Specialty Resins

A. Brent Strong

Vinyl Esters
Epoxy resins that have been modified so that they can be cured like a polyester
The modification is usually a reaction with an acrylic (acrylic modified epoxy) The modification must substitute a carboncarbon double bond for the epoxy ring

The name, vinyl ester, comes from old chemistry because the carbon-carbon bond (called a vinyl bond) is on the end and next to a polyester group

Vinyl Ester Structure

C (

C )n

Unsaturated end group

C
Unsaturated end group

Vinyl esters specific molecules

O
H

C C C O + C C C C C... Epoxy C
Methyl Acrylic Acid

O C C C O
Vinyl Ester

C C C C C...

Specialty Vinyl Esters

(C
O C C OH C O O C C C C O C C OH C O O C C C C

)n C
O C C OH C O O C C C C

Epoxy Novolac Vinyl Ester Resin

O C OH C C C OH O C

C C C O C C C O

O C C C O C C C

Bisphenol-A Epichlorohydrin-based vinyl ester

Vinyl esters Properties

Almost all properties of vinyl esters (and cost) are intermediate between polyesters and epoxies Some of the most important properties include:
Water and chemical resistance Electrical stability Thermal stability Toughness Low volatiles during manufacture Low shrinkage

Vinyl Esters

Phenolics
Key properties determining most of the applications of phenolics
Very low flammability and low smoke Very stiff and hard Very low heat transfer High thermal stability Good electrical properties Excellent adhesion Resistance to chlorinated solvents Moderately low price (10-15% above polyesters)

Phenolics polymerization and crosslinking

O C H
OH

OH

+
H

+
H

C H

+.
OH ...C C OH C...

Formaldehyde

Phenol

Loss of Water Vapor

C OH ...C C OH

C OH C OH C C...

3-D Phenolic Network

...C

C...

Phenolics
Applications
Handles for cooking pans Interiors of public transportation Glue for laminates (such as plywood) Electrical switches and other equipment Molded parts in moderately hot environments (such as near the motor of an automobile) Billiard balls Conversion to epoxy or vinyl ester resins Rocket exit nozzles and carbon-carbon composites (ablation)

Phenolic Flammability
Flame Spread Index
Vinyl Ester Specific Optical Density Vinyl Ester Epoxy FR Polyester Phenolic
100 200 300 400 500 600

Epoxy
FR Polyester Phenolic 10 20 40 30 (ASTM E-162 for thermoset composites)

(ASTM E-662 for thermoset composites)

NBS Smoke Chamber (Smoldering)

700600500-

Epoxy Polyester

Optical Density

400300200100-

Phenolic
2 4 6 8 10 12 14 16 18 20 22

Time (min)

Rocket exit nozzle

Nose Cone

Rocket Propellant

Rocket Motor

Ablative Material

Rocket Exit Throat

Exit Nozzle
10 oF 500 oF 4000 oF

Phenolics Processing
Problem Toxic monomer (formaldehyde) Condensation of water High shrinkage Solution B-staging to novolac (solid, 2-step with hexa) or resole (liquid,1-step) Slow cures and venting of mold (compression molding) Fillers (minerals, sawdust, wood flour, ground nut shells, etc.)

Brittleness
Inconsistent color

Fillers (selected) and thickness of parts

Black pigment

Phenolics

Carbon-Carbon Composites
Carbon matrix and carbon fibers Carbon matrix is made from phenolic resins that have been repeatedly charred and infiltrated with new resin
Very long process (up to 6 months for a part) Very costly

Extremely high thermal stability

Needs flammability coating (ceramic) at very high temperatures

Production Flow Chart for Carbon-Carbon Composites

Polymer or Pitch Binder Cured Carbon/Resin Part Carbon Fiber

Carbonization (up to 1000 oC)

Impregnation by Gas or Liquid

Graphitization 2500-3000 oC

Carbon/Carbon Composite 2500-3000 oC

Carbon-Carbon Composites Thermal Stability

106Epoxy Composites Advanced Metalics 105Polyimides Experimental

104Exposure Time 103(sec) 102101oF 0 oC -18

Carbon-Carbon

Ablative Materials (such as phenolics) 1000 538 2000 1093 Temperature 3000 1650 4000 2204

Carbon-Carbon

Brake Pads

Polyimides
Very high thermal stability Excellent solvent resistance Excellent mechanical properties Self-extinguishing Processing
Standard composite techniques Cures are much longer for polyimides than epoxies or polyesters Bis-maleimide (BMI) processes like a polyester

Polyimides specific molecules

...C C C C O C C C C ...C C C O C N N C O O C O O C N C O C N C O O C C... C C C C C C C C...

Crosslinked Polyimide (PMR-15)

O C C N C C O
Crosslink sites

O C C N C C O

Bismaleimide (BMI)

Polyimides

Cyanate esters
Superior dielectric loss properties
Radomes Skins covering antennae arrays

Low moisture absorption Low off-gassing

Space applications

Cyanate Esters
R R O C N N O C N C O R O N C R O C N N C N O R O C N C O R O C N N C N O R

R=

C C

C O R

C O R

Cyanate Esters

Polyurethanes
Very common plastic type and just now finding applications in composites
Excellent for resin infusion processes (RIM, RTM, etc.)

Properties can be easily tailored for an application

Varying the amount of aromatic and non-aromatic (aliphatic) content in both polyol and isocyanate (the monomers) Domains give additional selectivity (Spandex) Moderate cost (about like epoxies)

Tough and abrasion resistant

Polyurethanes
HO Polyol OH + O C=N = Di-isocyanate O N=C =

HO

O H O C N
= Urethane linkage

O N=C =

Polyurethane

Silicones
Widely used as a mold release
Can be a contamination that makes bonding difficult with some adhesives Silicone can be an adhesive itself

Not widely used in composites as a matrix but might be used as a matrix for special applications
Moderate thermal stability (Equivalent to a highperformance epoxy) Low moisture absorption Electrical applications Low flammability

Tooling (flexible)

Silicone

Non-breakable insulators