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1、ITSAPT seminar,Guimaraes,November 2005,DETERMINATION OF FREE FORMALDEHYDE ON TEXTILE SUBSTRATE BY HPLC,Bojana VONCINAUniversity of Maribor,Textile Department Smetanova 17,2000 Maribor,Slovenia,ITSAPT seminar,Guimaraes,November 2005,Formaldehyde is built in the atmosphere thought photochemical proces
2、ses of hydrocarbonsIt is produced during the uncompleted combustion of wood,oil,gas,tobaccoSource of formaldehyde:-Automobiles and airplanes70-80%-Heating and incineration 13-15%-Formaldehyde in chem.prod.1%,ITSAPT seminar,Guimaraes,November 2005,Formaldehyde is found in human body as a building blo
3、cks for amino acids and proteinsBlood2-3 mg/kgApple 17-22 mg/kgTomatoes6-7 mg/kgWood4-18 mg/kgFormaldehyde is often used as a building block for a number of important chemical products,intermediates and consumer goods:-urea-formaldehyde resins(25%),-phenol-formaldehyde resins(20%),-plastics(15%),-in
4、termediates(22%).,ITSAPT seminar,Guimaraes,November 2005,Toxicity DataFormaldehyde is readily absorbed through skin and is toxic byinhalation It is considered toxic,carcinogen,mutagen,corrosiveHealth Effects:Inhalation:formaldehide is extremely destructive to tissue of the mucous membranes and that
5、of the upper respiratory tract.Inhalation may be fatal as a result of spasm and inflammation.Eyes/Skin:extremely destructive to the tissue of the eyes and skin.Can cause allergic skin reactionsIngestion:Can cause gastrointestinal disturbances.May alter genetic material.This is considered a carcinoge
6、n.Target Organs:eyes,kidneys,liver,heart,potential cancer agent,testis,ovaries,ITSAPT seminar,Guimaraes,November 2005,The most effective crosslinking reagents for durable press finishing of cellulose fibers are formaldehyde adducts of urea which release formaldehyde during the production and wearing
7、 of in such way treated clothesFormaldehyde durable press finishers are applied to the textile substrate mainly in the form of N-methylol and N-alkoxymethyl compounds,ITSAPT seminar,Guimaraes,November 2005,Release of formaldehyde from the textile substrate can be measured by:,STANDARD TEST METHODSJa
8、pan Law 112(EN ISO 14184-1)AATCC-112The formaldehyde content below 20 mg/kg can not be shown to be caused by the formaldehyde which was released by the crosslinking reagent.ALTERNATIVE TEST METHODS edana recommended test method using HPLCHPLC,ITSAPT seminar,Guimaraes,November 2005,EN ISO 14184-1 sta
9、ndard test methodStandard solutions of formaldehyde with concentration levels of 0.3,0.6,0.9,3.0,6.0,15.0 and 30.0 mg/L in the 3,5,-diacetyl 1,4-dihydrolutidin forms were prepared.The formaldehyde derivative solutions were prepared in water and in matrix(extract from untreated cotton fibers).Six rep
10、licates of each concentration level were preparedFrom the textile substrateformaldehyde was extracted with water at 40C,filtered and then converted by using acetyl-acetone reagent to yellow colored compound,ITSAPT seminar,Guimaraes,November 2005,Validation of absorbance measurements on UV/Vis,With G
11、rubbs and Beck statistical test were shown that there were no aberrant valuesAn F test was applied to check heteroscedasticity:standard deviation increase with the concentrationCorrelation coefficient for standard water and matrix solutions was greater than 0.99Quality coefficient(QC)was lower than
12、permitted 5%Anova test shows that the experimental error was smaller than lack of fit(LOF)for the linear calibration curve Precision of standard water and matrix solutions was better than 10%The limit of detection(LOD)was 0.628 mg/lThe limit of quantification(LOQ)was 1.197 mg/l The amount of formald
13、ehyde extracted for each sample can be calculated by:Konc(x)=7,493 ABS-0,06356,ITSAPT seminar,Guimaraes,November 2005,Free formaldehyde measured by HPLC,Standard water and matrix solutions of formaldehyde with concentrations levels 0.075,0.15,0.3,0.6,0.9,3.0,6.0,15.0 and 30.0 mg/L in the 3,5,-diacet
14、yl 1,4-dihydrolutidin forms were preparedFormaldehyde was extracted from textile substrate with water at 40C,filtered and then converted by using acetylacetone reagent to yellow colored compoundHPLC Varian Prostar 210 pump,Varian Prostar 310 UV/Vis detector(at 410 nm),STAR Chromatography Workstation
15、 Varian 4.5,LiChrosorb RP-18 coloum with particle size 7 m,ITSAPT seminar,Guimaraes,November 2005,Validation of the HPLC analytical method,The optimisation of the method(the proper column,mobile phase,solvents,temperature of the column etc.)was done.The concentration of free formaldehyde in the aque
16、oussolution was determined usingpeak areas from the standardand sample chromatograms.,Mobile phase methanol-water(70:30 v/v).The retantion time for formaldehyde derivative was 2.7 min,ITSAPT seminar,Guimaraes,November 2005,Validation of the HPLC analytical method,With Grubbs and Beck statistical tes
17、t were shown that there were no aberrant valuesAn F test was applied to check heteroscedasticity:standard deviation increase with the concentrationCorrelation coefficient for standard water and matrix solutions was greater than 0.99Quality coefficient(QC)was lower than permitted 5%Anova test shows t
