Module – IV: Testing of Polymer

Properties
 Expert polymer and plastic
identification testing is required
during polymer product development,
competitive analysis, reverse
engineering, deformulation, layer
identification, for material
fingerprinting and polymer problem
solving.
 Identificationof plastics and polymers is
important to confirm if the correct
material has been used in an application
or to identify an unknown material.

 Identificationtesting can also help a

developer to compare several materials
assisting the selection of the most suitable
materials in terms of composition or
quality.
 Plastics
and polymer formulations
are usually comprised of a polymer
material and a range of other
additives such as UV absorbers,
colourants, or plasticizers.

 Experienced testing expertise is

required to identify the polymer
and to carry out the analysis using
a range of laboratory techniques.
 Here a details have provided for
plastic and polymer identification
testing for materials and finished
products, such as packaging, and
can support you during critical
innovation steps, helping you to
ensure that your materials and
products meet regulatory or
industry specifications and
requirements.
A range of specialized techniques
such as Infrared Spectroscopy
(FTIR), Raman Spectroscopy, UV-
visible spectroscopy and
chromatography methods such as
gel permeation chromatography
(GPC), and DSC (Differential
Scanning Calorimetry) are
deployed.
 Preliminary examination
 Elemental analysis (Lassaigne's Test)
 Solubility test
 IR analysis
 Flame Test/Melting Test
 Specific gravity determination
 Preliminary examination
 Elemental analysis (Lassaigne's Test)
 Solubility test
 IR analysis
 Flame Test/Melting Test
 Specific gravity determination
 Basedon a preliminary examination, a
polymer can sometimes be classified as
belonging to one of the following groups:

 rubber
 flexible thermoplastic
 rigid thermoplastic
 thermoset
 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.
 PETE - Polyethylene Terephthalate
 HDPE - High Density Polyethylene
 PVC - Polyvinyl Chloride
 LDPE - Low Density Polyethylene
 PP - Polypropylene
 PS - Polystyrene
 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).

 Elasticbands 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.

 Bulletproofglass, sunglasses and

reading glasses with plastic lenses
are polycarbonate.
 Teflon and polyethylene feel
waxy.

 Thermosets feel hard and sound

brittle when dropped or struck
with a metallic object.

 Rubbersare flexible and

sometimes stretchy.
 Most polymers are available in a
wide color range resulting from the
addition of various pigments.

 Phenol-formaldehyde thermosets
(Bakelite) are inherently dark
colored.

 Ifa polymer is light in color, it is

not a phenol-formaldehyde
thermoset.
 Inthe 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).
 Thepresence 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.
 Thermoplastics are soluble in
appropriate solvents whereas
thermosets may swell but are
insoluble.

 Plasticsmay require long exposure

to a solvent to dissolve.

 Agitation significantly reduces

dissolving time.
 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.
 I = insoluble, SW = swells, S = soluble
 Solubility behavior is shown at room temperature.
Heating can solubilize thermoplastics such as PE and
PP.
 “Thei n f ra r e d s p e c t r u m o f 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).
 Themelting 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.

 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.
 Polymer Specific Gravity Polymer Specific
Gravity

LDPE 0.91 Nylon 1.15

HDPE 0.95 polystyrene 1.06
ABS 1.04 phenoxy 1.17
polypropylene phenol
formaldehyde
0.89 1.27
polyurethane 1.18 PMMA 1.18
polyester poly(vinylidene
1.10 chloride) 1.70
polysulfone 1.24 polyallomer 0.89
epoxy (cast)
1.11 polycarbonate 1.20
 Soyou have a plastic part and you need to
know what it is made of but you have no
idea what plastic it is.

 Thiscan be a challenging task. Many

plastics look and feel alike but we will take
a closer look here at some of the ways
using a burn test.

 Pleasenote, this test should be done in an

industrial setting and not at home since
proper safety protocol must be observed.
 Flame-retardants can mask the
normal flame and smoke
characteristics of a material
although stock shapes usually do
not include these additives
unless.

 Not all these characteristics can

be used to examine every plastic.
We will discuss those that do
apply.
POLYMER FLAME ODOUR OBSERVATION
PVC Yellow with green acrid Strongly acidic
base fumes
PF resin Yellow Phenol and Very difficult to
HCHO ignite
UF resin Pale yellow light Fish like HCHO Alkaline very
blue green edge difficult to
ignite
Nylons Blue and yellow Resembling Melts sharply to
burning clear, flowing
vegetables, liquid
burnt hair Melt cannot be
drawn into
fibres
POLYMER FLAME ODOUR OBSERVATION
Polyethylene Yellow with blue Resembling Clear melt
flame burning paraffin
wax
Poly (𝜶- Yellow with blue Resembling Clear melt
olefins) flame burning paraffin
wax
Polyesters Yellow smoky Unpleasant Melts and giving
sweety smell acidic distillate
or black residue
PVA Yellow, candle Unpleasant smell Black residue
like limited
smoky
PVAc Yellow smoky Like acetic acid Sticky residue,
acidic volatile
SBR yellow, highly Fruity smell of Clear readily
smoky styrene
 Remember it is important to work in a
well ventilated area.

