Phenolic Resins and

Phenolic Molding Compounds

Greg SpaethProject Engineer,

Materials Engineering LaboratoryPlastics Engineering Company

Presented at 2013 SPE Thermoset Division TOPCON

Phenolic Resins

Phenolic resins are synthesized in a pressure vessel by repeatedly linking phenolic monomers

with aldehyde chemicalsTypically phenol and formaldehyde

Cresol Cashew nutshell oil

Furfural

Process variations can result in a assortment of resin structures each

demonstrating a wide range of properties

Other phenols include

Another aldehyde used

There are Two Types of Phenolic Resins

NovolacMolar excess of phenolRequire an external curing agent

Usually hexamethylenetetramine or “Hexa”Two Stage

Two year shelf life

ResolTypically there is a molar excess of formaldehydeDo not require an external curing agentSingle StageSix month shelf life

Phenolic Molding Compounds

Phenolic Molding CompoundsPhenolic Molding Compounds are produced by compounding

various fillers with Phenolic Resin

Typical Formula

50 % Phenolic Resin, resol or novolac 45 % filler

5 % colorants and lubricants

Woodflour

Glass FibersCotton

Carbon Fibers or graphite powder

Minerals, talc, clay, ATH, etc.

Carbon BlackZinc Stearate

The Oil and Natural GasMining Process

as a Case Study forPhenolic Materials

A well begins by drilling a large diameter hole extending below the fresh water

A surface casing is inserted to isolate fresh water and support the blow out preventer

Cement is pumped into the casing

The cement is forced out of the casing and up the well hole sealing of the aquifer

Wiper Plugs and Darts

Phenolic Core

Over molded rubber shell

Easy drill out with small debris

The molded phenolic core provides superior strength and rigidity to enable the wiper plug to withstand the high pressures involved in forcing hundreds of cubic feet of concrete through the well casing

Why Phenolic Molding Compounds?

High Modulus provides stiffness and stability for the darts mandrel core and tighter griping for the elastomer wiper segments

Heat resistance allowing plugs rated for use at 400ºF

The wiper plug is then drill out and the production well is drilled.

Production casing is lowered It takes more than 350 casings weighing more then 85 tons to case a 10,500 foot well

Cement is once again pumped into the well

Again using a wiper plug the cement is force back up the well securing the casing

Fracturing the well then begins by lowering a perforation gun down the well casing

Small shaped explosives blast holes through the casing, cement, and into the formation

Fracturing fluid is pumped into the well

The fluid under extreme pressure causes the formation to fracture

Fracturing fluids varies among regions and well types, but typically consists of water (90+%) proppant (9%) and chemicals (<2%)

Resin Coated Proppant Sand

Resin Coated Proppant Sand

Once the fracturing fluid is removed, the phenolic resin coated sand remains behind and works as a prop to keep the fissures from sealing on release of pressure

Phenolic’s high modulus and excellent heat and creep resistance resists fracture under pressure as proven in industry “Conductivity test”

Why Phenolic Resin?

Chemical Resistanceharsh chemicals found down hole can attack various proppantincluding ceramic proppant

Why Phenolic Resin?

Curable ProppantEnables the proppant to remain in place in wells with high pressure flow

The now fractured portion of the well is sealed off using fracturing ball

Fracturing Balls

Fracturing Balls

Customizable formulations allowing a specific gravity range of 0.8 to 3.5+

Phenolic Balls offer an excellent combination of chemical and heat resistance with superior tensile and compressive strength compared with other plastic balls.

Why Phenolic Molding Compound?

The perf gun is again lowered and detonated

Again fracturing fluid is pumped into the well to fracture the new section of the well while the already fractured section is isolated by the frac ball

The perf gun is again lowered and detonated

Fracturing Balls

Perforation and well fracturing is repeated as often as needed

Once fracturing is complete the balls are usually drilled or floated out

Surface equipment is put in place

Well begins production

Valve Components

Valve Components

A phenolic back-up ring allows internal pressure to anchor the seat within the valve body and prevents seat walking

Non-collapsible, stretch resistant, blow out proof, field replaceable

Non-collapsible, stretch resistant, blow out proof, field replaceable

Why Phenolic Molding Compounds?

