Effects of Fillers on Polyurethane

Resin-based Polyurethane Elastomeric

Bearing Materials for Passive Isolation

STEFAN OPREA*
Institute of Macromolecular Chemistry ‘Petru Poni’
Aleea Grigore Ghica Voda No. 41-A, 700487 Iasi, Romania

ABSTRACT: A series of cork and black carbon filler incorporated cross-linked

molded polyurethane (PU), based on polyethylene adipate diol and 4,40 diphenyl
methane diisocyanate with 1,4 butane diol or 1,6 hexane diol and glycerin as chain
extender, were synthesized. Mechanical properties were examined in composites
that had between 1 and 15% cork and carbon black between 2 and 3%. Therefore,
in order to understand the behavior of fillers, such as carbon black and cork added
to cross-link polyurethane resins, several thermal and mechanical tests were conducted
on samples, made of these new materials. The mechanical properties of the composites
were found to depend mostly on the type and amount of filler. The results show that
the polyurethane component ratios in cross-linked polymers, the types of filler, and
the amount of powder added all affect the properties of the filled cross-linked
polyurethanes. The addition of cork filler into polyurethane composites yields
an increase in Young’s modulus and a decrease in the elongation at break. This new
cross-linked polyurethane–matrix and polyurethane–cork composite materials with
better damping properties can be used as a bearing pad for acoustic and vibratory
isolation for railway and underground lines.

KEY WORDS: polymer-matrix composite, mechanical properties, hardness,

thermal properties.

INTRODUCTION

RBAN LAND AVAILABILITY for building new structures is becoming more limited,
U thereby accelerating the trend for building new constructions and other noise and
vibration-sensitive structures above, or in close proximity to existing railway lines, major
roads and other ‘noisy’ infrastructure. The acoustic-vibration isolation of a building
requires that the structure be supported on a system of isolating bearing pads designed to
perform under specific operating criteria.
Polyurethanes (PU) are known to be very attractive materials for various applications
such as electrical/electronic potting and encapsulation, constructions, water proofing

*E-mail: stefop@icmpp.ro

Journal of COMPOSITE MATERIALS, Vol. 42, No. 25/2008 2673

0021-9983/08/25 2673–13 $10.00/0 DOI: 10.1177/0021998308096329
ß SAGE Publications 2008
Los Angeles, London, New Delhi and Singapore
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2674 S. OPREA

membranes, asphalt extended membranes, highway sealants, sound and vibration

damping, automotive and rubber parts, etc. Due to their unique property, they offer
the elasticity of rubber combined with the toughness and durability of plastics.
The elasticity and toughness of the PU is dependent on the compositions of soft and
hard segments, chain extender and the additives used [1,2].
Recently, attempts have been made to use lignocellulose as raw material for PU
synthesis. Many studies have been carried out on the usage of biomass, such as
particle board, medium density fiberboard, pulp, and composites [3–6]. Generally, the
usage of biomass in lignocellulosic composites has several advantages such as low
density, greater capacity of deformation, less abrasiveness to equipment, biodegradability,
and low cost.
On the other hand these properties were also found to depend on the NCO to OH ratio.
It was found that the NCO to OH ratio contributed to the formation of a three-
dimensional network in PU preparation [7,8]. The effect of soft segment content along
with its molecular weight was studied. The results showed that the degree of cross-linking
and tensile properties depend mainly on the ratio of the soft to hard segment, and is
unaffected by variations in the length of the soft segment [9,10].
In most composite processing techniques, the resin in liquid form must penetrate fiber
composite in order to produce a sound material. Models have been proposed to describe
the behavior of fiber mats during compression. They have been confronted with
experimental stress–strain curves obtained for a range of types of composites [11–17].
In this article a series of cork and black carbon filler incorporated new cross-linked
molded polyurethane (PU), based on polyethylene adipate diol and 4,40 diphenyl methane
diisocyanate with 1,4 butane diol or 1,6 hexane diol and glycerin as chain extender, were
synthesized. This system has been synthesized and characterized in order to reveal
fundamental properties such as hardness, tensile properties, and thermal behavior.

EXPERIMENT

Materials

All chemicals used in this study are listed in Table 1 and were used as received from the
suppliers unless otherwise stated. Polyester and chain extenders were checked for the
content of moisture and, if necessary, dried under a vacuum until the content of water was
below 0.03%.

Table 1. Materials used to obtain cross-linked polyurethane

of the composite samples for passive isolation.

Mol. Melting Boiling Density Refract.

