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IDENTIFICATION OF PLASTICS

IDENTIFICATION OF PLASTICS

VISHAL VERMA
Technical Officer

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IDENTIFICATION OF PLASTICS

IDENTIFICATION
When working with plastics there is often a need to identify
which particular plastic material has been used for a given
product. This is essential to get an idea of the cost and likely
properties of the product. The identification of plastics is
generally very difficult due to:
 The wide range of basic polymers that is available for
use.
 The wide range of additives that can be used to modify
the properties of the basic polymer.
 The wide range of mixtures or compounds of polymers
that can be manufactured to get the required
properties.
Despite this there are some simple tests that can be carried
out to get a basic idea of the possible base polymer used for
the manufacture of any given product.

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IDENTIFICATION OF PLASTICS

CONTENTS
 Introduction
 Simple method
 cutting test

 hot wire penetration test

 flotation test

 bending test

 dropping test

 Burning test
 Pyrolysis test
 Specific gravity test
 Solubility test
 Softening and Melting point
 Elemental Analysis
 Confirmation test
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IDENTIFICATION OF PLASTICS

IDENTIFICATION BY SIMPLE METHOD


 Stage 1: Look at the sample
This will give you a lot of information. The colour of the plastic will give
you some information. Some polymers have restricted colour ranges,
particularly the thermosetting types. Others tend to be glossier in colour
(polypropylene), whereas some are both glossy and glassy (the acrylics).
 Stage 2: Feel the sample
After you have carried out the tests in the is series a few times you will
start to get the feel for various plastics. The polyolefins have a very
distinctive feel and you can generally tell if it is one of them. The presence of
glass fibre or other reinforcement materials can alter the feel and stiffness of
the sample but you can sometimes tell by the feel if there is reinforcement
present.
 Stage 3: Cut a thin sliver from the edge of the sample
Cut a small sliver off the sample. This tells you a lot about the type of
plastic you are trying to identify

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IDENTIFICATION OF PLASTICS

CUTTING TESTS
 If a shaving can be pared off with knife, it may be a
thermoplastic.
Note: PMMA and Polystyrene are brittle and difficult to
pare
 If the material is rigid and will not pare off instead flakes of

powders, it may probably a thermoset plastic.


 Scuff the sample with your fingernail.

Results
 Scuffs with fingernail - Urea formaldehyde resin.

 Does not scuff with fingernail - Melamine formaldehyde

resin.

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IDENTIFICATION OF PLASTICS

HOT ROD PENETRATION TEST

 Heat an electronic soldering iron to red hot and press


against the unknown sample.
 If the plastic material softens, and the rod penetrates the
sample is thermoplastic.
 If the plastic material does not soften and the rod does
not penetrate, the sample is thermoset plastic.

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IDENTIFICATION OF PLASTICS

FLOTATION TEST
This test will give the idea to distinguish the material
according to their density.

Floats on type Alcohol Vegetable oil water glycerin


of plastics
PET No No No No
HDPE No No Yes Yes
PVC No No No No
LDPE Yes No Yes Yes
PP Yes Yes Yes Yes
PS No No No Yes

Note:Filled polyolefin’s and cellular foams are exceptional


for this test.

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IDENTIFICATION OF PLASTICS

BENDING TESTS
Some plastics will exhibit particular characteristics in the manner
in which they respond to bending. The bending behaviour of some
plastics are given in Table
PLASTICS BENDING BEHAVIOUR
1. Polyethylene Bends, tends to remain
2. Polypropylene Unbends most of the way
3. Polystyrene Cracks but retains bend
4. ABS Bend tends to remain
5. PVC (Rigid) Bends easily and springs back quickly
6. Cellulose acetate Bend tends to remain
7. PMMA Cracks and splinters
8. Nylon Difficult to bend, springs back
9. Polycarbonate Tough to bend

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IDENTIFICATION OF PLASTICS

DROPPING TEST
When a polymer moulded component is dropped on hard
surface, it creates sound, which shall be either metallic
sound or dull sound. On the basis of sound polymer is
distinguished in two categories, which is tabulated in
Table

Metallic sound dull sound


PS, HIPS Cellulosics
SAN, ABS Polyamides
PC, PPS PTFE, PMMA
PPO Polyacetal
Polysulphone PVC , Polyolefins

