NATURAL FIBRES REINFORCED

POLYMER COMPOSITES

Maria WLADYKA-PRZYBYLAK
Krzysztof BUJNOWICZ

Institute of Natural Fibres and Medicinal Plants,

Poznań, 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 pineapple cotton coconut hardwood wheat

hemp banana kapok softwood oat
sunn hemp srew pine coir barley
Crotalia junceaL. abaca rice
kenaf (manila) bamboo
jute curaua bagasse
agaves reed
urena
mesta sisal corn
ramie henequen rape
roselle cabuja rye
(karkadeh) palm esparto
Isora elephant grass
african palm cannary grass
data-palm
 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 thermoplastics rubber&
plastics natural polymers

phenolic PF polypropylene india-rubber

epoxy EP polyamide modified
polyester SP polyethylene starch
polyimide PI polystyrene polylactide
polyurethane polyvinyl cellulose
PUR chloride esters
tannin
polyhydroxy-
butiric 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

Fiber–OH + NaOH  Fiber–O–Na+ + 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:

 Polypropylene-maleic anhydride (MAPP)
 Vinyl monomer
 Acrylonitrile
 Methyl methacrylate
 Styrene
Treatment with maleated polypropylene
PP
CHAIH O
O
O C C H2
O
O cellulose
fiber
HO C C H2
O C C C
 C C C H2
C H2 OH H
cellulose
fiber + O O
HO C C C O + H2O OH
H C C C
C C C H
O
O H
O
O C C H2
O cellulos
e
fiber
O O C C C
esterification H H H
the activation of copolymer by heating O
(t=170oC) before fiber treatment 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]
Average MLR, taken for scans after 10% of total mass loss and before 90% of
total mass loss has occurred
 Specific Extinction Area (SEA) [m2/kg]
Average SEA during full time of test
 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

2 Heat Realase Rate Heat Flux 35 kW/m2

Heat Realase Rate Heat Flux 35 kW/m
without spark igniter
with spark igniter
150 150

HRR [kW/m2 ]
HRR [kW/m2]

120 120
90 90
60 60
30 30
0 0
0 100 200 300 0 100 200 300
time [s] time [s]
cotton curaua abaca
cotton curaua abaca
hemp cabuya flax
hemp cabuya flax
 Flammability some Polymers
in acc. Cone Calorimeter test ISO 5660 at heat flux of 35 kW/m2.

1800

1600 PP
1400 PE
1200
PLA
HRR [kW/m2 ]

1000

800

600

400

200

0
0 30 60 90 120 150 180 210 240
Time [s]
 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 2-
4 mm
• Hemp and flax shives unmodified and FR
modified 1-2 mm – 30%
 Flammability 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.

Heat release rate
2000

PP pure
1800
PP+flax fibres 7.5%
1600
PP+flax fibres 12.5%

1400 PP+ flax fibres 20%

PP+ flax fibres 30%

1200
HRR [kW/m2]

1000

800

600

400

200

0
0 60 120 180 240 300 360 420 480
T ime [s]
 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
PP pure

PP+flax fibres 7.5%

30
PP+flax fibres 12.5%

25 PP+20% of flax fibres

MLR [g/s*m2]

PP+30% of flax fibres

20

15

10

0
0 60 120 180 240 300 360 420 480
T ime [s]
 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 PP pure

100 PP+flax 7.5%

90 PP+flax 12.5%

80 PP+flax 20%
PP+flax 30%
70
60
50
40
30
20
10
0
T otal HR Ave HOC Ave M LR IT [s]
[M J/m2] [M J/kg] [g/s*m2]
 Smoke production as extinction coefficient (EC)
of Polypropylene - Flax Fibres Composites comparison with PP

PP pure
5
PP+flax fibers 7,5%
4,5 PP+Flax fibes 12,5%

4 PP+Flax fibers 20%

PP+ flax fibers 30%
3,5
3
EC (1/m)

2,5
2
1,5
1
0,5
0
0 60 120 180 240 300 360 420 480 540 600
Time (s)
 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
PP
1350
PP + Flax
PP + Hemp
1200
PP + Jute
1050 PP + Coconut

900
HRR [kW/m2]

750

600

450

300

150

0
0 60 120 180 240 300 360 420 480 540 600
Time [s]
 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
1600 PP PP
1400 1400
PP-Hemp 30% PP-Flax 30%
1200 1200

HRR [kW/m2]
HRR [kW/m2]

PP-FRHemp30% PP-FR Flax30%

1000 1000
800 800
600 600
400 400
200 200
0 0
0 200 400 600 800 100 0 100 200 300 400 500 600 700
Time [s] 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

250 250

200 200
PP PP
150 PP-hemp 30% 150 PP-flax 30%
PP-FR hemp 30% PP-FR flax 30%
100 100

50 50

0 0
IT [s] Total HR Aver HOC Ave MLR IT [s] Total HR Aver HOC Ave MLR
[MJ/m2] [MJ/kg] [g/ms2] [MJ/m2] [MJ/kg] [g/ms2]
 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
PE
2000
PE+10%Flax

1600 PE+15% Flax

HRR [kW/m2]

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

100

Time to ignition
Time to ignition [s]
80

60
39 36
112
40

20

0
PE PE+10%Flax PE+15%Flax

172 45
180
146 131 44
160
140 43
THR [MJ/m2]

120
100 HOC [MJ/kg] 42

80 41

60 44,9
40 41,1 40,7
40
20 39

0 38
PE PE+10% Flax PE+15% Flax PE PE+10% Flax PE+15%Flax

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 PLA
PLA+Hemp
300 PLA+Hemp Mercer
PLA+Hemp Acetyl
200

100

0
0 40 80 120 160 200 240 280
Time [s]
 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
PLA
400 PLA+Flax
PLA+Flax Acetyl
300

200

100

0
0 40 80 120 160 200 240 280

Time [s]
 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 !