Polymers in Cables

A Comprehensive Approach to Wire & Cable Material Enhancement

Polymers in Cables

Cray Valley HSC2

Overview

• Curing Performance Rubber- Coagent Definition

- Performance Measures

- Applications

• Inorganic Mineral Dispersion- Mineral Dispersion

- NHFR Transition

- Property Balancing

• Flow & Processibility Optimization- Flow Modification

- Nylon Chain Extension

- TPE Flow Optimization

Polymers in Cables - 4/18/123

Coagent Function

• Coagents increase the quantity of crosslinks formed by

making more efficient use of radicals

- Minimize beta scission reactions

- Maximize crosslink-forming reactions

• Through the proper choice of coagents, the quality of the

crosslinks can be changed as well

- Alter the bond strength of linkage

- Alter network polarity


Coagent Types

• Type I Coagents: Increase both the rate and state of cure

- Generate very reactive radicals

- Polar molecules usually of low molecular weight

- Capable of homopolymerization as well as grafting

- Typical structures include acrylate and methacrylate esters, bismaleimides


Coagent Types

• Type II Coagents: Primarily increase the state of cure only

- Generate less reactive, more stable radicals

- Higher molecular weight unsaturated molecules, oligomers and polymers

- Can be used at higher loadings due to increased compatibility with most elastomer systems

- Contain allylic hydrogens capable of abstraction


Cure Profiles

• The addition of coagents to a compound alters the:

- Cure kinetics (scorch - t2, cure time - t90)

- Ultimate state-of-cure (maximum torque - S)

A – Peroxide cure

C – Type II coagent

B – Type I coagent

torq

ue

(dN

m)

time (minutes)

t2t2* t90

* t90

A

BC

S*

S

torq

ue

(dN

m)

time (minutes)

t2t2* t90

* t90

A

BC

S*

S


Rubber Study

Polymers

• EPDM (72, 6)• EPM (65)• EVA (18)• EVM (50)• CPE

Polymers

• EPDM (72, 6)• EPM (65)• EVA (18)• EVM (50)• CPE

Type II Coagent

High Vinyl Polybutadiene(Ricon® 154)

2 phr {3 phr in CPE}

Type II Coagent

High Vinyl Polybutadiene(Ricon® 154)

2 phr {3 phr in CPE}

Evaluation Criteria

• Rheometry Data (ODR)• Tensile Strength• Elongation• Modulus• Compression Set• Water Resistance• Heat Aging Properties• Electrical Properties

Volume Resistivity Dielectric Strength

Evaluation Criteria

• Rheometry Data (ODR)• Tensile Strength• Elongation• Modulus• Compression Set• Water Resistance• Heat Aging Properties• Electrical Properties

Volume Resistivity Dielectric Strength


Cure State, ODR Torque


Electrical Properties


Water Resistance


Wire & Cable Applications

Down Hole Oil Well Service Cables

- Deep well applications

- Temperatures >260oC

- Highly corrosive

- Ricon 154

- Highly loaded: 25 – 40 phr

Submarine Power Transmission

- Large diameter high voltage cables (>50 kV)

- Ricon 153 & 154

- Moisture resistance

- Insulation property

- Highly loaded: 25 – 40 phr


Dispersing Methodologies

Pre-treated (2 & 3) ATH tended to aerate less (EH&S Win)

Material process improvements: torque & throughput (Productivity Win)

Reduced dilution of EVA matrix (Formulation Win)


Improved Dispersion

No Dispersant Starve CoatedMechanical

Fewer instances of a large aggregate in coated samples and relative aggregate size reduction

Dispersion efficiency was comparable between mechanical and starve coating methods


Impact on Ductility

Mechanical coating and wet coating were equally viable methods

Integration of functional polybutadiene can coincide with mineral surface treatment


Influence on Flammability

UL94 V-2UL94 V-2 UL94 V-0UL94 V-0 UL94 V-2UL94 V-2

Pre-coating ATH with dispersant not only maintained the flammability performance, but also improved it

Dispersing augments the ‘self-extinguishing’ nature of the filled polymer


Heat & Smoke Generation

Heat Release Rate (HRR) improved with the introduction of dispersant

Rate of Smoke Release (RSR) was lowest in composition prepared using starve coating

Dispersant coatings in general imparted better HRR and RSR to EVA/ATH composite


Increase Flow

Nylon chain extension:

• Productivity

• Mechanical properties

• Thermal properties

Flow Control

TPE plasticization:

• Softness

• Flow

• Productivity

Flow Modification


THHN & THHW Cables

• High/Low Tg chain extension

• Melt flow control & optimization

• Hydrophobicity & dielectric

properties

Thermoplastic Nylon

• Moisture content

• Dial in MFR

• Recycled content

HIGH LOW


Flexible Wire

• Flexibility & softness

• Surface quality

• Relevant to:

- SBCs

- EVA

- Ethylene -olefins

Thermoplastic Elastomers


Cray Valley HSC

• Leading global supplier of hydrocarbon resins, diene-based resins,

and specialty monomers

- Wingtack® and Norsolene® (C5 & C9 tackifiers)

- Poly bd®, KrasolTM, and Ricon® (low molecular weight liquid

polybutadiene resins)

- SMA® (styrene-maleic anhydride copolymer resins)

- DymalinkTM (metal centered monomers)

• Annual sales over $350 million and has more than 340 employees

worldwide

• Company’s more than 250 products are manufactured at 9 sites in 4

countries


Cray Valley HSCA Division of Total SA

Upstream Downstream Chemicals

Focus

• Oil & gas exploration• Production• Gas & power • Alternative energy

• Trading & shipping• Refining & marketing• Commodity & specialty fluids

• Base chemicals• Industrial & consumer market specialty chemicals

Sales (billion)

$24.6 $163.4 $23.2

Employees

17,192 32,631 41,658

Total, a partner in your challenges


Cray Valley HSCFocus Markets


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Cray ValleyGlobal Presence

Research

Regional HQ

Sales Office

Global HQ

Manufacturing

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Cray Valley HSC

•For additional information about Cray Valley, its products

or its work in Hydrocarbon Specialty Chemicals,

visit www.CVPolymerAdditives.com.

Technology

Polymers in Cables