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IDENTIFICATION OF PLASTICS

BURNING TEST
A small sample is held in flame. If it ignites withdraw it
from the flame a distance of flame. Make observations
as listed below and record the observations, for
example:

Degree of flammability burns


Self extinguishing does not burn
Colour of flame yellow and orange; Blue; blue with yellow edges; clear,
Type of flame steady; tall; short; sputtering
Smoke none, black, thin and thick black with sooty streamers
Melt behaviour softens remains hard; flows; bubbles; swells; does not
char but melts; melts and chars
Odour Burning rubber; sweet – fruity; marigolds; burning
paper; acid; rancid butter

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IDENTIFICATION OF PLASTICS

Typical results of burning tests of polymers (thermoplastics)


Thermoplastics Melting Behaviour Colour of Flame/ kind Odour / smell
of smoke
PE Melt and bubbles fiercely Blue base Waxy (Burning Candle)
around the edge, Drips with yellow tip

PP Becomes soft, tends to Blue base Lubricating oil smell


form a ball, Drips with yellow tip

PTFE Does not melt, self – Will not burn None


Extinguishing

PS / SAN Melts and bubbles around Orange – Yellow, Heavy, Mari gold, Strong smell
the edge, spurting, burns Black, Sooty Smoke of Styrene and Burning
readily rubber
High Impact poly Melts and bubbles around Orange – Yellow, Heavy, Slight burning rubber
styrene the edge, spurting, burns Black, Sooty Smoke smell
readily
ABS Becomes soft but not fluid Orange – Yellow, Heavy, Slight burning rubber
Black, Sooty smell

PVC Soften and forms a ball, Yellow with green bottom Chlorine smell, pungent
chars at bottom, self – edge, Some White Smoke
Extinguishing

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IDENTIFICATION OF PLASTICS

Typical results of burning tests of polymers (thermoplastics) cont.

Thermo Melting Behaviour Colour of Flame/ kind Odour / smell


plastics of smoke
CA Melts and emits white smoke boils Yellow, burns brown at Smell of Vinegar (Acetic
and chars base, Some light Smoke acid)

CN Melts and emits white smoke – Hot, White Camphor (Mothball)


Burn Furiously, dangerous

CAB Melts and Char at the edge, drips Dark yellow with light blue Rancid butter (an Odour
base, Some light black of butyric acid)
Smoke
PMMA Boils and Bubbles Blue and Yellow Flame, Fruity, Floral smell
Some light black Smoke

PC Melt but chars, Bubbles develops a Orange yellow flame with Phenolic smell ( ink
cellular structure before black smoke smell)
decomposing, self – Extinguishing
PPO Melt but chars, self – Extinguishing Orange yellow flame with Phenolic smell ( ink
black smoke smell)

Nylon Melts round edges and chars, Blue with Yellow tip Burning hair / wool /
Froth formation and drips vegetarian

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IDENTIFICATION OF PLASTICS

Typical results of burning tests of polymers (thermoplastics) cont.

Thermo Melting Behaviour Colour of Flame/ kind of Odour / smell


plastics smoke
Acetal Melts, forms drops, Burns Pale blue Pungent smell of
readily Formaldehyde

PET/ PBT Melts, opacifies, blackens, Yellow, Slightly smoky Pleasant elusive odour
Molten Material drips

Polyvinyl Softens Dark Yellow, Spurts with black Vinyl acetate smell (Sweet
Acetate smoke odour)

Casein Swells and chars on Yellow, Grey smoke Burning milk


ignition, Self –
Extenguishing,
Poly Melt and char, self Orange yellow flame with black H2S smell or rotten egg
phenylene extinguish smoke smell
sulphide
PU Drip like oil Blue base yellow tip burns Faint apple smell or castor
continuously, no smokeYellow oil smellFiant apple smell
flame, black smoke or castor oil smell

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IDENTIFICATION OF PLASTICS

Typical results of burning tests of polymers (thermoset)

Thermoset Colour of Flame/ kind of smoke Odour/ smell


Phenol Resin Yellow flame, self extinguishing, Charcoal smell
Some sparks
Urea Resin Yellow with light blue edge, self Fishy smell
extinguishing

