1、August 2009DEUTSCHE NORM English price group 8No part of this standard may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS 83.180!$YAF“1543035www.d
2、in.deDDIN EN 13999-3Adhesives Short term method for measuring the emission properties of low-solventor solvent-free adhesives after application Part 3: Determination of volatile aldehydes (includes AmendmentA1:2009)English version of DIN EN 13999-3:2009-08Klebstoffe Kurzzeit-Verfahren zum Messen der
3、 Emissionseigenschaften von lsemittelarmen oderlsemittelfreien Klebstoffen nach der Applikation Teil 3: Bestimmung flchtiger Aldehyde (enthlt nderung A1:2009)Englische Fassung DIN EN 13999-3:2009-08SupersedesDIN EN 13999-3:2007-07www.beuth.deDocument comprises 12 pagesDIN EN 13999-3:2009-08 National
4、 foreword This standard has been prepared by Technical Committee CEN/TC 193 “Adhesives” (Secretariat: AENOR, Spain). The responsible German bodies involved in its preparation were the Normenausschuss Kunststoffe (Plastics Standards Committee), Technical Committee NA 054-04-06 AA Klebstoffe Terminolo
5、gie; physikalisch-chemische Prfungen and the Normenausschuss Materialprfung (Materials Testing Standards Committee). Amendments This standard differs from DIN EN 13999-3:2007-07 as follows: a) European Standard EN 13999-3:2007+A1:2009 has been adopted in full. b) In subclause 6.1, it has been specif
6、ied that the combined sampling flow rates shall not exceed 90 % of the test chamber supply air flow rate. Previous editions DIN V ENV 13999-3: 2003-02 DIN EN 13999-3: 2007-07 2 EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 13999-3:2007+A1 April 2009 ICS 83.180 Supersedes EN 13999-3:2007Englis
7、h Version Adhesives Short term method for measuring the emission properties of low-solvent or solvent-free adhesives after application Part 3: Determination of volatile aldehydes Adhsifs Mthodes de mesurage rapide des caractristiques missives des adhsifs teneur faible ou nulle en solvants aprs appli
8、cation Partie 3: Dosage des aldhydes volatiles Klebstoffe Kurzzeit-Verfahren zum Messen der Emissionseigenschaften von lsemittelarmen oder lsemittelfreien Klebstoffen nach der Applikation Teil 3: Bestimmung flchtiger Aldehyde This European Standard was approved by CEN on 8 March 2007 and includes Am
9、endment 1 approved by CEN on 3 April 2009. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning su
10、ch national standards may be obtained on application to the CEN Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own langua
11、ge and notified to the CEN Management Centre has the same status as theofficial versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxe
12、mbourg, Malta, Netherlands, Norway, Poland, Portugal,Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2009 CEN All righ
13、ts of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 13999-3:2007+A1:2009: EEN 13999-3:2007+A1:2009 (E) 2 Contents PageForeword 3 SAFETY STATEMENT .4 1 Scope 4 2 Normative references 4 3 Principle 4 4 Reagents .5 5 Apparatus .5 6 Procedure .5 7 Ide
14、ntification and calculation .7 8 Interferences 8 9 Precision and bias .8 10 Test report 8 11 Quality control 9 Bibliography . 10 DIN EN 13999-3:2009-08 EN 13999-3:2007+A1:2009 (E) 3 Foreword This document (EN 13999-3:2007+A1:2009) has been prepared by Technical Committee CEN/TC 193 “Adhesives”, the
15、secretariat of which is held by AENOR. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by October 2009, and conflicting national standards shall be withdrawn at the latest by October 2009. This docum
16、ent includes Amendment 1, approved by CEN on 2009-04-03. This document supersedes !EN 13999-3:2007“. The start and finish of text introduced or altered by amendment is indicated in the text by tags ! “. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the fo
17、llowing countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, S
18、lovenia, Spain, Sweden, Switzerland and United Kingdom. DIN EN 13999-3:2009-08 EN 13999-3:2007+A1:2009 (E) 4 SAFETY STATEMENT Persons using this European Standard should be familiar with the normal laboratory practice, if applicable. This European Standard does not purport to address all of the safe
