Thermosetting resins

Epoxy resins
Epoxy (glycidyl) groups

O
CH2 CH CH2 CH2(O)CH-CH2-

Epoxy

Glycidyl
NB: bond angles of 60°, rather than 109°28´ of sp3 hybrid:
highly strained,  highly reactive
 Properties
• The primary reason for epoxy’s popularity is
its superb mechanical strength.
• Welding with epoxy is very easy. Epoxy is
nearly always cheaper and faster than
welding.
• Epoxy also has excellent resistance to
chemicals. After setting, there is no worry of
a chemical reaction that will weaken the seal.
• It has good heat resistance property which
makes it ideal for electronics and electrical
systems and other industrial applications.
• It shows good adhering dissimilar substrates.
• It shows light weighting, sound and vibration
dampening.
• It shows good corrosion resistance.
• Its asthetic appeal and appearance is also very
good.
• Epoxy is an adhesive formulation that meets
all of those concerns.
• Its thermal and electrical properties,
strength, and durability are very good.
• In general, epoxies are known for their
excellent adhesion, chemical and heat
resistance, good-to-excellent mechanical
properties and very good electrical insulating
properties.
Epoxy resin
• Epichlorohydrin: CH2(O)CH-CH2-O-Cl
• Bisphenol-A: HOΦ-C(CH3)2-ΦOH

 CH2(O)CH-CH2-OΦ-C(CH3)2-ΦOH + HCl

O O
CH3
CH2CH-CH2-O- -C- -O-CH2CH-CH2
CH3

Di Glycidyl Ether of Bisphenol-A (DGEBA)

DGEBA

• methylene (-CH2-) and ether (-O-) groups

give free movement of atoms before cure:
o less steric hindrance and higher reactivity for
terminal rather than internal epoxy (oxirane)
o terminal epoxy groups mean
crosslink sites are free of mobile chain ends
so higher Tg achieved.
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Cure of epoxy resins
• Reactive site is the 3-atom epoxy ring
o which may yield an hydroxyl group
• Curing agents include:
o amines
o amides
o carboxylic acids
o anhydrides: 2 carboxylic acids with water removed
Epoxy cure temperatures
• low temperature
o ambient to 60°C
• medium temperature
o up to 120°C
• high temperature
o up to 180°C

• pot-life: time from mixing to 1500 mPas

o fibres stick to the brush during lamination
o only tow surfaces are wetted.
Gel time of epoxy resin
Post-cure
• full cure uses 100% of reactive sites
• but constrained movement of polymer chain may
lead to incomplete cure:
o lower glass transition temperature
o lower resin density
 fewer bonds/m3  lower moduli and strengths
o additional free volume
 easier diffusion of chemicals  reduced durability
• to achieve optimum high-performance composites,
post-cure at higher temp’ shortly after production:
o unreacted sites may become inactive over time.
Tg for high-performance epoxy
• DGEBA/DICY Tg ~180-190ºC
o di glycidyl ether of bis phenol A
o aliphatic dicyandiamide
• TGDDM/DDS Tg ~240-260ºC
o tetra glycidyl-4,4‘-diamino diphenyl methane
o aromatic diamino diphenyl sulphone
 advantages:

– low cure reactivity … long storage times

– strength retention after time at temperature
 disadvantages

– low strain to failure

– high moisture absorption
– poor hot/wet performance
Epoxy (vs polyester) resin
• outstanding adhesion
• excellent static and fatigue strengths
• outstanding corrosion protection
• excellent chemical resistance
• excellent weather resistance
• very low shrinkage on curing
• good toughness
• good heat resistance
from AB Strong “Fundamentals of Composites Manufacturing” (1989)
Epoxy (vs polyester) resin
• medium to high cost
• relatively difficult to handle
• potential toxicity of uncured material
• poor appearance after weathering

from AB Strong “Fundamentals of Composites Manufacturing” (1989)