Melamine Resin Yellow with light blue edge, self Fishy smell
extinguishing

Polyester Resin Burn with orange yellow flame, Black Ester smell
(Unsaturated) smoke

Epoxy Yellow flame, Black smoke Charred flour


smell

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IDENTIFICATION OF PLASTICS

Typical results of burning tests of polymers (Elastomer)

Elastomer Colour of flame/ smoke Odour/ smell Other notable


Flame characteristics
& kind of smoke

Poly butylene Yellow, blue base Smoky Disagreeable, Sweet Chars readily
Styrene - butadiene Burns continuously Pungent smell of styrene Chars readily, dry
Yellow sooty powdery
Ethylene propylene Burns continuously no Waxy smell Dry powdery
dienemer (EPDM) smoke, blue base yellow tip
NBR Yellow sooty Unpleasant Tacky
Butile rubber (IIR) Smoke free, candle like Hydrocarbon smell Melt does not char
readily, tacky
Polyisoprene (NR) Yellow sooty Pungent like burn rubber Chars & crack
Polychloroprene (CR) Self extinguishing Pungent smell Strongly acidic fumes,
Yellow & smoky of chlorine black residue dry
powdery
Silicone rubber Burns continuously, glow No odour Dry white powdery
with white smoke powdery

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IDENTIFICATION OF PLASTICS

PYROLYSIS TESTS
 In this testing, heat few milligrams of the sample in an ignition tube and
test the pyrolytic vapour with a moistened indicator paper. The behaviour
of vapour to indicator paper is given as follows:
 ACID: turns blue litmus to red
 BASIC: turns red litmus to blue.
 ACID VAPOURS: may come from carbohydrate polymers & their
derivatives. [e.g., cellulose acetate]
 HIGH ACID VAPOURS: often indicates the presence of chlorine. e.g.,
PVC or rubber neutral vapors] evolved from hydro carbon
polymers, silicones and some polyesters hydrochloride.
 ALKALINE VAPOURS: indicate the presence of N2. e.g. polyamide,
proteins & amino formaldehyde resins.

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IDENTIFICATION OF PLASTICS

Floats in water (S.G. 1) Specific Gravity ≤ 1


SPECIFIC GRAVITY TEST PP 0.90
LDPE 0.92
A simple test for differentiating HDPE 0.96
between different types of Sink in Water floats in 1 ≤ Specific Gravity
plastics can be carried out by Hypo ≤ 1.1
placing specimens in water. PS 1.07
Some will sink and some will SAN 1.1
float depending on their specific
gravity as shown in Table . ABS 1.1
NYLON 1.1
Sinks in Hypo Specific Gravity ≥
Those with the higher specific 1.1
gravities will sink as shown in PMMA 1.2
the Table. Accurate specific PMMA 1.2
gravity results can be obtained
by the standard method of CA 1.3

relating weight of the material to PVC 1.4

weight of water displaced. ACETAL RESIN 1.4


UREA RESIN 1.5
PTFE 2.75

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IDENTIFICATION OF PLASTICS

SOLUBILITY TESTS
Solubility tests form a basis of some older identification schemes for
main types of plastic materials. However, in many cases solubility
varies considerably for different samples of the same resin and it is
difficult to interpret the results Solubility of plastics may vary
according to the grade or to the whether or not other constituents
are present in the sample. The data in Table refer in principle to pure
polymers, although even those polymers may exhibit differences in
solubility. The solubility test should be carried out directly in a test
tube. To about 100 mg of a powdered sample add 10ml of solvent,
mix occasionally shake the contents of the test tube and observe for
a few hours swelling may occur before complete dissolution of the
polymer.