18、hat the experimental error was smaller than lack of fit(LOF)for the linear calibration curvePrecision of standard water and matrix solutions was better than 10%The limit of detection(LOD)was 0.0199 mg/lThe limit of quantification(LOQ)was 0.066 mg/l The amount of formaldehyde extracted for each sampl
19、e can be calculated by:Konc(x)=0,2055*10-4 AREA 0,222,ITSAPT seminar,Guimaraes,November 2005,CONCLUSIONS,The results obtained by the standard test method,JapanLaw112,were compared with the results obtained by HPLCmethod where separation was performed on RP C 18 column with water-MeOH as a mobile pha
20、se.The limit of detection(LOD)for Japan Law 112 was 0.628 mg/l and the limit of quantification(LOQ)was 1.197 mg/l The limit of detection(LOD)for HPLC method was 0.0199 mg/l and the limit of quantification(LOQ)was 0.066 mg/l Matrix has no influence on the formaldehyde content in the analysed solution
21、.,ITSAPT seminar,Guimaraes,November 2005,FORMALDEHYDE IN MICROENCAPTULATED TEXTILE MATERIALS,Bojana VONCINAUniversity of Maribor,Textile Department Smetanova 17,2000 Maribor,Slovenia,ITSAPT seminar,Guimaraes,November 2005,Introduction,Essential oils from plants Lavandula sp.(lavender),Rosmarinus sp(
22、rosemary)andSalvia sp.(sage)are natural fungicide andantibacterial agents.These oils were microencapsuled in melamine-formaldehyde microcapsules and cross linked onPES nonwoven textile materials.Such textile material is capable ofreleasing formaldehyde by decompositionof microcapsules.,ITSAPT semina
23、r,Guimaraes,November 2005,Sources of the formaldehyde,Textile material(PES)cross-linking reagent microcapsules,wall:melamine-formaldehyde resins core:25%mixture of essential oils,75%solvent 80%mixture of essential oils,20%solvent mixture of essential oils:-lavender 70%-rosemary 20%-sage 10%solvent:i
24、sopropyl mirystate,ITSAPT seminar,Guimaraes,November 2005,Experimental,Release of formaldehyde from the textile substrate was determined by EN ISO 14184-1(Japan Law 112 method),AATCC test 112-1998,HPLC method,where the separation was achieved with elution using methanol-water,as eluents on a reverse
25、 phase column and was monitored at 410 nm with a UV/VIS detector.In all three methods the extracted formaldehyde was converted by using acetylacetone reagent to yellow coloured compound.,ITSAPT seminar,Guimaraes,November 2005,The formaldehyde contents were determined in different textile samples:a)u
26、ntreated textile material(PES nonwoven)b)textile material with cross-linking reagent(suspension of latex and acrilate emulsifier)c)textile material with empty microcapsules,d)textile material with cross-linkinked empty microcapsules,e)textile material with cross-linked microcapsules filled with oils
27、(25%mixture of essential oils,75%solvent)f)textile material with cross-linked microcapsules filled with oils(80%mixture of essential oils,20%solvent)The formaldehyde contents were determine also in mixture of oils and pure rosemary and sage oil.,ITSAPT seminar,Guimaraes,November 2005,Untreated texti
28、le material and cross-linking reagent do not contain formaldehyde(7 mg/kg).Microcapsules walls contribute to the amount of of the formaldehyde significantly:The average formaldehyde content for the microencaptulated textile material with empty microcapsules is 715 mg/kg and 766 mg/kg for microencapt
29、ulated textile material with microcapsules filled with oils(both results are obtained by Japan Law method).Results from AATCC test for the same samples are 5.126 mg/kg and 4.174 mg/kg respectively.,Results and conclusions,ITSAPT seminar,Guimaraes,November 2005,Results obtained by HPLC method:indicat
30、e that only formaldehyde is released from the textile samples microencaptulated with and without essential oil.Although some amount of formaldehyde is proved in pure essential oils,amount of essential oil which is applied on textile material with microcapsules(160 g/m2)contribute very little to tota
31、l amount of formaldehyde.This was proved by the measurements of released formaldehyde after the mechanical damages of microcapsules on the textile substrate,ITSAPT seminar,Guimaraes,November 2005,Lavender:0,54 ml/LRosemary:0,15 ml/LSage:0,32 ml/Lmixture of essential oils:Average amounts of formaldeh
32、yde:0,61 ml/LResults:from 0,18 to 0,75 ml/L(dependent on extraction conditions),Formaldehyde measurementsin essential oils:,ITSAPT seminar,Guimaraes,November 2005,Conclusion,Results given by AATCC test 112-1978 method are expected proportionally higher as results given by EN ISO 14184-1 method.,The
33、average results obtained from samles prapered in production line are lower.Those samples satisfy eco-labeling systems requirement.The explanation for this phenomenon is found in different processes of curing and drying.,By HPLC it was proven that there are no other aldehydes or ketones present on microcapsulated textile materiale,It was proven that the amount of formaldehyde in essential oils is negligible,Microcapsules wall contributes to the highest degree of the amount of formaldehyde,After washing of textile substrate,the results are considerable lower,
