1、 FORD LABORATORY TEST METHOD BZ 156-01 Date Action Revisions Rev. 1 2011 07 14 Revised S.Riewer, FoE 2009 01 23 Activated S.Riewer, FoE Controlled document at www.MATS Copyright 2011, Ford Global Technologies, LLC Page 1 of 9 DETERMINATION OF FORMALDEHYDE, ALDEHYDE, AND KETONE EMISSIONS FROM NON MET
2、ALLIC COMPONENTS, PARTS AND MATERIALS IN THE VEHICLE INTERIOR Application The test method describes the measurement procedure for determining formaldehyde, aldehyde, and ketone emissions from components, parts and materials in the interior of vehicles. The procedure is used for testing the distribut
3、ion of aldehyde and ketone emissions between components. Subject to certain restrictions, it can also be used for material development and for acceptance testing. As to its technical content, Part A is for determining formaldehyde content in accordance with the modified bottle method and conforms to
4、 VDA 275 (German Automotive Association). Part B is to analyze aldehyde and ketone emissions by high performance liquid chromatography (HPLC). The bottle method was developed for the purpose of determining the formaldehyde emission from woven textiles and untreated particle boards. It has subsequent
5、ly been applied in different variants for the testing of other materials. Conditioning and Test Conditions All test values indicated herein are based on material conditioned in a controlled atmosphere of 23 +/- 2 C and 50 +/- 5% relative humidity for not less than 24 hours prior to testing and teste
6、d under the same conditions unless otherwise specified. PART A. PHOTOMETRIC DETERMINATION OF FORMALDEHYDE EMISSION FROM NON METALLIC COMPONENTS, PARTS AND MATERIALS IN VEHICLE INTERIORS Materials Required Acetyl acetone, p.a. Sodium thiosulphate (c(Na2S2O3)= 0.1 mol/L), p.a. Ammonium acetate, p.a. S
7、odium hydroxide (c(NaOH)= 1 mol/L), p.a. Formaldehyde solution (35-40%), p.a. Starch, p.a. Lodine soultion (C(I2)= 0.05 mol/L), p.a. Sulphuric acid (c(H2SO4)= 1 mol/L), p.a. Distilled water Note: Commercially available ready-mixed solutions can be used if the same results are achieved. FORD LABORATO
8、RY TEST METHOD BZ 156-01 Controlled document at www.MATS Copyright 2011, Ford Global Technologies, LLC Page 2 of 9 Apparatus Required - Analytical balance with a 1 mg scale - Heating chamber with air circulation - Spectrophotometer test apparatus - Polyethylene bottles with a volume of 1 litre with
9、a lid (see fig. 1) - Hook made of stainless steel with seals, positioned inside the lid of the test bottle - Precision burette, 50 mL, calibrated at 20 C - Graduated flasks, 1000 mL, calibrated at 20 C - Graduated flasks, 100 mL, calibrated at 20 C - Pipette, 5 mL, calibrated at 20 C - Pipette, 10 m
10、L, calibrated at 20 C - Pipette, 15 mL, calibrated at 20 C Method 1. Number of tests: The determination shall be performed five times. The test pieces shall be evenly distributed over the width of the component and taken at suitable, representative points. The size of the test pieces shall be 40 mm
11、x 100 mm x subject material thickness. At least 6 test pieces shall be taken from each component. Five of these are for the formaldehyde test and one for determining the moisture content. 2. Determination of moisture content The moisture content is determined in accordance with BS EN 322 Wood-based
12、sheets - Moisture quotient -Testing). 3. Determination of formaldehyde emission One or 2 holes are positioned 10 mm from the upper edge of the test piece to permit them to be hung with the help of hooks. The test piece is weighed prior to the start of the analysis on an analytical balance with an ac
13、curacy of 0.01 g. Using a pipette, 50 mL of distilled water are added to each of the polyethylene bottles. After placing the test pieces on the hooks (see fig. 1), the vessel is sealed and kept for at least 3 h in the heating cabinet at a constant temperature of 60 C. At the end of the test period,
14、the vessels are removed from the heating cabinet. After having stood for 60 min at room temperature, the test pieces are removed from the test bottle. FORD LABORATORY TEST METHOD BZ 156-01 Controlled document at www.MATS Copyright 2011, Ford Global Technologies, LLC Page 3 of 9 Figure 1 4. Blind tes
15、t. This test is performed in parallel without test pieces. 5. Determination of formaldehyde concentration in the aqueous solution The determination of the formaldehyde level in the aqueous solution is performed photometrically by the acetyl acetone method. 5.1 Principle The determination is based on
16、 the Hantzsch reaction in which formaldehyde in aqueous solution reacts with ammonium ions and acetyl acetone to form diacetyl dihydrolutidin (DDL). DDL has an absorption maximum at 412 nm. The reaction is specific to formaldehyde. CH3COCH2COCH3 + HCHO NH4+ -3 H2O-H+ NOHCH3CH3CH3OCH3+DDL 5.2 Reagent
17、s Acetyl acetone solution 4 mL of acetyl acetone are poured into a 1000 mL graduated flask, which is then topped up with water to the 1000 mL mark. The solution is kept under a gas-tight seal and protected from the light for up to 4 weeks. Ammonium acetate solution 200 g of ammonium acetate are weig
