NATURAL FIBRES REINFORCED POLYMER COMPOSITES

Maria WLADYKA-PRZYBYLAK Krzysztof BUJNOWICZ

Institute of Natural Fibres and Medicinal Plants, Pozna, Poland

Introduction

Composite is a material that contains

at least two different components, clearly separated one from another and uniformly filling its volume, produced in

order to create particular properties.

matrix

fiber

Introduction (2)
Lignocellulosic natural fibres are an excellent raw materials for production of wide range of composites for different applications. The interest in using natural fiber such as different plant fiber as reinforcement in polymers increased during last years.

Natural Fiber and Fibrous raw materials for reinforcing Composites

Plant fibers - cellulose fibers
bast leaf seed fruit wood grasses and reeds

flax hemp kenaf jute

sunn hemp Crotalia junceaL.

pineapple banana srew pine abaca

(manila)

cotton kapok coir

coconut

hardwood softwood

urena mesta ramie roselle (karkadeh) Isora

curaua agaves sisal henequen cabuja palm

african palm data-palm

wheat oat barley rice bamboo bagasse reed corn rape rye esparto elephant grass cannary grass

They are widely used for different applications as constructions, furnishings and transportation

Building industry

conventional boards, insulatind boards, flame retardant composites

 Furniture industry conventional boards,

flame retardant composites, non-wovens

Floor coverings New Linoleum

Marboleum

The natural vegetable fibres in different car structure elements of Daimler-Benz

Source: K. Bledzki, 1997

Wheel shield

Bumper, Engine shield

Rear shelf

Roof

Cellulose-polymer composite soon in every car !

Sun shields
Upholstery, Door covering (racks), cover, electronic device

Natural Fibers Reinforced Polymers

The interest in natural fiber reinforced polymer composite materials is rapidly growing both in terms of industrial applications and fundamental research. They are renewable, cheap, completely or partially recyclable and biodegradable. These fibers are incorporated into a matrix material such as thermosetting plastics,
thermoplastics or biopolymers.

The use of lignocellulosic materials in the form of fibres or particles results not only in a considerable increase in biodegradability of a composite but also changes its properties, including flame retardancy characteristic.

Advantages of Composites Containing Natural Vegetable Fibers

They are environmentally friendly materials at the stage of production, processing and waste.
Environmentally friendly production of natural vegetable fibers - annual renewability and lower energy inputs in production per unit. Commonly known processing methods.

Properties comparable to those of materials reinforced with glass fiber. Better elasticity of polymer composites reinforced with natural fibers, especially when modified with crushed fibers, embroidered and 3-D weaved fibers.
They display acoustic insulation and absorb vibrations and large quantities of energy when subjected to destruction.

 Lower density of polymer composites reinforced with natural fibers than those reinforced with glass fiber. The price of polymer composites reinforced with natural fibers is from two to three times lower than that of polymers reinforced with glass fiber. Natural vegetable fibers can be applied to the reinforcement of the natural polymers such as starch, lignin, hemicellulose and India-rubber and the material obtained in this way is 100% biodegradable.

Reaction to fire of composites based on lignocellulosic fibres is much more beneficial comparing to polymers significant reduction of heat release rate

Matrixs of natural fibre reinoforced composites

Polymers
thermosetting plastics thermoplastics rubber& natural polymers

phenolic PF epoxy EP polyester SP polyimide PI polyurethane PUR

polypropylene polyamide polyethylene polystyrene polyvinyl chloride

india-rubber modified starch polylactide cellulose esters tannin polyhydroxybutiric acid

These modern composites can be manufactured by classical methods such as extrusion and vacuum molding but also by pultrusion. They will be used in new lighter constructions and air transport. The composites will show other features like current conductivity and surface self cleaning.

Modification Methods
Physical:

Surface fibrillation Electric discharge, e.g. corona, cold plasma treatment

Physico-chemical:

Mercerization, Acetylation

FiberOH + NaOH FiberONa+ + H2O

Modification Methods

In Sweden, a continous process of acetylation has been developed. The pilot plant for wood fibre or particles acetylation of capacity 500 kg/h is jointly owned by A-Cell and GEA Evaporation Technology AB, and located in Kvarntorp.

Chemical Modification Methods

Grafting copolymerization with:

PP CHAIH O HO HO C C O C H2 C H C O

O O
cellulose fiber

Polypropylene-maleic anhydride (MAPP) Vinyl monomer Acrylonitrile Methyl methacrylate Styrene

Treatment with maleated polypropylene
O C C O C O
cellulos e fiber

C H2 C H C

C O C O

C H2 + C H C H2O

cellulose fiber

OH OH

C + O

C H2 C H C

O O O H O H C C O C H2 C H C

the activation of copolymer by heating (t=170oC) before fiber treatment

esterification of cellulose

Chemical Modification Methods

Silanization with organosilanes Silane is a chemical compound with chemical formula SiH4.

