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IDENTIFICATION OF A POLYMER

Techniques used to identify a polymer include the following:


1. Preliminary examination
2. Elemental analysis (Lassaigne's Test)
3. Solubility test
4. IR analysis (KBr disc)
5. Flame Test/Melting Test
6. Specific gravity determination
Preliminary Examination:
Based on a preliminary examination, a polymer can sometimes be classified as belonging to one of the
following groups:
a. rubber
b. flexible thermoplastic
c. rigid thermoplastic
d. thermoset
Manufacturer's Labeling Code: The composition of an increasing number of plastic products is identified
using the SPI (Society for Plastics Industry) recycling code, which is usually stamped on the bottom of the
product. The number is often enclosed in the triangular arrows recycling symbol. The code is as follows:
1. PETE - Polyethylene Terephthalate
2. HDPE - High Density Polyethylene
3. V - Vinyl / Polyvinyl Chloride (PVC)
4. LDPE - Low Density Polyethylene
5. PP - Polypropylene
6. PS - Polystyrene
7. Other
End Use: In the case of a finished article, the intended use can very often indicate the nature of the
polymer. For example:
 Elastic bands and tires are rubbers (elastomers). Elastic bands are usually natural rubber
(cis-1,4-polyisoprene). Automobile tires are usually a blend of styrene butadiene rubber (SBR)
and natural rubber.
 Pot handles and cutlery handles are usually thermosets (e.g., phenolics). Dishes are likely
to be melamine-formaldehyde thermosets.
 Garden hoses, shower curtains and raincoats are usually PVC.
 Tents and screens are usually nylon.
 Floating rope is usually polypropylene.
 Foam upholstery cushions are usually polyurethanes.
 Bulletproof glass, sunglasses and reading glasses with plastic lenses are polycarbonate.

Feel: Teflon and polyethylene feel waxy. Thermosets feel hard and sound brittle when dropped or struck
with a metallic object. Rubbers are flexible and sometimes stretchy.
Color: Most polymers are available in a wide color range resulting from the addition of various pigments.
Phenol-formaldehyde thermosets (Bakelite) are inherently dark colored. If a polymer is light in color, it is
not a phenol-formaldehyde thermoset.
In the absence of additives, pure amorphous polymers have high optical clarity (transparent),
whereas crystalline polymers are translucent to opaque. The following are examples of transparent
polymers: PET (pop bottles), PMMA (Plexiglas), PC (bulletproof glass), PVAc (blister packaging).

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Elemental Analysis (Lassaigne's Test):
The presence of N (e.g., polyamides), halogens [e.g., PVC or poly(vinylidene chloride) - Saran wrap] and
S (vulcanized rubber and polysulfide caulkings) can be identified by inorganic qualitative analysis after
sodium fusion. Additives may interfere; e.g., some flame-retardants contain Cl or Br.
Solubility:
Thermoplastics are soluble in appropriate solvents whereas thermosets may swell but are insoluble.
Plastics may require long exposure to a solvent to dissolve. Agitation significantly reduces dissolving time.
The following table illustrates polymer solubility behavior. The general rule of like-dissolves-like applies,
i.e.; hydrocarbon solvents tend to dissolve non-polar polymers, whereas polar solvents tend to dissolve
polymers containing polar functional groups.
Plastic Gasoline Toluene Acetone Cyclohexanone
ABS SW S S S
LDPE, HDPE I I I I
PA (polyamides) I I I I
PET I I I I
PMMA I SW S S
PP I I I I
PPO I SW S S
PS S S S S
PVC I SW SW S
I = insoluble SW = swells S = soluble
Solubility behavior is shown at room temperature. Heating can solubilize thermoplastics such as
PE and PP.
IR Analysis:
The infrared spectrum of a polymer sample that has been ground into a KBr disc will identify major
functional groups such as carbonyl stretches (polyesters), N-H stretches (polyamides), aromatic bends
(polystyrene), alkene stretches (cis-1,4-polyisoprene), O-H stretches [poly(vinyl alcohol)], C≡ N stretches
(polyacrylonitrile), and C-H stretches (polyethylene).
Flame Tests/ Melt Tests:
The melting range of a thermoplastic can be determined after melting a few chips of the plastic in a test
tube. A thermometer or thermocouple lead immersed in the melt can be used to measure the temperature
at which solidification occurs. During freezing, the rate of cooling levels out as the latent heat of fusion is
released. The melting point range can be compared to tables available from the literature.
Flame tests identify the ease of ignition, rate of burning, color of flame and soot, as well as odors of
combustion products. A detailed procedure is attached.
Specific Gravity:
The relative density of a polymer is very helpful in determining its identity. Polyethylenes, polypropylenes
and polyallomers (block copolymers of ethylene and propylene) float in water (s.g. < 1.0) whereas virtually
all other (non-cellular) polymers sink. Although the addition of fillers can change the relative density of
polymers, even so, the method narrows down the number of possible choices. A detailed procedure is
attached.