 Applications
• The applications for epoxy-based materials
are extensive and include coatings,
adhesives.
• These are also used in composite materials
such as those using carbon fiber and
fiberglass reinforcements.
• Epoxies can be modified (for example silver-
filled epoxies to give good electrical
conductivity.
•
 Electrical and Electronics

• Epoxy offers high thermal insulation, or thermal

conductivity combined with high electrical
resistance makes it suitable for electrical and
electronics applications.
• Epoxy resins are excellent electrical insulators and
protect electrical components from short circuiting,
dust and moisture.
• Epoxy resin formulations are employed in motors,
generators, transformers, switchgear, bushings,
and insulators.
• In the electronics industry epoxy resins are the
primary resin used in overmolding integrated
circuits, transistors and hybrid circuits, and making
printed circuit boards.
• Epoxy resins are used to bond copper foil to circuit
board substrates, and are a component of the
solder mask on many circuit boards.
 An epoxy encapsulated hybrid
circuit on a printed circuit board

The interior of a pocket calculator. The dark lump of epoxy

in the center covers the processor chip
 Adhesives
• Epoxy adhesives are a major part of the class of
adhesives called "structural adhesives" or
"engineering adhesives" (that includes polyurethane,
acrylic, cyanoacrylate.
• These high-performance adhesives are used in the
construction of aircraft, automobiles, bicycles, boats,
golf clubs, skis, snowboards, and other applications
where high strength bonds are required.
• They can be used as adhesives for wood, metal,
glass, stone, and some plastics. They can be made
flexible or rigid, transparent or opaque/colored, fast
setting or slow setting.
• Epoxy adhesives are better in heat and
chemical resistance than other common
adhesives. In general, epoxy adhesives cured
with heat will be more heat- and chemical-
resistant than those cured at room
temperature. The strength of epoxy
adhesives is degraded at temperatures above
350 °F (177 °C).
Paints and coatings

• Epoxy coatings used for heavy duty service

on metal substrates uses less energy than
heat-cured powder coatings.
• These systems provide a tough, protective
coating with excellent hardness.
• Some epoxy coatings are formulated as an
emulsion in water, and can be cleaned up
without solvents.
• Epoxy coatings are often used in industrial
and automotive applications since they are
more heat resistant than latex-based and
alkyd-based paints. Epoxy paints tend to
deteriorate, known as "chalking out", due to
UV exposure.
• Fusion Bonded Epoxy Powder Coatings (FBE)
are extensively used for corrosion protection
of steel pipes and fittings used in the oil and
gas industry, potable water transmission
pipelines (steel), and concrete reinforcing
rebar.
Industrial tooling and composites
• Epoxy systems are used in industrial tooling
applications to produce molds, master
models, laminates, castings, fixtures, and
other industrial production aids.
• This "plastic tooling" replaces metal, wood
and other traditional materials.
• Epoxies are also used in producing fiber-
reinforced or composite parts to produce
stronger and more temperature-resistant
thermoset polymer matrix composite parts.
 Consumer and marine applications
• Epoxies typically are not used in the outer layer of
a boat because they deteriorate by exposure to UV
light. They are often used during boat repair and
assembly, and then over-coated with conventional
or two-part polyurethane paint or marine-varnishes
that provide UV protection.
• There are two main areas of marine use-
• i. where a high strength/weight ratio is required.
• ii. where area is that their strength, gap filling
properties and excellent adhesion to many
materials including timber have created a boom in
amateur building projects including aircraft and
boats.
• As adhesives, epoxies bond in three ways:
• a) Mechanically- because the bonding
surfaces are roughened;
• b) By proximity- because the cured resins are
physically so close to the bonding surfaces
that they are hard to separate;
• c) Ionically- because the epoxy resins form
ionic bonds at an atomic level with the
bonding surfaces.
 Aerospace applications
• In the aerospace industry, epoxy is used as a
structural matrix material which is then
reinforced by fiber. Typical fiber
reinforcements include glass, carbon, Kevlar,
and boron. Epoxies are also used as a
structural glue. Materials like wood, and
others that are 'low-tech' are glued with
epoxy resin.
 Biology
• Water-soluble epoxies such as Durcupan are
commonly used for embedding electron
microscope samples in plastic so they may
be sectioned (sliced thin) with a microtome
and then imaged.
Art

