[PPT] - NOVEL NYLON/HALOGENATED BUTYL RUBBER BLENDS IN PROTECTION AGAINST PowerPoint Presentation

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NOVEL NYLON/HALOGENATED BUTYL RUBBER BLENDS IN PROTECTION AGAINST WARFARE AGENTS

Marek Gnatow ski, Polymer Engineering Company Ltd, Burnaby, B.C., Canada J.D. ( Jack) Van Dyke, Trinity Western University, Langley, B.C., Canada Andrew Burczyk, Defence R&D Canada-Suffield, AB, Canada

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Special Gear to Protect Humans and Resources Against an Aggressive and Hostile Environment

Space Underwater Natural or man made disasters War

Polymeric Materials in Protective Gear

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Polymeric Materials are Used in Protective Gear for the Following Reasons:

Wide range of mechanical properties
Relatively resistant to hostile and aggressive environment

(if properly selected)

Easy moulding
Wide range of coefficient of friction
Light weight
Variety of colours

Polymeric Materials in Protective Gear

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Polymeric Materials in Protective Gear

Materials Properties

Material Elastom eric Behaviour Modulus of Elasticity MPa Density g/ cm 3 Coefficient

f Friction

Barrier Properties

Yes

(in selected materials)

Variable Excellent Excellent No No Polymers

10 – 40,000 0.8 – 2.3 0.05 - 4

Metals

300 – 400,000 2 - 20 0.15 - 5

Ceramics and Glasses

200,000 – 450,000 2.5 - 6 0.6 - 1

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Polymeric Materials in Protective Gear

Properties of selected commercial polymeric materials

4 – excellent 3 – good 2 – acceptable 1 – unacceptable

a. immersion in hot water
b. requires modification
c. ebonite
d. CW – chemical warfare agent

* long term exposure

Resistance to Mechanical Behaviour CWd Water* Oil and Fuels Engineered Plastic Elastomer Butyl, Halogenated Butyl Rubber (C,B) IIR 4 4 1 1 4 2-3 Natural Rubber (polyisoprene) NR 1 1-3 1 1(3)c 4 2-3 Chloroprene CR 1-2 2-3 4 1 4 2-3 Nitrile Rubber NBR 1-2 3 4 1 4 2-3 Santoprene (PP/EPDM) TPE 1 3 1-2 1 4 4 Polyurethane Elastomer PU 1-2 2-3 3-4 1 4 3-4 Polyamides (Nylons) PA 3-4 3 (1)a 4 4 1 3-4 Aromatic Polyesters (PBT, PET) PET, PBT 4 4 (2)a 4 4 1 3-4 Polyvinyl Alcohol (PVOH) PVA 2-4 1 4 3 1 1-3b Polystyrene PS 1 4 1 2-3 1 4 HDPE HDPE 1 4 3-4 2-3 1 4 Processing Friendly Material

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Polymeric Materials in Protective Gear

Compression moulding Injection moulding Extrusion

Easy Moulding

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Materials Selection for Blending

A. Nylon 12
Excellent barrier properties
Excellent mechanical properties
Relatively low processing

temperature (190 – 220oC)

Commercially available
B. (Halogenated)

Butyl Rubber

Good mechanical properties
Good warfare agent resistance
Commercially available

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Nylon Chlorobutyl Rubber Blend

Challenges in Blending

Physical incompatibility of nylon and

halogenated butyl rubbers

Incorporation of over 50% rubber into the

blend

Maintaining thermoplastic properties and

good mechanical properties of blend

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Nylon Chlorobutyl Rubber Blend

Extrusion Batch Mixing Blending Procedure

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The Dynamic Vulcanization Process

regular blending dynamic vulcanization

Nylon Chlorobutyl Rubber Blend

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Nylon Chlorobutyl Rubber Blend

Potential Compatibilization of Blend

O O N H N H O N H CH2* O O N H N H O N H

+

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Nylon Chlorobutyl Rubber Blend

20 40 60 80 100 120 Butyl Bromobutyl Chlorobutyl % Insolubles

Non Vulcanized Dynamically Vulcanized % Insolubles – Non-vulcanized vs. Dynamically Vulcanized

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Nylon Chlorobutyl Rubber Blend

2 4 6 8 10 12 14 16 P A 1 2 / B I I R P A 1 2 / B I I R D V P A 1 2 / C I I R P A 1 2 / C I I R D V P A 1 2 / I I R P A 1 2 / I I R D V Ultim ate Tensile Strength (MPa)

Comparison of Tensile Strength Non-vulcanized vs. Dynamically Vulcanized

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Nylon Chlorobutyl Rubber Blend

Comparison of Elongation Non-vulcanized and Dynamically Vulcanized

50 100 150 200 250 300 350 400 P A 1 2 / B I I R P A 1 2 / B I I R D V P A 1 2 / C I I R P A 1 2 / C I I R D V P A 1 2 / I I R P A 1 2 / I I R D V Elongation at Break (%)