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SIMPLE TESTS FOR IDENTIFYING POLYMERS
Flame Tests:
 Test the flammability of each kind of polymer listed below by holding it in a flame for 5 to 10
seconds and then remove it from the flame. Hold the sample over an asbestos pad to catch
any drips. Work in or near a fume hood and try to direct as many of the fumes as possible
into to the fume hood.
 Observe and record the characteristics identified in the table of results below. Discuss the
characteristics with your partners and fill in as much of the table as possible.
 Perform the Beilstein test on PVC and any other samples you wish. A copper wire heated in
a flame with melting polymer burns bright green if a halogen is present. Halogenated
polymers can be identified in this way.
 Many polymers have characteristic odors when burned or melted. It is not advisable to inhale
these odors since most are unhealthy. Odors of melted polymers (e.g., in test tubes) are
more characteristic than the odors of burning polymers. It is not uncommon for people
working in polymer businesses, e.g., polymer recycling, to ignite a small piece of plastic with a
cigarette lighter and identify the polymer based on flame test and odor.
 Based on the flame tests, identify which polymers are thermoplastic (T. Plastic) and which are
thermoset (T. Set). Thermoplastics melt (Touch the hot polymer to the asbestos pad and see
if the polymer is liquid). Thermosets are decomposed at high temperature, but do not melt.
They char and smoke but do not melt.
 Compare your results with the handouts "ID your plastics by flame tests".

Specific Gravity:
 Polyolefins, i.e., polyethylene, polypropylene and polyallomers (block copolymers of ethylene
and propylene) float in water (s.g. < 1.0). Most other polymers sink in water (s.g. > 1.0). Test
the specific gravity on any samples for which you can readily obtain a small piece. Drop a
small piece in a beaker of water. Be sure that the sample is wetted i.e., overcome surface
tension by pushing the plastic under the surface. Specific gravity tests do not apply to
plastics that are produced as expanded foams. Enclosed gas cells within the plastic will
cause even dense polymers to float. For simplicity, polymer s.g. is determined vs. H2O @
23ºC.
 Specific gravity can be accurately measured by weighing a polymer sample in air and in a
fluid, e.g., water. The s.g. can be calculated as follows…
B = wt. of sample + wire in air For C, immerse only as
B −A
s.g . = A = wt. of wire in air much of the wire as was
B − A − D +C C = wt of wire in water immersed when weighing
D = wt. of sample + wire in water the sample.

density of object wt. of sple. (in air) (wt. of sple. + wire in air) - (wt. of wire in air)
s.g . = = = =
density of water wt. of H 2 O (displaced by sple.) (wt. of sple. in air) - (wt. of sple. in H 2O)

[Archimedes principle: An object immersed in water is buoyed up with a force equal to the weight of water it displaces.]

For plastics that are less dense than water (olefins), secure the wire so that the sample is
held under water or hang a lead weight on the sample and incorporate this into the
calculation.