19、ty problems, if any, associated with its use. It is the responsibility of the user to establish appropriate health and safety practices and to ensure compliance with any regulatory conditions. 1 Scope This European Standard specifies a procedure for the determination of volatile aldehydes (especiall
20、y formaldehyde and acetaldehyde) and other carbonyl compounds in the exhaust air of an emission test chamber after application of a low-solvent or solvent-free adhesive as defined in EN 923. The method is based on chemosorption of volatile carbonyl compounds with 2,4-dinitrophenylhydrazine (in the f
21、ollowing: DNPH) impregnated silica tubes or cartridges with subsequent solvent desorption, clean-up and liquid chromatographic analysis. The method permits measurement of several aldehydes including formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, isovaleraldehyde, hexanal,
22、 benzaldehyde, 2,5-dimethylbenzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, crotonaldehyde in the concentration range of approximately 10 g/m to 1 mg/m (see ISO 16000-3). 2 Normative references The following referenced documents are indispensable for the application of this document. Fo
23、r dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN 1232, Workplace atmospheres Pumps for personal sampling of chemical agents Requirements and test methods EN 13999-1, Adhesives Short term m
24、ethod for measuring the emission properties of low-solvent or solvent-free adhesives after application Part 1: General procedure EN ISO 16000-9, Indoor air Part 9: Determination of the emission of volatile organic compounds from building products and furnishing Emission test chamber method (ISO 1600
25、0-9:2006) ISO 16000-3, Indoor air Part 3: Determination of formaldehyde and other carbonyl compounds Active sampling method 3 Principle A sufficient volume of test chamber air is drawn with an appropriate flow through silicagel tubes or cartridges impregnated with 2,4-dinitrophenylhydrazine (DNPH) r
26、eagent. Any organic aldehydes and other carbonyl compounds present will react to form non-volatile dinitrophenylhydrazones. Desorption is done with acetonitrile. The resultant solution is concentrated and analysed by high performance liquid chromatography (HPLC) with ultraviolet (UV) detection. Dini
27、trophenylhydrazone peaks from formaldehyde, acetaldehyde and other aldehydes are identified on the basis of both their respective retention times and their UV responses at more than one wavelength and/or by diode array detection (DAD) and comparison with a derivative product (where available) or sta
28、ndard. Quantification is done by comparison with a relevant aldehyde or a dinitrophenylhydrazone standard. DIN EN 13999-3:2009-08 EN 13999-3:2007+A1:2009 (E) 5 4 Reagents 4.1 Acetonitrile Acetonitrile of HPLC grade. 4.2 Standards Commercially available DNPH-aldehyde derivatives (or their solution(s)
29、 in acetonitrile). If the DNPH-aldehyde derivatives are prepared in the laboratory, the respective reagents described in ISO 16000-3 shall be used. 5 Apparatus 5.1 Sampler Commercially available tubes or cartridges filled with DNPH coated silica. If the samplers are prepared in the laboratory the re
30、spective reagents described in ISO 16000-3 shall be used. The ratio of the silica gel bed diameter to bed length shall not exceed 1:1. The capacity of the tube or cartridge for formaldehyde shall be at least 75 g and adsorption efficiency at least 95 % at the sampling rate applied. 5.2 Sampling pump
31、 The pump shall fulfil the requirements of EN 1232 or equivalent. 5.3 Tubing Tubing of appropriate diameter to ensure a leak-proof fit to both pump and sample tube. PTFE tubes shall be used upstream of the sorbent to avoid loss of substance due to reaction with tubing walls. 5.4 Flow meter calibrato
32、r Bubble meter or other appropriate suitable device for gas flow calibration. 5.5 High performance liquid chromatograph (HPLC) A typical apparatus for HPLC, with ultraviolet (UV) detector. 5.6 Emission test chamber An emission test chamber as described in EN 13999-1 or EN ISO 16000-9 shall be used.
