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Training on Formaldehyde test (ISO 14184-1/ISO 14184-2/JIS 1041 A)

TUV Rheinland Bangladesh Ltd.


Zahidur Rahman, Laboratory Manager
Determination of Formaldehyde -
Part 1: Free and Hydrolyzed Formaldehyde (Water Extraction
Method)

(ISO 14184-1: 1998)


Introduction

1. This training material serves to cover the following aspects:


1. Background information,
2. Testing techniques,
3. Method of evaluation, and
4. Important notes
for the subsequent test in order to ensure the testing uniformity, result consistency & reproducibility.

• As this training material focuses on the general information only, it is anticipated for trainee without
background knowledge. Experienced staff, however, can refer the materials as reference guidelines.

• Practical training followed with an assessment is highly recommended to testify and reinforce the
understanding of the trainee on the subsequent test.

• A procedure checklist is available for the assessment


Summary Free and Hydrolized Formaldehyde (ISO 14184-1)

1. Scope & Principle


2. Apparatus
3. Sample Preparation (Accompanied with movie illustration)
4. Test Procedures (Accompanied with movie illustration)
5. Confirmation Test
6. Calibration Curve
7. Result Evaluation
8. Example of Formaldehyde Calculation
9. ISO, AATCC, JIS & BS Test Comparison
1 Scope & Principle Free and Hydrolyzed Formaldehyde (ISO 14184-1)

• To determinate the amount of free formaldehyde and formaldehyde extracted


partly through hydrolysis by means of water extraction method

• It is applicable to testing of textile samples in any form

• Formaldehyde is extracted from textile sample with water at 40°C. The


amount of formaldehyde is then determined colorimetrically

• The procedure is intended for use in the range of free and hydrolysed
formaldehyde on the fabric between 16mg/kg and 3500mg/kg when
determined by this method. The lower limit is 16mg/kg.

• Below this limit the result is reported as “not detectable”


2 Apparatus Free and Hydrolized Formaldehyde (ISO 14184-1)

UV-Visible Spectrophotometer or colorimeter


3 Sample Preparation Free and Hydrolized Formaldehyde (ISO 14184-1)

1. Cut two specimens approximately 1g of pieces. If the formaldehyde content is


low, increase the test specimen weight to 2.5 g.

2. Put the weighed pieces into 250ml flask with stopper and add 100ml of water.

3. Stopper tightly and place in a water bath at 40 ± 2°C for 60 ± 5 min with
shaking at least every 5 min.

4. Filter the solution into another


flask through a filter.

Important Notes:

• Do not condition the test


specimen before test

• Storage the test specimen in a


polyethylene bag and wrapped
in aluminum foil.
5 Test Procedures Free and Hydrolyzed Formaldehyde (ISO 14184-1)

Aliquot & Blank Solution Preparation


1. Prepare four Test Tube A to D as
55ml
mlfiltered
filtered 5 ml standard 5 ml 55ml
mlfiltered
filtered
follows: test
test specimen formaldehyde 5 ml Nash
Nash test specimen
test
specimen
solution + 5ml solution + 5ml reagent + solution + 5ml
specimen
reagent
solution 5ml water water
1. Tube A: 5ml of the filtered Nash reagent Nash reagent solution

test specimen solution +


5ml of Nash reagent
2. Tube B: 5ml of the standard 0.15 0.75
ppm ppm
formaldehyde solutions +
5ml of Nash reagent
3. Tube C: 5ml of Nash
reagent + 5ml of water
(Blank)
4. Tube D: 5ml of filtered test
specimen solution + 5ml of
water (Blank)
5 Test Procedures Free and Hydrolized Formaldehyde (ISO 14184-1)

Aliquot & Blank Solution


Preparation
2. Keep the Tubes A & B in a
water bath at 40 + 2C for 30 +
5min and then at ambient
temperature for 30±5min
3. Measure the absorbances using
a spectrometer in a 10mm
absorption cell at a wavelength
of 412mm against water.