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Specific Gravity of Some Common Polymers
POLYMERS S.G. POLYMERS S.G.
(Alphabetized) S.G. (Range) (SG prioritized) S.G. (Range)
acetal 1.42 oak 0.86
acrylic 1.18 polyallomer 0.89
ABS 1.04 polypropylene 0.89
aluminum 2.50 polyethylene, L. D. 0.91 0.91-0.92
cellulose acetate 1.30 ionomer 0.94
cellulose nitrate 1.25 polyethylene, H. D. 0.95 0.94-0.96
diallyl phthalate 1.50 1.34-1.78 ABS 1.04
epoxy (cast) 1.11 poly(phenylene oxide) 1.06
FEP 2.14 polystyrene 1.06 1.04-1.10
glass 2.50 polyester 1.10 1.01-1.20
ionomer 0.94 epoxy (cast) 1.11
melamine formaldehyde 1.48 Nylon 1.15 1.13-1.20
Nylon 1.15 1.13-1.20 phenoxy 1.17
oak 0.86 acrylic 1.18
phenoxy 1.17 PMMA 1.18
phenol formaldehyde 1.27 1.25-1.30 polyurethane 1.18 1.11-1.25
PMMA 1.18 polycarbonate 1.20
poly(vinylidene chloride) 1.70 polysulfone 1.24
polyallomer 0.89 cellulose nitrate 1.25 1.16-1.35
polycarbonate 1.20 poly(vinyl chloride) 1.25
polyester 1.10 1.01-1.20 phenol formaldehyde 1.27 1.25-1.30
polyethylene, L. D. 0.91 0.91-0.92 cellulose acetate 1.30
polyethylene, H. D. 0.95 0.94-0.96 acetal 1.42
poly(phenylene oxide) 1.06 melamine formaldehyde 1.48
polypropylene 0.89 diallyl phthalate 1.50 1.34-1.78
polystyrene 1.06 1.04-1.10 poly(vinylidene chloride) 1.70
polysulfone 1.24 silicone 1.75
polyurethane 1.18 1.11-1.25 FEP 2.14
poly(vinyl chloride) 1.25 1.16-1.35 tetrafluoroethylene 2.16 2.14-2.20
silicone 1.75 aluminum 2.50
steel 7.70 glass 2.50
tetrafluoroethylene 2.16 2.14-2.20 steel 7.70

The specific gravity of a given polymer may vary due to the method of polymerization and the
method by which the polymer is processed.
The method of polymerization may affect the extent of chain branching. For example,
compare highly-branched LDPE with sparsely-branched HDPE.
The method of processing may affect the extent of crystallization. Rapid cooling produces an
amorphous (less dense) polymer. Slow cooling or cooling under stress (e.g., melt spinning or
gel spinning) often induces crystallization, resulting in a more dense polymer.
The addition of a filler is another cause for variation of s.g. of a given polymer.

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POLYMER IDENTIFICATION – FLAME TEST
Polymer SE Speed of Chars (C) Drips Flame Smoke Sinks (↓) TP
or Burn or Color Colo or or
P (slow, med., Melts (M) r TS REMARKS
Floats (↑)
fast) in water

PVC (Tygon tubing)

Vulcanized black
rubber

PS

Melamine
(Melmac dish)

PMMA (Plexiglass)

Polycarbonate (Lexan)

FRP Epoxy

PP

ABS (drain pipe)

PE

SE = Self Extinguishing, P = Propagating; TP = Thermoplastic, TS = Thermoset

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POLYMER IDENTIFICATION LAB

Procedure:
1. Perform a flame test and a float/sink test on all the types of polymers for which samples have
been provided. There is a set of small beakers containing small polymer chips for these two
tests.

For the float/sink test, do not use a piece of plastic that has been burned. Use a fresh piece
of plastic. Ensure that the surface of the plastic is completely wetted. Using tweezers, shake
the piece under water to release any air bubbles adhering to the surface of the plastic.
Adhering air bubbles may cause a dense plastic to float.

Record observations for all the characteristics listed on the Polymer Identification Flame Test
(Float/Sink Test) chart.

Do not burn any other plastics without the instructor’s permission and be sure to work in a
fume hood over an asbestos pad or gypsum board to catch all drips. See the Flame Test
instructions for details on performing the test.

Each student must submit his/her own copy of the results next week.

2. Accurately determine the specific gravity (s.g.) of 3 different polymer samples supplied by the
instructor. Compare the results with the s.g. values listed on the table of Specific Gravities
handout supplied by your instructor. Also consider other physical properties such as
sink/float, feel, stiffness, clarity, color, etc. Do not burn any of the S.G. samples.

Report the Sample Identification number (‘ρ -A’, ‘ρ -B’, ‘ρ -C’, ‘U-1’, ‘U-2’, etc.), the calculated
s.g., and the polymer identity you have determined. Calculations are not required.