(R1O)3 Si R2 X where R1O hydrolyzable alkoxy group, and X- functional organic group

TESTING METHOD
Cone calorimeter method - Standard ISO 5660

The composite materials were tested in an ATLAS cone calorimeter to obtain their heat release rate (HRR) and smoke evolution characteristic. Conditions of the test:

specimen position: horizontal heat flux: 35 kW/m2 spark igniter was used
scan: 5 s

What Cone Calorimeter Determines?

After test, the reduce program calculates the following parameters:

Heat Release Rate* (HRR)
[kW/m2]
Average HRR after 1, 3 and 5 minutes from ignition, and until the end of test Peak HRR (at time)

Total Heat Released (THR) [MJ/m2] Effective Heat of Combustion (HOC) [MJ/kg]
Average HOC during full time of test

Mass Loss Rate* (MLR)

[g/m2s] [m2/kg]

Average MLR, taken for scans after 10% of total mass loss and before 90% of total mass loss has occurred Average SEA during full time of test

Specific Extinction Area (SEA)

CO and CO2 Production

[kg/kg]

Average CO and CO2 yield, taken for scans after 10% of total mass loss and before 90% of total mass loss has occurred

* Predicted values of these parameters are displayed during test on the screen

Thermal Stability of Natural Fibers

in acc.Cone Calorimeter test ISO 5660 at heat flux of 50 kW/m2
Heat Realase Rate Heat Flux 35 kW/m with spark igniter
2

Heat Realase Rate Heat Flux 35 kW/m2 without spark igniter

150 120 90 60 30 0

150 120 90 60 30 0 0 100

cotton hemp

100
cotton hemp

200 time [s]

curaua cabuya

300
abaca flax

HRR [kW/m2 ]

2 HRR [kW/m ]

time [s]

200

300
abaca flax

curaua cabuya

Flammability some Polymers

in acc. Cone Calorimeter test ISO 5660 at heat flux of 35 kW/m2.

1800 1600 1400

HRR [kW/m2 ]

1200 1000 800 600 400 200 0 0 30 60 90 120 Time [s] 150 180

PP PE PLA

210

240

Flammability of Lignocellulosic- Polymer Composites

Polypropylene Natural Fibres Composites

Materials
Isotactic polypropylene (PP) Malen F-401; density 0,9g/cm3; MFI index 2,4-3,2g/10min and tacticity 95% Natural fibers unmodified flax fibers, length 24 mm Hemp and flax shives unmodified and FR modified 1-2 mm 30%

Polypropylene - Flax Fibres Composites comparison with PP

Flammability of Lignocellulosic- Polymer Composites

in acc. Cone Calorimeter test ISO 5660 at heat flux of 35 kW/m2.

Heat release rate

2000 1800 1600 1400 1200 1000 800 600 400 200 0 0 60 120 180 240 T ime [s] 300 360 420 480 PP pure PP+flax fibres 7.5% PP+flax fibres 12.5% PP+ flax fibres 20% PP+ flax fibres 30%

HRR [kW/m2]

Mass loss rate [MLR] of Lignocellulosic- Polymer Composites Polypropylene - Flax Fibres Composites comparison with PP

in acc. Cone Calorimeter test ISO 5660 at heat flux of 35 kW/m2.

35 30 25
PP pure PP+flax fibres 7.5% PP+flax fibres 12.5%

MLR [g/s*m2]

PP+20% of flax fibres PP+30% of flax fibres

20 15 10 5 0 0 60 120 180 240 T ime [s]

300

360

420

480

Flammability of Lignocellulosic- Polymer Composites Polypropylene - Flax Fibres Composites comparison with PP

Total HR, Ave HOC, Ave HOC, Ave MLR, IT

in acc. Cone Calorimeter test ISO 5660 at heat flux of 35 kW/m2
120 110 100 90 80 70 60 50 40 30 20 10 0 T otal HR [M J/m2] Ave HOC [M J/kg] Ave M LR [g/s*m2] IT [s] PP pure PP+flax 7.5% PP+flax 12.5% PP+flax 20% PP+flax 30%

Smoke production as extinction coefficient (EC) of Polypropylene - Flax Fibres Composites comparison with PP

5 4,5 4 3,5

PP pure PP+flax fibers 7,5% PP+Flax fibes 12,5% PP+Flax fibers 20% PP+ flax fibers 30%

EC (1/m)