Important Notes
• Exposure of the developed yellow colour to direct sunlight for a period of time will
cause some fading. Care should be taken to protect the tubes such as by covering
them with a formaldehyde free enclosure
5 Confirmation Test Free and Hydrolized Formaldehyde (ISO 14184-1)

• Confirmation test (using dimedone) can be carried out to confirm the


absorption is due to formaldehyde or extracted colouring agent.
• Dimedone reacts with formaldehyde , and thus no colour resulting from
formaldehyde reaction will be observed.
Test procedures:
1. 5ml of sample solution (5ml water for blank solution) mix with
1ml of ethanol solution of dimedone and shake
2. Warm the solution in water bath at 40oC for 10min
3. Add 5ml Nash reagent, shake and continue warm in the same
water bath for 30min
4. Cool down the solution to room temperature for 30min
5. Determine the absorbance of sample & blank solution at 412nm
6. Theoretically, no absorbance will be observed at 412nm
5 Calibration Curve Free and Hydrolized Formaldehyde (ISO 14184-1)

Formaldehyde Stock Solution (1500 mg/l) Preparation


Dilute 3.5 ml of formaldehyde solution to one liter with water.
Record the accurate concentration of this standardized stock solution by
reacting the formaldehyde solution with an excess of sodium sulfite followed
by a back-titration with acid solution in the presence of thymolphthalein as
indicator.
The stock Solution will keep for up to four weeks and is used to prepare
standard dilutions.

Calibration solutions Preparation


Dilute aliquots (1, 2, 5, 10, 15, 20, 30 & 40ml) of the standard solution with
distilled water in 500 mL volumetric flasks to give standard formaldehyde
solutions containing approximately (0.15, 0.30, 0.75, 1.50, 2.25, 3.00, 4.50
& 6.00) g/mL formaldehyde respectively.
6 Result Evaluation Free and Hydrolized Formaldehyde (ISO 14184-1)

Absorbance of the test specimen:


A = As - Ab - (Ad)
• A = corrected absorbance
• As = measured absorbance of the test specimen (Tube A)
• Ab = measured absorbance of the blank reagent (Tube C)
• Ad = measured absorbance of the blank specimen (Tube D), only in case of discoloration or
the contamination

Amount of the formaldehyde extracted for each specimen (F) to the nearest mg/kg
𝐶×𝑉
F = × 𝐷. 𝐹
𝑊
Where,
C = Concentration of formaldehyde in sample solution as read from
calibration graph , mg/L
V = Volume of water extract, 100 mL
W = Sample weigh, 1 g / 2.5 g
D.F. = Dilution factor

If the result is less than 20mg/kg report as “not detectable”


5 Example of
Formaldehyde Calculation
Free and Hydrolized Formaldehyde (ISO 14184-1)

For Example:
1. Calibration
curve
development

2. Measure
the absorbance 3. Find the
of aliquot intersection point

4. Formaldehyde
content in the
aliquot
Thank you.
14 3/31/2019
1
Released Formaldehyde (Vapor Absorption
Method)/ISO 14184-2
Scope & Principle

• To determinate the amount of formaldehyde released under the conditions of


accelerated storage from textiles in any form by means of a vapor absorption
method.
• It is applicable to testing of textile samples in any form
• A weighed fabric specimen is suspended over water in a sealed jar. The jar is
placed in an incubator at a controlled temperature for a specified length of
time. The amount of formaldehyde absorbed by the water is then determined
colorimetrically.

• This procedure is intended for use in the range of releasable formaldehyde on


the fabric between 20 mg/kg and 3500 mg/kg when determined by this
method.
• Below this limit the result is reported as “not detectable”
2
Released Formaldehyde (Vapor Absorption
Method)/ISO 14184-2
Apparatus

UV-Visible Spectrophotometer or colorimeter


3
Released Formaldehyde (Vapor Absorption
Method)/ISO 14184-2
Sample Preparation

1. Cut the textile specimen to about 20 mm x 20 mm in size approximately 1g of


pieces. Prepare duplicate (for ISO 14184-2 and GB/T 2912-2) of specimen
per each sample.
2. Pipette 50 mL of water into 1 L jar .
3. Suspend the specimen (9.2.3) above the water level in each jar such as is
shown In figure1.

