ITSAPT seminar, Guimaraes, November 2005 DETERMINATION OF FREE FORMALDEHYDE ON TEXTILE SUBSTRATE BY...
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Transcript of ITSAPT seminar, Guimaraes, November 2005 DETERMINATION OF FREE FORMALDEHYDE ON TEXTILE SUBSTRATE BY...
ITSAPT seminar, Guimaraes, November 2005
DETERMINATION OF FREE DETERMINATION OF FREE FORMALDEHYDE ON TEXTILE FORMALDEHYDE ON TEXTILE
SUBSTRATE BY HPLCSUBSTRATE BY HPLC
Bojana VONCINA
University of Maribor, Textile Department
Smetanova 17, 2000 Maribor, Slovenia
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 70-80%
- Heating and incineration 13-15%
- Formaldehyde in chem. prod. 1%
ITSAPT seminar, Guimaraes, November 2005
Formaldehyde is found in human body as a building blocks for amino acids and proteins
Blood 2-3 mg/kgApple 17-22 mg/kgTomatoes 6-7 mg/kgWood 4-18 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
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
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
C
O
N CH2OH
CH
OH
CH
OH
NHOH2C
C
O
N CH2
CH
OH
CH
OH
NCH2 O CH3OCH3
DMDHEU modified DMDHEU
ITSAPT seminar, Guimaraes, November 2005
Release of formaldehyde from the textile substrate can be measured by:
STANDARD TEST METHODSJapan Law 112 (EN ISO 14184-1)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 HPLCHPLC
ITSAPT seminar, Guimaraes, November 2005
EN ISO 14184-1 EN ISO 14184-1 standard test methodstandard 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 40C, filtered and then converted by using acetyl-acetone reagent to yellow colored compound
C
O
CH3
CH2
C
O
CH3
+
C
O
HH
N
H
HH
CH2
C
O
C
O
CH3
CH3C
O
CH3CH2
C
CN
C
C
H
CH3
C
O
CH3
CH3
ITSAPT seminar, Guimaraes, November 2005
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 0.628 mg/l The limit of quantification (LOQ) was 1.197 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
Free formaldehyde measured by HPLCFree 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 40C, 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
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.
2.25
2.50
2.75 Minutes
0
50
100
150
200
250
300
mAU
Retention time [min]
30 mg/L 15 mg/L 1,5 mg/L 0,3 mg/L
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 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 0.0199 mg/l The limit of quantification (LOQ) was 0.066 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
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 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.
ITSAPT seminar, Guimaraes, November 2005
FORMALDEHYDE IN MICROENCAPTULATED TEXTILE MATERIALS
Bojana VONCINA
University of Maribor, Textile Department
Smetanova 17, 2000 Maribor, Slovenia
ITSAPT seminar, Guimaraes, November 2005
Introduction
• Essential oils from plants Lavandula sp.(lavender), Rosmarinus sp (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 seminar, Guimaraes, November 2005
Sources of the formaldehyde
Textile material (PES) cross-linking reagent microcapsules
wall : wall : melamine-formaldehyde resinsmelamine-formaldehyde resins core :core : 25 % 25 % mixture of essential oilsmixture of essential oils, 75 % , 75 % solventsolvent
80 % 80 % mixture of essential oilsmixture of essential oils, 20 % solvent, 20 % solvent mixture of essential oilsmixture of essential oils: - lavender 70 %: - lavender 70 %
- rosemary 20 - rosemary 20 %%
- sage 10 %- sage 10 % solvent: isopropyl solvent: isopropyl mirystatemirystate
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 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) 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
• 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 5.126
mg/kg and 4.174 mg/kg respectively.
.
Results and conclusions
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
Lavender: 0,54 ml/LLavender: 0,54 ml/L Rosemary: 0,15 ml/LRosemary: 0,15 ml/L Sage: 0,32 ml/LSage: 0,32 ml/L
mixture of essential oilsmixture of essential oils : : Average amountsAverage amounts of formaldehyde of formaldehyde: 0,61 ml/L: 0,61 ml/L Results: from 0,18 to 0,75 ml/L (dependent Results: from 0,18 to 0,75 ml/L (dependent
on extraction conditions)on extraction conditions)
FormaldehydeFormaldehyde measurements measurementsin essential oils:in essential oils:
ITSAPT seminar, Guimaraes, November 2005
ConclusionConclusion
Results given by AATCC test 112-1978 method are expected Results given by AATCC test 112-1978 method are expected proportionally higher as results given by EN ISO 14184-1 method.proportionally higher as results given by EN ISO 14184-1 method.
The aThe average results verage results obtained from samles prapered in production line obtained from samles prapered in production line are are
lowerlower. T. Those samples hose samples satisfysatisfy eco-labeling system’s requirement. eco-labeling system’s requirement. TThe he explanation for this phenomenon is found in different processes of curing and explanation for this phenomenon is found in different processes of curing and drying. drying.
By HPLC it was proven that there are no other aldehydes or ketones present on microcapsulated textile materiale
IIt was provent was proven that the amount of formaldehyde in essential oils is negligible that the amount of formaldehyde in essential oils is negligible
Microcapsule’s wall contributes to the highest degree of the amount of formaldehyde
After washing of textile substrate, the results are considerable lowerAfter washing of textile substrate, the results are considerable lower