• Epoxy resin, mixed with pigment, may be

used as a painting medium, by pouring
layers on top of each other to form a
complete picture.[15]
 Health risks
• The primary risk associated with epoxy use is
often related to the hardener component and
not to the epoxy resin itself.
• Amine hardeners in particular are generally
corrosive, but may also be classed as toxic or
carcinogenic/mutagenic.
• Aromatic amines present a particular health
hazard (most are known or suspected
carcinogens), but their use is now restricted
to specific industrial applications.
• Liquid epoxy resins in their uncured state are
mostly classed as irritant to the eyes and skin,
as well as toxic to aquatic organisms. Solid
epoxy resins are generally safer than liquid
epoxy resins, and many are classified non-
hazardous materials.
• One particular risk associated with epoxy
resins is sensitization. Exposure to epoxy
resins can, over time, induce an allergic
reaction.
• Allergic reaction sometimes occurs at a time which
is delayed several days from the exposure. Allergic
reaction is often visible in the form of dermatitis,
particularly in areas where the exposure has been
highest (commonly hands and forearms).

• Epoxy use is a main source of occupational asthma

among users of plastics.[18] Bisphenol A, which is
used to manufacture a common class of epoxy
resins, is a known endocrine disruptor.
Polyurethanes
primarily for RIM processes
 number common chemistry

Bismaleimide 2
3
di
tri-
bis-
tris-
4 tetra- tetrakis-
imide group
Note:
O
C delocalisation across
N • benzene ring
C • both C=O groups
O
• p-orbital on N
 stiff molecule
Unsaturated
polyesters
Curing of polyester resin
-A-B-A-B-A-B-
where B block contains unsaturation (double bonds)
in backbone of polymer chain, leading to a 3D network
plus styrene (S: ΦCH=CH2 ) reactive diluent

- A - B - A - B - A - B -
| | |
S S S
| | |
- A - B - A - B - A - B -
| | |
S S S
| | |
- A - B - A - B - A - B -
Curing of polyester resin

Unsaturated polyester and A broken bond Molecules move closer together

styrene both have double bonds. = two free radicals. Free radicals pair-up and rotate to form cross-link.
Polyester chain top and bottom, Assume all double bonds break. to make new bonds Net shrinkage of system results.
with 3 styrene molecules Five double bonds are Note two remaining
between. now ten free radicals reactive sites.
Vinyl esters
• epoxy backbone
• addition-type curing

Methacrylics
• methylmethacrylate instead of
styrene as reactive diluent
Summary (key polymers)

Polymern Curing Properties

Ph-F condensation condensation low-cost, brittle, FST

high-cost,
Epoxy condensation ring-opening
high-performance
intermediate cost
UPE condensation addition
balanced performance

and finally, vitrimers …

Vitrimers/CAN
• new class of materials from ~2010
• covalent adaptable networks (CAN)
o cross-link exchange mechanisms
• bulk synthetic organic polymers, processable like glass or metal
• radical generation triggered by
o heat: nanoparticles + electromagnetic heating,
o light: photoinitiator or photothermal dyes
o pH: acidity or basicity of solvent.

• claims for easy reprocessing, recycling or repair

• self-healing/mendable, triggerable shape change, stress reduction

• Tv = topology freezing transition temperature

o Tv may occur above or below Tg (but latter of minimal interest)
Vitrimers
HOT
viscoelastic liquid (1012 Pa s)

Tv topology freezing transition temperature

viscoelastic solid
rubbery (tough/viscoelastic)

Tg glass transition temperature

glassy (brittle /elastic)

COLD
Summary of thermosetting resins lecture

• phenol-formaldehyde (phenolic resin)

• epoxides (generally diglycidyl ethers)
• polyurethanes
• bismaleimides (BMI)
• unsaturated polyesters (UP or UPE)
• vinyl esters
• methacrylics
• vitrimers ( covalent adaptable networks: CAN )