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IDENTIFICATION OF PLASTICS

PLASTIC MATERIAL SOLVENTS


Cellulose esters Ketones, esters
Poly (vinyl chloride) Dimethylformemide, tetrahydrofuran, cyclohexenone
ABS Methylene chloride
Vinyl chloride / Vinyl acetate Methylene chloride, cyclohexanone, tetrahydrofuran
Polytetrafluoroethylene Fluorocarbon oil e.g. C21 F44 {hot)
Polyacrylonitrile Dimethylformamide, butyrolactone, nitrohenel, mineral acids,
dimethylsulphoxide, aqueous solutions of some inorganic salts.
Poly (Methacrylic acidesters) Arimatic hydrocarbons dioxen, chlorinated hydracarbons, esters, ketones.
Polyamides Phenols, formic acid, tetrafluoropropanel, conc. Mineral acids.
Poly (vinyl acetal) Esters, Retones, tetrahydro – furan
Poly (vinyl alcohol) Formamide water
Polycarbonates Chlorinated hydrocarbons, dioxan, cyclohexanene.
Polyesters, unsaturated Ketenes, styrene, acrylic esters.
Polyethylene Dichloroethylens, tetralin, hot hydrocarbons
Polyformaldehyde Hot selvantas phenels, benzyl alcohol, dimethylformide.
Polypropylene At elavator temp, aromatic and chlorinated hydrocarbons, tetralin
Polystyrene Aromatic and chlorinated hydrocarbons, pyridinc, ethylacetate, methylethyl
ketone, diovan totralin.

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IDENTIFICATION OF PLASTICS

SOFTENING AND MELTING POINTS


The temperature range of softening and melting – point can be used to
characterize/ identify the material.
Procedure: Place the 2 to 3 mg portion on a clean glass slide and cover
with No 1 cover glass. Heat the slide, sample and cover on a hot plate
to slightly above the softening point of the polymer so that a thin film
can be formed. By slightly pressure on the cover glass form a thin film
0.01 to 0.04 mm, and allow it to cool slowly by turning of the hot plate
power to promote crystallization. Keep the slide on hot plate melting
point apparatus. Adjust the hot plate temperature about 10 deg C below
the melting point of sample. Then adjust the temperature ramp at 0.5
deg C/ min. observe the sample through microscope and note down the
temperature where the material starts melting.

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IDENTIFICATION OF PLASTICS

Melting and softening point of polymer materials

S. No. Polymer material Softening Point Melting Point


1. PET 140 260
2. HDPE 120 130
3. Poly Urethane Linear 125 150 – 185
4. PP 110 165 – 170
5. 6, 10 Polyamide 180 210 – 215
6. 6, Polyamide 120 215 – 220
7. 6,6 Nylon 140 255
8. PC 200 220 – 360
9. PTFE 277 325 – 360

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IDENTIFICATION OF PLASTICS

CONFIRMATION TEST - Thermoplastics

Tests for Polyolefins


A piece of dry sample is pyrolysed in a tube closed with a
filter paper which is drenched with a solution of 0.5 g
yellow mercury (II) oxide in sulphuric acid (1.5 ml conc.
Sulphuric acid added to 8 ml. Water). If the vapour gives a
golden yellow spot, indicates polyisobutylene, butyl
rubber and polypropylene (the latter only after a few
minutes). Polyethylene does not react. Natural and nitrile
rubber, as well as polybutadiene yield a brown spot.

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IDENTIFICATION OF PLASTICS

CONFIRMATION TEST - Thermoplastics Cont.

Test for Chlorine containing polymers


Copper wire test
 Take the piece of copper wire about 5 mm long. Push on end
of the wire in to a small cork.
 Place one pellet or plastics sample near your Bunsen burner.
This is the sample you will be testing.
 Hold the free end of the copper wire in the burner flame until
it is red-hot and the flame no longer has a green colour.
 Remove the wire from the flame and torch the hot wire to the
plastics pellet or sample you will be testing. A small amount
of the plastics should melt onto the wire.
 Place the end of the wire, with small amount of plastic on it,
into the flame. You should see a slight flash of a luminous
flame (a yellow- orange colour). If the flame turns green in
colour, then the sample contains chlorine.
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IDENTIFICATION OF PLASTICS

Cont.
CONFIRMATION TEST - Thermoplastics

Test for Caprolactum in Nylon 6


About 0.5 gm of sample is heated in 5.0 ml of distilled
water and allowed to boil for 10 to 15 min. After cooling,
2-3 drops of con. H2SO4 is added to 0.5 ml of the above
solution followed by addition of 2 ml. of potassium iodo
bismuthate ( a solution of 5 gm. of basic bismuth nitrate
and 25 gm. of potassium iodide in 10 ml. of 2% H2SO4).
Precipitation of an orange red complex indicates the
presence of caprolactum.