4. Seal the jar and place it in the oven at 49 ± 2º C


for 20 hours ± 15 minutes.

5. Cool down at room temperature for 30 ± 5


minutes after incubation.

6. Remove the specimen from the jar.

7. Recap the jar immediately and shake it to mix


any condensation formed on the jar sides.
3
Released Formaldehyde (Vapor Absorption
Method)/ISO 14184-2
Sample Preparation

Important Notes:

• Do not condition the test specimen before test

• Storage the test specimen in a polyethylene bag and wrapped in


aluminum foil.
5
Released Formaldehyde (Vapor Absorption
Method)/ISO 14184-2
Test Procedures

Aliquot & Blank Solution Preparation


1. Prepare four Test Tube A to D as
55ml
mlfiltered
filtered 5 ml standard 5 ml 55ml
mlfiltered
filtered
follows: test
test specimen formaldehyde 5 ml Nash
Nash test specimen
test
specimen
solution + 5ml solution + 5ml reagent + solution + 5ml
specimen
reagent
solution 5ml water water
1. Tube A: 5ml of the filtered Nash reagent Nash reagent solution

test specimen solution +


5ml of Nash reagent
2. Tube B: 5ml of the standard 0.15 0.75
ppm ppm
formaldehyde solutions +
5ml of Nash reagent
3. Tube C: 5ml of Nash
reagent + 5ml of water
(Blank)
4. Tube D: 5ml of filtered test
specimen solution + 5ml of
water (Blank)
5
Released Formaldehyde (Vapor Absorption
Method)/ISO 14184-2
Test Procedures

Aliquot & Blank Solution


Preparation
2. Keep the Tubes A & B in a
water bath at 40 + 2C for 30 +
5min and then cool down at
ambient temperature for
30±5min
3. Measure the absorbances using
a spectrometer in a 10mm
absorption cell at a wavelength
of 412mm against water.
Important Notes
• Exposure of the developed yellow colour to direct sunlight for a period of time will
cause some fading. Care should be taken to protect the tubes such as by covering
them with a formaldehyde free enclosure
5
Released Formaldehyde (Vapor Absorption
Method)/ISO 14184-2
Confirmation Test

• Confirmation test (using dimedone) can be carried out to confirm the


absorption is due to formaldehyde or extracted colouring agent.
• Dimedone reacts with formaldehyde , and thus no colour resulting from
formaldehyde reaction will be observed.
Test procedures:
1. 5ml of sample solution (5ml water for blank solution) mix with
1ml of ethanol solution of dimedone and shake
2. Warm the solution in water bath at 40oC for 10min
3. Add 5ml Nash reagent, shake and continue warm in the same
water bath for 30min
4. Cool down the solution to room temperature for 30min
5. Determine the absorbance of sample & blank solution at 412nm
6. Theoretically, no absorbance will be observed at 412nm
5
Released Formaldehyde (Vapor Absorption
Method)/ISO 14184-2
Calibration Curve

Formaldehyde Stock Solution (1500 mg/l) Preparation


Dilute 3.5 ml of formaldehyde solution to one liter with water.
Record the accurate concentration of this standardized stock solution by
reacting the formaldehyde solution with an excess of sodium sulfite followed
by a back-titration with acid solution in the presence of thymolphthalein as
indicator.
The stock Solution will keep for up to four weeks and is used to prepare
standard dilutions.

Calibration solutions Preparation


Dilute aliquots (1, 2, 5, 10, 15, 20, 30 & 40ml) of the standard solution with
distilled water in 500 mL volumetric flasks to give standard formaldehyde
solutions containing approximately (0.15, 0.30, 0.75, 1.50, 2.25, 3.00, 4.50
& 6.00) g/mL formaldehyde respectively.
6
Released Formaldehyde (Vapor Absorption
Method)/ISO 14184-2
Result Evaluation

Absorbance of the test specimen:


A = As - Ab - (Ad)

• A = corrected absorbance
• As = measured absorbance of the test specimen (Tube A)
• Ab = measured absorbance of the blank reagent (Tube C)
• Ad = measured absorbance of the blank specimen (Tube D), only in case of discoloration or
the contamination

Amount of the formaldehyde extracted for each specimen (F) to the nearest mg/kg
F = (C x 100) / W

• C = concentration of formaldehyde in solution (in mg/l) as read form the calibration graph
• W = Mass

If the result is less than 20mg/kg report as “not detectable”


JIS L 1041 A & B

 To determine free formaldehyde in textiles by acetylacetone method.