18、hed into a 1000 mL graduated flask, dissolved in distilled water and topped up to 1000 mL. FORD LABORATORY TEST METHOD BZ 156-01 Controlled document at www.MATS Copyright 2011, Ford Global Technologies, LLC Page 4 of 9 5.3 Method 10 mL of the aqueous solution (para. 3) are taken up with a pipette an
19、d mixed in a 50 mL bottle with 10 mL of acetyl acetone solution and 10 mL of ammonium acetate solution. The bottle is closed, shaken and heated for 15 min in a water bath at a temperature of +40 C 1 C. The by now greenish-yellow solution shall then be left in an area protected from the light at a te
20、mperature of 23 C 2 C for 1 h. The concentration of this solution is determined at a wavelength of 412 nm against distilled water by means of a spectrophotometer. A blind value is determined in parallel with distilled water, and account is taken of the blind test in the calculation. Note: After each
21、 determination, the polyethylene bottles shall be cleaned in a laboratory washing machine. If this is not sufficient, it is recommended that the bottles are heated to 70 C in a heating chamber for approx. 16 h. 6. Calibration curve The calibration curve is produced by means of a formaldehyde standar
22、d solution, the concentration of which is determined by iodometric titration. The calibration curve shall be verified at least once a week. 6.1 Formaldehyde Standard Solutions Reagent Solutions: lodine C(I2) = 0.05 mol/L Sodium thiosulphate c(Na2S2O3) = 0,1 mol/L Sodium hydroxide c(NaOH) = 1 mol/L S
23、ulphuric acid c(H2SO4) = 1 mol/L Starch solution, 1 % m/m The concentration of the solution shall be verified before use. Approx. 1 g of formaldehyde solution (concentration 35 to 40 %) is poured into a 1000 mL graduated flask, which is then filled with distilled water up to the mark. The precise fo
24、rmaldehyde concentration is determined as follows: 20 mL of the formaldehyde solution are mixed with 25 mL of iodine solution and 10 mL of sodium hydroxide. This mixture shall be left to stand protected from the light for 15 min, after which 15 mL of sulphuric acid are added. Any surplus iodine is r
25、e-titrated with the thiosulphate solution. At the end of the titration, a few drops of starch solution are added as an indicator. A blind test is performed in parallel with 20 mL of distilled water. The formaldehyde content is calculated according to the following formula: c(HCHO) = (V0-V) x 15 c(Na
26、2S2O3) x 1000/20 where: c(HCHO) formaldehyde concentration in mg/L Vo volume of thiosulphate solution for the blind test, in mL V volume of thiosulphate solution in mL cNa2S2O3) concentration of thiosulphate solution in mol/L Note: 1 mL of 0,1 mol/L thiosulphate solution is equivalent to 1 mL of 0.0
27、5 mol/L iodine solution and 1.5 mg formaldehyde. FORD LABORATORY TEST METHOD BZ 156-01 Controlled document at www.MATS Copyright 2011, Ford Global Technologies, LLC Page 5 of 9 6.2 Formaldehyde calibration solution (length of bulb: 1 cm) Using a pipette, a volume of the formaldehyde standard solutio
28、n, containing 15 mg of formaldehyde is placed in a 1000 mL graduated flask, after which the flask is topped up with distilled water to the mark. 1 mL of this solution contains 15 g of formaldehyde. 6.3 Determination of calibration curve: Using a pipette, 0, 5, 10, 20, 50 or 100 mL of the formaldehyd
29、e calibration solution are each placed in a 100 mL graduated flask and topped up with distilled water) Using a pipette, a volume of the formaldehyde Standard solution containing 3 mg of formaldehyde is placed in a 1000 mL graduated flask, after which the flask is topped up to the mark. 10 mL of each
30、 mixture are analyzed photo metrically. The absorption is plotted graphically against the formaldehyde concentrations (between 0 and 15 (g/mL). The slope of the curve is determined graphically or calculated. Formaldehyde calibration solution (length of bulb: 5 cm with distilled water to the mark. 1
31、mL of this solution contains 3 g of formaldehyde. 7. Calculation of results 7.1 Moisture content The moisture content H (in mass % m/m) of the component can be calculated with the following formula: where: m1: mass of the sample before drying, in grams m0: mass of the sample after drying, in grams 7
32、.2 Formaldehyde emissions according to the bottle method The total quantity of absorbed formaldehyde is calculated from the slope of the photometric determination curve and the total volume of water in the absorption liquid (here 10 mL). This quantity of formaldehyde is calculated in relation to the
33、 weight of the test piece in mg/kg corrected to the dry weight. Calculation of formaldehyde emissions in mg/kg: As Absorption of the analyzed solution AB Absorption of the analysis with distilled water f Slope of the calibration function (in g/mL) m Mass of the test piece in g H Moisture content of