Strength, rigidity, dimensional stability, creep resistance

Chemical resistance and high hardness

Provide valve components that resists corrosive environments and do not deform under pressure allowing for repeated ball sealing

Corrosive coatings forStorage tanks, semi tank trailers, railroad tank cars, fans blowers, and fin tube coils

Other Applications

Binder forFriction pads, brake pads, grinding wheels, plywood and particle board

Wear ResistanceGas meter valves, pump seals, caster wheels

Dimensional Stability &Thermal PerformanceBrake pistons, transmission parts, electrical motor brush cards

Electrical insulationterminal strips, commutators, capacitor cans and caps

Offshore Applications

Why Phenolic Resin?

Superior Creep ResistanceStrength and stability under load

Low weight high strength and modulusStrength and rigidity

Chemically ResistantHarsh marine environment

Excellent flammability resistance and low smoke and toxicity Increased level of safety

High carbon and char yieldRetains level of strength and integrity should fire break out

Chemical Resistance

Phenolic Properties

Transmission oil,150ºC (302ºF)

Salt water, 65ºC (150ºF)

Beach, 65ºC (150ºF)

Unleaded gasoline, 22ºC (72ºF)

E85 Unleaded gasoline, 22ºC (72ºF)

SAE 30 Motor oil, 150ºC (302ºF)

Propylene glycol, 100ºC (212ºF)

Crude oil, 22ºC (72ºF)

Chemical Resistance

Phenolic Properties

Chemical Resistance

Phenolic Properties

Chemical Resistance

Phenolic Properties

Chemical Resistance

Phenolic Properties

Chemical Resistance

Phenolic Properties

Comparison of Phenolic molding compound to engineering grade thermoplastics

Phenolic Properties

Data for PLENCO materials available from PLENCO.com, all thermoplastic data from matweb.com overview average values

Thermoplastics20% fiber glass filled ABS 20% fiber glass filled Acetal20% fiber glass filled PPA20% fiber glass filled PPS20% fiber glass filled Nylon66

Phenolic Molding CompoundGlass and mineral filledPLENCO 06404 glass and mineral filledPLENCO 02311 general purpose woodflour filled

Hardness

Phenolic Properties

Data for phenolic and PLENCO materials are approximated from E scale

Data for PLENCO materials available from PLENCO.com, all thermoplastic data from matweb.com overview average values

Strength and modulus

Phenolic Properties

Data for PLENCO materials available from PLENCO.com, all thermoplastic data from matweb.com overview average values

Strength and modulus

Phenolic Properties

Data for PLENCO materials available from PLENCO.com, all thermoplastic data from matweb.com overview average values

Compressive Strength

Phenolic Properties

Data for PLENCO materials available from PLENCO.com, all thermoplastic data from matweb.com overview average values

Heat Resistance

Phenolic Properties

Flammability resistance

Phenolic Properties

UL V-0 at 0.5mm

IEC 60695 Glow Wire GWFI and GWFI Rating 960ºC+ at 0.75mm

ASTM E162 Flame Spread 0.85*

*Source: Composites WorldAuthor: Michael LeGault Posted on: 2/14/2013

Post bake

Phenolic Properties

What is it?• Postbaking is a manufacturing step where molded parts are heated in an

oven after being removed from the die.

Why do it?• Dimensional stabilize a part, especially for high temperature applications• Out-gas residual ammonia which is a by product of two stage cure• Improve strength• Sometimes only because the print tells you to

How is it done?• Ramp oven from room temperature to 15ºC below parts initial tg at 5º/min• Ramp oven to desired temperature at 0.5-0.25ºC/min to keep the oven

temperature under the parts instantaneous tg

Do I need to do it?• Many Applications do not require a postbake, only a thorough

understanding of the reasons to postbake will help you answer this question

Thank You

Questions?

Greg SpaethProject Engineer,

Materials Engineering LaboratoryPlastics Engineering Company

Presented at 2013 SPE Thermoset Division TOPCON