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Nylon Halogenated Rubber Blend

Swelling index and elongation at break for dynamically vulcanized blends in CHCl3

1 2 3 4 5 6 7 10 20 30 40 50 60 70 80 90 100 % Polyamide

Swelling Index

50 100 150 200 250 300

Elongation at Break

Swelling Index Elongation at Break

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Nylon Halogenated Rubber Blend

Blend Microstructure

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Nylon-Chlorinated Butyl Rubber Blend

Effect of Moulding Conditions on Tensile Strength and Elongation at Break

5 10 15 20 25 30 35 40 45 50 Injection Moulding Compression Extrusion Injection Moulding Compression Extrusion

Tensile Strength at Break (MPa)

50 100 150 200 250 300

Elongation at Break (% )

PA12/CIIR 30/70 PA12/CIIR 40/60

Tensile strength at break Elongation at break (Video)

PA12/CIIR 30/70 PA12/CIIR 40/60 Testing according to ASTM D 638M, specimen type M-III

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Nylon-Chlorinated Butyl Rubber Blend

Effect of Moulding Conditions on Tensile Modulus

50 100 150 200 250 300 350 400 450 I n j e c t i

n

M

u

l d i n g C

m

p r e s s i

n

E x t r u s i

n

I n j e c t i

n

M

u

l d i n g C

m

p r e s s i

n

E x t r u s i

n

Modulus (Mpa)

PA12/CIIR 30/70 PA12/CIIR 40/60

PA12/CIIR 30/70 PA12/CIIR 40/60 Testing according to ASTM D 638M, specimen type M-III

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Nylon-Chlorinated Butyl Rubber Blend

Effect of Moulding on Hardness

20 25 30 35 40 45 50 55 60 Injection Moulding Compression Extrusion Injection Moulding Compression Extrusion Shore D Hardness

PA12/CIIR 30/70 PA12/CIIR 40/60

PA12/CIIR 30/70 PA12/CIIR 40/60 Testing according to ASTM D 638M, specimen type M-III

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5 10 15 20 25 30 35 40 45 50 As Moulded cut from Impact Bar As Moulded cut from Impact Bar Tensile Strength at Break (MPa) 50 100 150 200 250 300 Elongation at Break (%)

PA12/CIIR 30/70 PA12/CIIR 40/60

50 100 150 200 250 300 350 400 450 As Moulded cut from Impact Bar As Moulded cut from Impact Bar

M

d

u lu s (M p a )

PA12/CIIR 30/70 PA12CIIR 40/60

Injection moulded Die cut

Nylon-Chlorinated Butyl Rubber Blend

Effect of Flow in Mould on Mechanical Properties

Tensile strength at break (Mpa) Elongation at break (Video) (%) PA12/CIIR 30/70 PA12/CIIR 40/60 PA12/CIIR 30/70 PA12/CIIR 40/60

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Nylon-Chlorinated Butyl Rubber Blend

Effect of Flow on Blend Microstructure

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Nylon-Chlorinated Butyl Rubber Blend

Penetration* for all samples was 0 µg at testing conditions

* method of testing described in C.L. Stevens presentation “Nylon-12 Nanocomposite Thin Films as Protective Barriers”

Reemission* vs. Nylon Content in Blends

10 20 30 40 50 60 15 20 25 30 35 40 45 Nylon Content (Wt%) Re-emission (µg)

Sulfur ZDEDC / ZnO

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Polymeric Materials in Protective Gear

Increase protection efficiency
Decrease the burden on personnel
Decrease manufacturing costs

New Development of Special Polymeric Materials Will Bring Revolutionary Changes to Protective Equipment

Post World War II 1980’s The Future

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Conclusions

1. Nylon can be blended with butyl or halogenated butyl rubber to obtain material with thermoplastic elastomer properties 2. Properties of the blends depend on nylon/ rubber ratio, mixing conditions, and vulcanizing agent used 3. Mechanical properties also depend on moulding conditions and mould geometry 4. Nylon-chlorobutyl thermoplastic elastomers showed excellent resistance to penetration and reemission of warfare agents 5. Nylon-chlorobutyl blends showed significantly better resistance to hydrocarbon and chlorinated hydrocarbon solvents than could be expected from the rubber content in the blend

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Acknowledgments

Laboratory Support

Polymer Engineering Company

Andrew Koutsandreas
Dave Lesewick
Christine Mah
Beverley Start
Kate Mao

Trinity Western University

Andrea Lengkeek
Leanne Edwards
Sebastian Temple

DRDC - Dockyard Laboratory Pacific

Bruce Kaye

DRDC – Suffield

Benoit Lacroix

Materials Suppliers

Exxon Mobil
Bayer
EMS Grivory