33、6 Procedure 6.1 Test chamber air sampling Open the sealed tubes or remove the caps from the sampler and assemble the sampling line. Always use a sampler with a sampling section and a control section, or use two samplers in series with the downstream sampler serving as a control section. Prepare the
34、test chamber sampling port as described in EN 13999-1 or in EN ISO 16000-9. If the sampling flow rate is determined with a calibrator, start the pump, note and record the sampling flow rate. DIN EN 13999-3:2009-08 EN 13999-3:2007+A1:2009 (E) 6 Connect the sampler to the chamber sampling port, note a
35、nd record the time the sampler was connected. !Never use more than 90 % of the test chamber supply air flow“ rate as the combined sampling flow rates. At the end of the sampling period disconnect the sampler from the chamber sampling port, note and record the time of disconnection, repeat the sampli
36、ng flow determination, turn off the pump. Disconnect the sampler or the samplers from the sampling line and seal both ends using inert caps. NOTE The recommended sampling flow rate is in the range of 0,2 l/min. The recommended air volume is 24 l. 6.2 Storage of loaded samplers Store each sampler so
37、that it is isolated from other samples and from sources for volatile aldehydes, protected from light. If not analysed on the same day that the sample is collected, store the samplers at a temperature below 10 C. The time between sampling and analysis shall be as short as possible and shall not excee
38、d 14 days. 6.3 Blanks Take at least one blank sample which is a sampler equivalent to the ones used for sampling. Subject the blank samples to the same handling procedure in the laboratory as the actual samples except for the actual period of sampling, i.e. repeat the sampling procedure up to the po
39、int of actual sample collection. Do not perform sampling but repeat normal post-sampling procedure for the sampling tubes. Mark, store and analyse blank samples in sequence with the actual samples. For blank control of the test chamber see EN 13999-1. 6.4 Analysis 6.4.1 Cleaning of glassware Before
40、use, clean all glassware to remove any residual grease or chemicals by soaking overnight in laboratory detergent solution and then rinsing thoroughly with water. Alternatively, use a laboratory washing machine. 6.4.2 Sample desorption (cartridges) Desorb samples, blanks and standards by slowly passi
41、ng a small amount of acetonitrile through the cartridges as described in ISO 16000-3. 6.4.3 Sample desorption (tubes) Desorb samples, blanks and standards by separately emptying the content of the sections of the tube, adding a small amount of acetonitrile as described in ISO 16000-3 and letting it
42、stand at room temperature in the dark for at least 30 min with occasional agitation. 6.4.4 Standard solutions Prepare standard solutions in the analytical range of interest from commercially available DNPH-aldehyde derivatives (or their solution(s) in acetonitrile), or from self-produced DNPH-aldehy
43、de derivatives as described in ISO 16000-3. Store all standard solutions in tightly capped containers in a refrigerator and keep protected from light. Allow them to equilibrate to room temperature before use. They should be replaced after four weeks. 6.4.5 Calibration of liquid chromatograph Calibra
44、te the system by injecting a known fixed volume (e.g. 25 l) of at least five standard solutions covering the analytical range of interest into the liquid chromatograph using UV detection as described below. A standardised injection technique is required to obtain reproducible peak heights/areas. Pre
45、pare a calibration graph of UV response versus analyte concentration in the standard solutions as described in ISO 16000-3. DIN EN 13999-3:2009-08 EN 13999-3:2007+A1:2009 (E) 7 Once linear response (correlation coefficient of at least 0,999 for response versus concentration) has been documented, an
46、intermediate concentration standard near the anticipated levels of component, but at least ten times the detection limit, should be chosen for daily calibration. The day to day response of the analytical system for the various components shall be registered on a control card or in a corresponding el
47、ectronic data system and should be within 20 %. If greater variability is observed the system shall be checked, re-calibrated and fresh standards shall be prepared. 6.4.6 Analysis of desorbed sample solutions Inject a known fixed volume (25 l) of the desorbed sample solution into the liquid chromato
48、graph. Determine the UV response at the retention times being specific for the respective DNPH-aldehyde derivatives and read the concentration of the analyte in the sample from the calibration graph. Analyse the sample blank in the same way. NOTE A variety of chromatographic conditions can be used f
49、or the analysis of volatile aldehydes in solution. The choice will depend largely on the nature of interfering compounds, which may affect the chromatographic analysis. Typical conditions are as follows: - column dimensions 250 mm length 4,6 mm internal diameter, two columns in series; - column packing C18; - mobile phase acetonitrile / water, linear gradient; - flow rate 1 ml/min; - UV detector 360 nm and/or diode array detector. 7 Identification and calculation 7.1 Identification aldehydes For identification of the aldeh
