 x V1 x V2 C1 Cald_ket = _ = 100 mL *_ M0 x V3 M0 Where: Cald_ket = concentration of aldehyde or ketone (g/g) in test sample. C1 = concentration of aldehyde or ketone by HPLC (g/mL). M0 = weight of the dry sample (g), calculated
44、 according to 4.1.1.1. V1 = total volume solution of the derivatized reaction (2.0 mL). V2 = volume of test water (50 mL). V3 = analyzed volume solution of the derivatized reaction (1.0 mL). 5.1.2.1 The final result gives the concentration of the aldehydes and ketones in micrograms per gram (g/g) te
45、st sample. 5.2 Interpretation of Results. Not applicable. 5.3 Test Documentation. 5.3.1 The aldehyde and ketone concentration shall be expressed as the average value of 2 or 3 determination in micrograms per gram (g/g) and referred to this test method. 5.3.2 A report documenting all of the condition
46、s for this analysis and the results shall be prepared according to Appendix D, Data Sheet D1. 5.3.3 Test Data. The analytical work is to be performed by a laboratory that conforms to ISO/IEC 17025 and should be acceptable to GM. 5.3.3.1 Test reports must conform to Appendix D, Data Sheet D1. 5.3.3.2
47、 Supplier shall submit aldehydes/ketones and acrolein test results according to the Production Part Approval Manual under Materials Test Results (see GMW3059). 6 Safety This standard may involve hazardous materials, operations, and equipment. This standard does not propose to address all the safety
48、problems associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. 7 Notes 7.1 Glossary. Not applicable. 7.2 Acronyms, Abbreviations, and Symbols. DAD Dio
49、de Array Detector DNPH 2,4-dinitrophenylhydrazine Copyright General Motors Company Provided by IHS under license with General Motors CompanyNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-GM WORLDWIDE ENGINEERING STANDARDS GMW15635 Copyright 2012 General Motors Company All Rights Reserved Augu