 It is as per JIS Law No. 112 October 12th, 1973.


 It is for resin finished textiles implying woven, knitted fabrics and also lace.

 JIS test method A -For babies or infants within 24 months after birth
 JIS test method B-Over 24 months .

 Textile products for Infants and babies (Infants and babies means the age within 24 months)
including underwear, nappies, bedding, gloves, socks, clothing etc.
JIS L 1041: Preparation of test specimens

• Cut the textile specimen to about 5 mm x 5 mm in size.

 The test portion should be taken from extremities and the central part to ensure its
homogeneity.

 For Method A, weigh 2.50 ± 0.01 g of the sample and put it into a 200 ml Erlenmeyer
flask with stopper.

 For Method B, weigh 1.00 ± 0.01 g of the sample and put it into a 200 ml Erlenmeyer
flask with stopper.
JIS L 1041: Preparation of the aqueous extract

 Pipette 100 mL of water into a flask containing test sample and sealed with stopper.

 Place the flask into a shaking water bath at 40 ± 2 oC (4.11). Providing a to-and-fro
movement at a rate approximately 20 min-1

 Shake mechanically for 1 hour.

 Filter the aqueous extract by a filter paper (4.8) when the solution is still warm
JIS L 1041: Color development of sample solution

 Transfer 5 mL of sample extract into 2 reaction vials respectively.

 Pipette 5 mL of Nash reagent into a first vial (Sample solution, AN).

 Pipette 5 mL of ammonium acetate buffer into a second vial in as sample background


solution,(Ab).

 Place the vials in shaking water bath at 40 ± 2 oC for 30 minutes.

 Cool down the vials at room temperature for 30 minutes after shaking.
JIS L 1041: Color development in working standards solution
& calibration check solution
 Pipette 5 mL of each standard working solution into 5 reaction vials respectively.
 Pipette 5 mL of Nash reagent into each of vials.

 Pipette 5 mL of 0.3 mg/L calibration check standard (5.5.1) into a reaction vial.
 Pipette 5 mL of Nash reagent (5.2.18) into the vial.
Calculations

 Construct a calibration curve by plotting the absorbance against the concentration of


formaldehyde standard solutions.
 For each test specimen corrected the absorbance (Acorrect) of the specimen, to the
nearest 0.001 as
 below equation: Acorrect = A – Ao = (AN – Ar) –(Ab- Asb)
 Where
 A = Absorbance of sample solution (AN) against reagent blank (Ar); (AN – Ar)
Ao = Absorbance of sample background solution (Ab) against solution blank; (Ab-
Asb)
9 ISO, JIS AATCC &
BS Test Comparison

Comparison of ISO 14184-1, JIS S & B (L 1041 ), ISO 14184-2, AATCC 112, & BS 6806
standards on formaldehyde
ISO 14184-1 JIS A & B (L1041) ISO 14184-2 AATCC 112 BS 6806 Part 2 & 3
Objects
For free For free For released For released For free & released
Scope
formaldehyde formaldehyde Formaldehyde Formaldehyde formaldehyde
2.0g for free
2.5 g for A formaldehyde
Weight of specimen 1g 1g 1.0 g
1.0 g for B 1.0g for released
formaldehyde
25oC for free
Extraction formaldehyde
40oC 40oC 49 ± 2º C 65oC
temperature 49oC for released
formaldehyde
20 min or free
20 hours ± 15 formaldehyde
Extraction time 1 hr 1 hr 4 hrs
minutes 20 hrs for released
formaldehyde

Reagent for reaction


Nash Nash Nash Nash Chromotropic acid
with formaldehyde

Wavelength for
absorbance 412 nm 415 nm 412 nm 412 nm 570 nm
measurement