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IDENTIFICATION OF PLASTICS

Cont.
CONFIRMATION TEST - Thermoplastics

Test for Adipic acid in Nylon 6,6


About 0.2 gm of sample is heated in low flame in a test
tube and the vapour coming out of the tube is passed over
a filter paper moistened with a saturated solution of O-
nitrobenzaldehyde in 2N aqueous NaOH. A deep violet
colour confirms the presence of adipic acid.
A yellowish green colour develops in the case of
polyethylene-terephthalate and polybutylene-terephthalate
confirming the presence of terephthalic acid.

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IDENTIFICATION OF PLASTICS

Cont.
CONFIRMATION TEST - Thermoplastics
Test for Polycarbonate
About 1.0 gm of sample is pyrolysed in an ignition tube,
which is plugged with cotton. The cotton is removed and
immersed in 1% methanolic solution of p-dimethylamino
benzaldehyde and then one drop of 5 N-Hydrochloric acid
is added.
A dark blue colour appears in the case of
polycarbonates.
A red colour that does not change to blue is observed in
the case of polyamides.
The cotton floak in which the prolysed vapours of the
sample absorbed is treated with dilute (1:1) HCI. An
intense red colour which is unaffected by methanol,
indicates the presence of polycarbonate.

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IDENTIFICATION OF PLASTICS

Cont.
CONFIRMATION TEST - Thermoplastics

Test for PMMA


About 1 gm of sample is heated in an ignition tube and the
pyrolysate is collected in a test tube wrapped with a wet
filter paper. To the distillate, 1 ml. of conc. HNO3 is added
and heated just to boiling. After cooling, 5 ml. of water is
added an then sodium nitrite (0.1 gm) is added. A blueish
green colour confirms the presence of
polymethylmethacrylate.

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IDENTIFICATION OF PLASTICS

Cont.
CONFIRMATION TEST - Thermoplastics

Test for Polyacetals


Polyacetals produce formaldehyde on heating. A small
amount of sample is heated with 2 ml. conc. Sulphuric acid
and a few crystals of chromotropic acid for about 10 min
at 60 -70C. A strong violet colour indicates
formaldehyde.

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IDENTIFICATION OF PLASTICS

Cont.
CONFIRMATION TEST - Thermoplastics

Tests for PET and PBT


PET and PBT are soluble in nitrobenzene. A small sample
is pyrolysed in a glass tube covered with filter paper. The
filter paper is drenched with a saturated solution of O-
nitrobenzaldehyde in dilute sodium hydroxide. A blue-
green colour, which is stable against dilute hydrochloric
acid, indicates terephthalic acid. Then PET and PBT are
differentiated based on melting points.

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IDENTIFICATION OF PLASTICS

Cont.
CONFIRMATION TEST - Thermoplastics

Test for polyurethane


About 0.5 gm of sample is dissolved in 10 ml of glacial
acetic acid and 0.1 gm of p-dimethylamino benzaldehyde is
added. The solution turning yellow after several minutes
shows the presence of polyurethane.

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IDENTIFICATION OF PLASTICS

Cont.
CONFIRMATION TEST - Thermoplastics
Test for Cellulose Ethers:
The important cellulose ethers are Methyl cellulose, Ethyl.
Cellulose and Benzyl cellulose.
Reaction to Heating and Burning:
Cellulose ethers melt and char after heating and
continuously burn after ignition. Nature of flame and smell
of the cellulose ethers are as follows:
Methyl cellulose Brilliant yellow flame Odour of
burnt
Ethyl cellulose less brilliant flame accompanied by dripping paper

Benzyl cellulose Brilliant sooty flame smells like bitter almonds

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IDENTIFICATION OF PLASTICS

Cont.
CONFIRMATION TEST - Thermoplastics

Polyvinyl Alcohol
A Sample (about 0.02g) is dissolved in water 5ml and
iodine reagent described above (5 drops) added. The
formation of Blue colour confirms the presence of
Polyvinyl alcohol.

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IDENTIFICATION OF PLASTICS

Cont.
CONFIRMATION TEST - Thermoplastics

Casein
A sample about (0.02g) is dissolved in concentrated HNO3
(2ml) by boiling for about 5mn. The solution is cooled and
excess 5N ammonium hydroxide added. The formation of
orange colour confirms the presence of casein.