3 2,5 2 1,5 1 0,5 0 0 60 120 180 240 300 360 Time (s) 420 480 540 600

Comparison of heat release rate (HRR) composites based on PP and different plant fibres (content 30% by weight) in acc. Cone Calorimeter test ISO 5660 at heat flux of 35 kW/m2
1500 1350 1200 1050 PP PP + Flax PP + Hemp PP + Jute PP + Coconut

HRR [kW/m2]

900 750 600 450 300 150 0 0 60 120 180 240 300 Time [s] 360 420 480 540 600

Comparison of heat release rate (HRR) composites based on PP and different and FR protected Flax and Hemp Shives

in acc. Cone Calorimeter test ISO 5660 at heat flux of 35 kW/m2

1600 1400
HRR [kW/m2]

PP PP-Hemp 30%
HRR [kW/m2]

1600 1400 1200 1000 800 600 400 200 0

PP PP-Flax 30% PP-FR Flax30%

1200 1000 800 600 400 200 0 0 200

PP-FRHemp30%

400 600 Time [s]

800

100

100

200 300

400 500 600

700

Time [s]

Comparison of IT, Total HR, Ave HOC, Ave MLR, composites based on PP and different and FR protected Flax and Hemp Shives in acc. Cone Calorimeter test ISO 5660 at heat flux of 35 kW/m2
250 200 150 100 50 0 IT [s] Total HR [MJ/m2] Aver HOC [MJ/kg] Ave MLR [g/ms2] PP PP-hemp 30% PP-FR hemp 30%

250 200 150 100 50 0 IT [s] Total HR [MJ/m2] Aver HOC [MJ/kg] Ave MLR [g/ms2] PP PP-flax 30% PP-FR flax 30%

Flammability of Polyethylene - Flax Fibres Composites

Materials: Polyethylene (low density Malen E GGNX 23DO22) PKN Orlen in Plock, Poland Short flax fibers (2-3m) 10%, 15 % by weight

Flame Retardancy of Polyethylene - Flax Fibres Composites comparison with PE in acc. Cone Calorimeter test ISO 5660 at heat flux of 35 kW/m2

Heat release rate

2000 1600
HRR [kW/m2]
PE PE+10%Flax PE+15% Flax

1200 800 400 0 0 30 60 90 120 150 180 210 240 270 300 330 360 390 Time [s]

Comparison of IT, Total HR, Ave HOC Polyethylene Flax Fibres Composites with PE

120

Time to ignition [s]

Time to ignition

100 80 60 40 20 0 PE PE+10%Flax PE+15%Flax 112 39

36

180 160 140

172 146 131

45 44 43

THR [MJ/m2]

HOC [MJ/kg]

120 100 80 60 40 20 0 PE PE+10% Flax PE+15% Flax

42 41 40 39 38 PE PE+10% Flax PE+15%Flax 44,9 41,1 40,7

Total heat released THR

Effective heat of combustion (HOC)

Flame Retardancy of Poly(lactic acid) PLA Flax, Hemp Fibres Composites comparison with PLA

Materials
PLA Hycail HM 1010 Unmodified flax and hemp fibers, length 1-3 mm, 10% by weight Flax and hemp fibers after mercerization process, length 1-3 mm, 10% by weight Acetylated flax fibers, length 1-3 mm, 10% by weight

Comparison of heat release rate (HRR) from composites based on PLA Resin with hemp fiber and chemical modyfication hemp fiber
in acc. Cone Calorimeter test ISO 5660 at heat flux of 35 kW/m2
600

Heat Released Rate [kW/m2]

500 400 300 200 100 0 0 40 80 120 160 200 240 280 Time [s] PLA PLA+Hemp PLA+Hemp Mercer PLA+Hemp Acetyl

Comparison of heat release rate (HRR) from composites based on PLA Resin with flax fiber and acetylation flax fiber

600

Heat Release Rate [Kw/m2]

500 400 300 200 100 0 0 40 80 120 160 Time [s] 200

PLA PLA+Flax PLA+Flax Acetyl

240

280

Conclusions
1. Nowadays a lot of attention is paid to environmentally-friendly materials. This resulted in growing interest in natural lignocellulosic materials and composites based on them.
2. Lignocellulosic Composites are much more safety during fire than man-made polymers because of lack of dangerous melting and less toxic gases and smoke production.

3. Interesting

results were obtained while studying pure PP, PE and that with an admixture of flax, hemp, fibres and shives.

Heat release rate HRR and mass loss rate MLR curves show that thermal decomposition and combustion of the mentioned samples occur in a different way. The addition of fibres, specially in amount above 20% resulted in an increase in flame retardancy of composite compared to PP, PE alone.

Institute of Natural Fibres and Medicinal Plants

Wojska Polskiego 71 b PL 60 630 Poznan Tel: (+ 48 61) 822 48 15 Fax: (+ 48 61) 841 78 30 http://inf.poznan.pl

Thank you for your attention !