34、the test material, as a percentage V Volume of the absorber solution (50 mL) ato Absolutely dry test material F Factor for calculating the analysis result in kg mg/kg; F=10 100001 =mmmHatokgmgHCHOFm HVfAA BS /1000 )100()( = +FORD LABORATORY TEST METHOD BZ 156-01 Controlled document at www.MATS Copyr
35、ight 2011, Ford Global Technologies, LLC Page 6 of 9 8. Test Report The test report shall include the following points: - a reference to this test method - all the necessary details for identifying the test object - documented results for each test, also indicating a mean value - any Special charact
36、eristics of the test pieces noted during testing and their condition - date of manufacture and manufacturer of the test material, if known - date of sampling - origin of test material - place, position and condition of the material at the time of sampling, especially the moisture content - date of f
37、ormaldehyde determination - moisture content %) at the time of the test - formaldehyde emission according to the bottle method (mg formaldehyde/kg ato material) PART B. DETERMINATION OF ALDEHYDE AND KETONE EMISSION FROM NON METALLIC COMPONENTS, PARTS AND MATERIALS IN VEHICLE INTERIORS BY HIGH PERFOR
38、MANCE LIQUID CHROMATOGRAPHY (HPLC) Apparatus and Materials Required - Analytical balance with a 1 mg scale - Heating chamber with air circulation - High performance liquid chromatography (HPLC) instrument - with binary pump, solvent degasser, heated column and wavelength or diode array detector - HP
39、LC column capable of separating derivates of 2,4-di-nitrophenylhydrazin (DNPH) of ketones and aldehydes using gradient elution - Polyethylene bottles with a volume of 1 litre with a lid (see fig. 1 part A) - Hook made of stainless steel with seals, positioned inside the lid of the test bottle - volu
40、metric flask 50 mL and 1000 mL - Graduated pipette 15 mL - Volumetric pipette 50 mL - Perchloric Acid (conc.) p.a. - Acetonitrile HPLC grade - Water HPLC grade - DNPH (2,4-dinitrophenylhydrazine) - Calibration standards for aldehydes and ketones in acetonitrile e.g. ERA-037by Ceriliant, TO11/IP-6-A
41、by Supelco or any other suitable supplier FORD LABORATORY TEST METHOD BZ 156-01 Controlled document at www.MATS Copyright 2011, Ford Global Technologies, LLC Page 7 of 9 Method 1. Number of tests: The determination shall be performed five times. The test pieces shall be evenly distributed over the w
42、idth of the component and taken at suitable, representative points. The size of the test pieces shall be 40 mm x 100 mm x subject material thickness. 2. Determination of moisture content The moisture content is determined in accordance with BS EN 322 Wood-based sheets - Moisture quotient -Testing).
43、3. Determination of aldehyde and ketone emission One or 2 holes are positioned 10 mm from the upper edge of the test piece to permit them to be hung with the help of hooks. The test piece is weighed prior to the start of the analysis on an analytical balance with an accuracy of 0.01 g. Using a pipet
44、te, 50 mL of distilled water are added to each of the polyethylene bottles. After placing the test pieces on the hooks (see fig. 1), the vessel is sealed and kept for at least 3 h in the heating cabinet at a constant temperature of 60 C. At the end of the test period, the vessels are removed from th
45、e heating cabinet. After having stood for 60 min at room temperature, the test pieces are removed from the test bottle. 4. Blind test This test is performed in parallel without test pieces. 5. Determination of aldehydes and ketones concentration in the aqueous solution The determination of specific
46、aldehyde and ketone levels in the aqueous solution is performed by high performance liquid chromatography (HPLC). 5.1 Principle Aldehydes and ketones are derivate by 2,4-di-nitrophenylhydrazin (DNPH): O2N NO2NHNH2O2N NO2NHNA1A2OA1A2+ OH2+The individual derivation products are separated by high perfo
47、rmance liquid chromatography (HPLC). FORD LABORATORY TEST METHOD BZ 156-01 Controlled document at www.MATS Copyright 2011, Ford Global Technologies, LLC Page 8 of 9 5.2 Reagents Perchloric acid solution 4.5 mL of concentrated perchloric acid are pipetted into a 50mL graduated flask. The flask is fil
48、led up with acetonitrile. DNPH (2,4-di-nitrophenylhydrazine) solution 1.23g DNPH (6.1 mmol) and 12.5 mL perchloric acid solution are added into a 1000mL graduated flask. The flask is filled up with acetonitrile. 5.3 Method Derivation of aldehydes and ketons by DNPH (2,4-di-nitrophenylhydrazine) 1 mL
49、 of DNPH solution and 9 mL of the aqueous absorbent solution (para. 3) are mixed together and stirred for about 30 minutes. Afterwards the solution can be placed on the HPLC instrument. 6. Calibration Calibration standard solutions are prepared by dissolving aldehydes and ketons in water. The range of concentration has to set according to expected concentration of carbonyl compound. Typically the range is between 0.1 g and 15 g/L Co