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IDENTIFICATION OF PLASTICS

Cont.
CONFIRMATION TEST - Thermoplastics

Shellac
A sample (0.05g) is dissolved in ethanol (1ml) with
warming. To the cooled solution is added water (about 1ml)
to give an emulsion like precipitate. 5N aqueous NaOH 2
drops is added to the mixture. The colour change is
reversed on acidification with 5N HCL. The formation of
Violet - red colour confirms the presence of Shellac.

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IDENTIFICATION OF PLASTICS

CONFIRMATION TEST - THERMOSET PLASTICS

Test for formaldehyde


A small amount of sample is boiled in water in presence of
H2SO4 and filtered. Few drops of 5% aqueous chromotropic
acid solution (1,8-dihydroxynaphthalene-3, 6-disulphonic
acid) and excess of cone. H2SO4 are added to the filterate
and heated at 1000 C for few minutes. In the presence of
formaldehyde, the solution turns violet/dark violet. Poly
(vinyl formal), polyoxymethylenes, PF, UF and MF resins
contain formaldehyde.

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IDENTIFICATION OF PLASTICS

Cont.
CONFIRMATION TEST - THERMOSET PLASTICS

Test for Phenol in PF


Million's Reagent: About 10 gm of Hg is dissolved in 10 ml.
of HNO3 by gentle heating and then diluted with 15 ml. of
distilled water.
The sample is heated to boiling for two minutes with 1 ml.
of clear million's reagent. Red colour indicates the
presence of phenol in the sample.

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IDENTIFICATION OF PLASTICS

Cont.
CONFIRMATION TEST - THERMOSET PLASTICS

Test for Urea in UF


About 0.5 gm. of sample is refluxed for 30 min. with 20%
acetic acid (50 mI.). The mixture is cooled and filtered. To
the filterate added a solution of (2 ml.) xanthydrol in
methanol (1% solution) and boiled for 1-2 minutes. White
bulky precipitate confirms the presence of urea.

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IDENTIFICATION OF PLASTICS

Cont.
CONFIRMATION TEST - THERMOSET PLASTICS

Test for Melamine in MF


About 0.5 gm of sample is refluxed with 80% acetic acid
(25 ml.) for 30 min., cooled and filtered. Then the filterate
is evaporated to dryness and added 2 ml. of water, cooled
and filtered. To the filtrate one drop of saturated aqueous
picric acid is added. Yellow precipitate indicates the
presence of melamine.

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IDENTIFICATION OF PLASTICS

Cont.
CONFIRMATION TEST - THERMOSET PLASTICS
Tests for Epoxy Resin
Foucry Test:
About 0.25 gm. of sample is dissolved in 98% H2SO4 by
slight warming. After cooling 1 ml. of 63% HNO3 is added.
After shaking, the mixture is poured into 100 ml. of 5%
aqueous NaOH. A bright red or orange red colour
indicates the presence of epoxy resin.

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IDENTIFICATION OF PLASTICS

Rubber Testing: For identification of CR, NBR, SBR, NR / IR, IIR type of
rubbers
Test Procedure: Heat strongly 0.5gm of sample in a test tube until sample begins
to decompose and pass the fume in solution II and I and observe change in
colour initially and after heating. (Refer the following table)
 Solution - I : Dissolve one gram of p - dimethyl amino benzaldehyde in
5ml of HCl and add 10ml of ethylene glycol. Adjust the density to 0.851
gm /cc. by addition of methanol.
 Solution - II : Dissolve 2gm sodium citrate , 200mg of citric acid , 300mg
of bromo cresol green and 300mg of metanil yellow in 500ml of water.
RUBBER Solution - I Solution II
Initial After Heating

Blank Solution Pale Yellow Pale Yellow Green


CR Yellow Pale Yellow Green Red
NBR Orange Red Red Green
SBR Yellow Green Green Green
NR / IR Brown Violet Blue Green
IIR Yellow Droplet Floats Pale Blue Green Green

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IDENTIFICATION OF PLASTICS

Identification code of plastics

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IDENTIFICATION OF PLASTICS

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