 H eat a m etal or g las s r od, f or

exam p le a s tir r in g r od to
500°F/2 6 0 °C. Press it again st
th e s am p le.

 Ifit is a thermoplastic it will melt,

but if it is a thermoset it will not.
❑ ABS has an acrid smell when a heat
source is applied.

 The flame is yellow with blue edges and will

not drip. ABS will continue to burn when the
flame source is removed and the odor
continues to be acrid, the flame color is the
same yellow with blue edges and the
material will drip. The rate of burning is
slow and black smoke with soot is admitted
into the air.
 Test for Natural rubber and Synthetic rubber

0.1 g sample gently heated Polyisoprene

add chromic acid Yield acetic
solution acid(Residue)

add phenol heat

purple colour
 5 % solution of + few drops of
PVC in pyridine 10% alch. NaOH/KOH

Mixture changes from colourless through light

yellow, dark brown to black with time
 When a strip of filter paper soaked in a
fresh solution of o-nitrobenzaldehyde in
dil. NaOH is held over the pyrolytic
vapours of polyamides.

A black colour is developed while

vapours of polyamides from diacids
polyamides from adipic acid give grey
colour.
 Nylon 6/6 is an off-white plastic material.

 Itis fairly hard and cannot be marred with

a fingernail.

 When burned it gives off the odor of burnt

wool or hair.

 The flame is blue with a yellowish tip.

Additionally, the material drips when flame
is applied.

 Itwill continue to burn slowly after the

flame source is removed.
 Polypropylenesmells acrid when a flame is
applied and the flame is yellow in color.

 Itwill continue to burn after the flame

source is removed giving off a sweet smell.

 The flame at this point is blue with a

yellow tip. PP produces drips as it
continues to burn slowly.

 When bent, polypropylene sheet will turn

white on the crease line. Interestingly, PP
floats in water.
 Polycarbonategives off a faint,
sweet aromatic ester smell.

 The flame is orange in color and

PC will drip when a flame is
applied.

 Thesmoke is black and gives off

soot into the air.
 PTFEis a fluorocarbon.

 Itis very white and has a waxy feel. It is

also fairly soft. You can mar it with your
thumb nail.

A piece of PTFE with no flame applied

gives off the faint smell of burned hair.

 When a flame is applied, the material does

not drip. PTFE has one of the lowest
coefficients of friction of all the
thermoplastics.

 When rubbed against a surface, it will slide

easily but will not wear well.
 Polyesters, when burned, smell of
hydrochloric acid and the flame is yellow in
color.
 There are no drips.

When the flame source is removed the

material will continue to burn.

 The smell is nondescript but the flame is a

yellow color with blue edges.

 Again.there are no drips and the material

burns slowly. Polyesters will crack and
break when flame is applied.
 Phenolics smell like formaldehyde and
phenol with no flame applied.

 When a flame source is present the

materials will smell of phenols and wood or
paper.

 The flame color is yellow and the material

will not drip.

 The heat source may make phenolics crack.

POLYMER CHARACTERISTICS CHARACTERIS FLAME COLOUR EXTINGUISH
ON BURNING TICS SMELL CHARACTERISTIC

Natural Continuous Distinctive Black fumes Materials melts

ubber burning smell-organic after burning and
matter hair residue is tacky

Nitrile Continuous Acrylic Black fumes Residue is tacky

ubber burning with minor pungent giving black soot
cracking unpleasant
smell
PVC-Nitrile Burns continuously Bread burning Minor bluish color No stickiness on
on flame with like smell at base surface,
minor-cracking

Chloropren Inconsistent General Copious pale Self extinguishing

e burning on flame plastic yellow fumes immediately after
Neoprene) burning smell removal from
flame, no
stickiness on
surface, charred
MER CHARACTERISTICS CHARACTERISTICS FLAME EXTINGUISH
ON BURNING SMELL COLOUR CHARACTERISTI
ne Continuous Unpleasant wax White fumes Not easily
iene rubber burning with minor burning smell extinguishable.
cracking on flame Residue non-tac

sulphonated Continuous Sulphur burning type Black outline Stickiness observ

thylene burning on flame smell of flame after burning
lon)

ene Continuous Polyethylene burning Black fumes Melts and goes

lene Diene burning smell tacky & charred
mer (EPDM)

ne Inconsistent Mild swell smell White fumes Self extinguishin

burning (Peroxide) immediately aft
removal from
flame, goes to a
white ash
FKM Very difficult to Mild swell smell White fumes Self extinguishin