1. DETERMINATION OF FREE FORMALDEHYDE ON TEXTILE SUBSTRATE BY HPLC
Bojana VONCINA University of Maribor, Textile Department Smetanova 17, 2000 Maribor, Slovenia
ITSAPT seminar, Guimaraes, November 2005

2. ITSAPT seminar, Guimaraes, November 2005
Formaldehyde is built in the atmosphere thought photochemical processes of hydrocarbons
It is produced during the uncompleted combustion of wood, oil, gas, tobacco
Source of formaldehyde:
- Automobiles and airplanes %
- Heating and incineration %
- Formaldehyde in chem. prod. 1%
ITSAPT seminar, Guimaraes, November 2005

3. ITSAPT seminar, Guimaraes, November 2005
Formaldehyde is found in human body as a building blocks for amino acids and proteins
Blood mg/kg
Apple mg/kg
Tomatoes 6-7 mg/kg
Wood mg/kg
Formaldehyde 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%),
- intermediates (22%).
ITSAPT seminar, Guimaraes, November 2005

4. ITSAPT seminar, Guimaraes, November 2005
Toxicity Data
Formaldehyde is readily absorbed through skin and is toxic by
inhalation
It is considered toxic, carcinogen, mutagen, corrosive
Health Effects:
Inhalation: formaldehide is extremely destructive to tissue of the mucous membranes and that 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 reactions
Ingestion: Can cause gastrointestinal disturbances. May alter genetic material. This is considered a carcinogen.
Target Organs: eyes, kidneys, liver, heart, potential cancer agent, testis, ovaries  
ITSAPT seminar, Guimaraes, November 2005

5. 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 of in such way treated clothes Formaldehyde 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

6. Release of formaldehyde from the textile substrate can be measured by:
STANDARD TEST METHODS
Japan Law 112 (EN ISO )
AATCC-112
The 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 HPLC
HPLC
The accuracy of the standard test method for the the free formaldehyde determination, depends on the formaldehyde content of the sample.The formadehyde content below 20 ppm can not be shown to be caused by the formaldehyde which was released by the DMDHEU.
ITSAPT seminar, Guimaraes, November 2005

7. ITSAPT seminar, Guimaraes, November 2005
EN ISO standard test method Standard 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 replicates of each concentration level were prepared From the textile substrateformaldehyde was extracted with water at 40C, filtered and then converted by using acetyl-acetone reagent to yellow colored compound
Formaldehyde content in standard solutions and in extracts from textile materal was analysed by using UV/VIS spectrophotometric detection at a wavelength of 412 nm against water.
ITSAPT seminar, Guimaraes, November 2005

8. Validation of absorbance measurements on UV/Vis
With Grubbs and Beck statistical test were shown that there were no aberrant values
An F – test was applied to check heteroscedasticity: standard deviation increase with the concentration
Correlation coefficient for standard water and matrix solutions was greater than 0.99
Quality coefficient (QC) was lower than 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 mg/l
The limit of quantification (LOQ) was mg/l
The amount of formaldehyde extracted for each sample can be calculated by:
Konc (x) = 7,493 ABS - 0,06356
ITSAPT seminar, Guimaraes, November 2005

9. 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, - diacetyl –1,4-dihydrolutidin forms were prepared
Formaldehyde was extracted from textile substrate with water at 40C, filtered and then converted by using acetylacetone reagent to yellow colored compound
HPLC Varian Prostar 210 pump,
Varian Prostar 310 UV/Vis detector (at 410 nm),
STAR Chromatography Workstation Varian 4.5,
LiChrosorb RP-18 coloum with particle size 7 m,
ITSAPT seminar, Guimaraes, November 2005

10. 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 aqueous
solution was determined using
peak areas from the standard
and 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

11. Validation of the HPLC analytical method
With Grubbs and Beck statistical test were shown that there were no aberrant values
An F – test was applied to check heteroscedasticity: standard deviation increase with the concentration
Correlation coefficient for standard water and matrix solutions was greater than 0.99
Quality coefficient (QC) was lower than 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 mg/l
The limit of quantification (LOQ) was mg/l
The amount of formaldehyde extracted for each sample can be calculated by:
Konc (x) = 0,2055 * 10-4 AREA – 0,222
ITSAPT seminar, Guimaraes, November 2005

12. ITSAPT seminar, Guimaraes, November 2005
CONCLUSIONS
The results obtained by the standard test method, Japan
Law112, were compared with the results obtained by HPLC
method where separation was performed on RP C 18 column
with water-MeOH as a mobile phase.
The limit of detection (LOD) for Japan Law 112 was mg/l and the limit of quantification (LOQ) was mg/l
The limit of detection (LOD) for HPLC method was mg/l and the limit of quantification (LOQ) was mg/l  
Matrix has no influence on the formaldehyde content in the analysed solution.
ITSAPT seminar, Guimaraes, November 2005

13. FORMALDEHYDE IN MICROENCAPTULATED TEXTILE MATERIALS
Bojana VONCINA
University of Maribor, Textile Department
Smetanova 17, 2000 Maribor, Slovenia
ITSAPT seminar, Guimaraes, November 2005

14. ITSAPT seminar, Guimaraes, November 2005
Introduction
Essential oils from plants Lavandula sp.
(lavender), Rosmarinus sp (rosemary) and
Salvia sp. (sage) are natural fungicide and
antibacterial agents.
These oils were microencapsuled in melamine-
formaldehyde microcapsules and cross linked on
PES nonwoven textile materials.
Such textile material is capable of
releasing formaldehyde by decomposition
of microcapsules.
ITSAPT seminar, Guimaraes, November 2005

15. 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: isopropyl mirystate
ITSAPT seminar, Guimaraes, November 2005

16. ITSAPT seminar, Guimaraes, November 2005
Experimental
Release of formaldehyde from the textile substrate was determined by
EN ISO (Japan Law 112 method),
AATCC test ,
HPLC method, where the separation was achieved with elution using methanol-water, as eluents on a reverse 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

17. ITSAPT seminar, Guimaraes, November 2005
The formaldehyde contents were determined in
different textile samples:
a) untreated 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 (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

18. Results and conclusions
Untreated textile material and cross-linking reagent do not contain formaldehyde (7 mg/kg).
Microcapsule’s 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 microencaptulated textile material with microcapsules filled with oils (both results are obtained by Japan Law method).
Results from AATCC test for the same samples are mg/kg and mg/kg respectively. .
ITSAPT seminar, Guimaraes, November 2005

19. ITSAPT seminar, Guimaraes, November 2005
Results obtained by HPLC method:
indicate 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 total 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

20. ITSAPT seminar, Guimaraes, November 2005
Formaldehyde measurements
in essential oils:
Lavender: 0,54 ml/L
Rosemary: 0,15 ml/L
Sage: 0,32 ml/L
mixture of essential oils :
Average amounts of formaldehyde: 0,61 ml/L
Results: from 0,18 to 0,75 ml/L (dependent on extraction conditions)
ITSAPT seminar, Guimaraes, November 2005

21. ITSAPT seminar, Guimaraes, November 2005
Conclusion
Microcapsule’s wall contributes to the highest degree of the amount of formaldehyde
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
Results given by AATCC test method are expected proportionally higher as results given by EN ISO method.
After washing of textile substrate, the results are considerable lower
The average results obtained from samles prapered in production line are lower. Those samples satisfy eco-labeling system’s requirement. The explanation for this phenomenon is found in different processes of curing and drying.
ITSAPT seminar, Guimaraes, November 2005