Designation (Wt.) point (8C) point (8C) (g/cm3) Index Obs.
1,4 butane diol (BD) 90.12 16 230 1.017 –
1,6 hexane diol (HD) 118.1 38 250 –
glycerin 92.9 182 1.261 1.474
4,40 diphenyl methane 250.14 42–44 152–156/ – –
diisocyanate (MDI) 0.2–0.3 mm
Polyethylene adipate 2000 – – 1.175 – COH ¼ 56 mg
diol (PEA) KOH/g

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Polyurethane Resin-based Polyurethane Elastomeric Bearing Materials 2675

Preparation of Polyurethane/Filler Composites

Typically, synthesis of PU was done by the following procedure, and the moles of the
added reagents for the various PU were shown in Table 2.
The synthesis of cross-linked PUs was performed in a one liter glass reactor at
normal pressure, under a nitrogen blanket and vigorous agitation. The NCO/OH ratio of
all formulations was 1.03–1.05. The cork sizes used in this study were 1 and 3 mm. The PU
composite was produced through prepolymer process. In the case of the prepolymer
procedure, in the first step the filler was mixed with polyester, followed by the addition
of MDI at 808C for 1 h, yielding a prepolymer that was mixed in the second step with a
chain extender at 908C for 10 min. The resulting material was poured into a mold and
left to cure at 1008C for 20 h, while post-curing of the PU proceeded at laboratory
temperature for 7 days. Under these conditions, the addition of catalysts was not
necessary. The polyurethane sheets thus prepared were used for the determination of
physico-mechanical properties.
Samples were produced by molding using cross-linked polyurethane resins doped with
0.05 mm sized carbon black particles. The carbon black fillers had a dual purpose: to
provide protection against UV rays and to reduce costs.

Characterization

Infrared spectroscopy (FT-IR) was done using a VERTEX 7 Instrument equipped with a
Golden Gate single reflection ATR accessory, with a spectrum range of 600–4000 cm1.
The thermal stability test of polyurethanes was performed on a DERIVATOGRAF
Q-1500 D apparatus (Hungary). The rate of the TGA scans was 108C/min in air atmosphere.
The initial weight of the samples was about 50 mg and the temperature range 30–7008C.
Mechanical property. The prepared cross-linked PU was characterized for physical
properties such as surface hardness. The tests for mechanical properties such as tensile
strength, percentage elongation at break, and tensile modulus have been performed as per

Table 2. Formulation and hardness of the polyurethane composites obtained.

Rate polyester/ Chain

Designation diisocyanate/chain extenders Hardness
No. samples extenders glycerin Q Filler % shore A
1. PUB 1:2:1 BD – 46
2. PUB 3 1:2:1 BD Cork 3 mm 3% 54
3. PUB 5 1:2:1 BD Cork 3 mm 5% 55
4. PUB 10 1:2:1 BD Cork 3 mm 10% 63
5. PUB 15 1:2:1 BD Cork 3 mm 15% 65
6. PUH 1:3:2 HD – 53
7. PUH 1 1:3:2 HD Cork 1 mm 1% 75
8. PUH 2 1:3:2 HD Cork 1 mm 2% 75
9. PUH 3 1:3:2 HD Cork 1 mm 3% 76
10. PUH 4 1:3:2 HD Cork 1 mm 4% 78
11. PUH 5 1:3:2 HD Cork 1 mm 5% 84
12. PUH 10 1:3:2 HD Cork 1 mm 10% 87
13. PUHb 2 1:3:2 HD Carbon black, 2% 64
14. PUHb 3 1:3:2 HD Carbon black, 3% 55

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the EN ISO 527-1 (1996) method using a TIRA-test 2161 apparatus, from Germany.
A minimum of five samples were tested at room temperature for each formulation and the
average values were reported.
Hardness was measured on Instron Shore Durometer using scale-A.

RESULTS AND DISCUSSION

FTIR spectra of the raw polyurethane materials are shown in Figure 1. The absorption
of –NCO groups from the PU, taking place at 2270 cm1 in IR spectra was not observed in
the resulting composite sheets, indicating the absence of free –NCO groups. The peaks for
the sheets narrowed and shifted to higher than 3400 cm1, compared with the broad
absorption of the –OH stretching vibration in the range of 3350 to 3450 cm1 for the raw
materials. This implies that there is contribution of –NH stretching vibration from the PU.
It was noted that the peaks at 1746 cm1 (stretching vibration of urethane carbonyl
groups) [18], 1640 cm1 (Amide I), and 1560 cm1 (Amide II), occurred in PU, displaying
the formation of urethane bonds in the sheets.

Mechanical Analysis

Table 2 shows the results of the hardness tests on the Shore A scale for composite
samples, measured at five different points in each sample. As can be seen, the hardness of
the cross-linked resin containing cork filler in varying mass proportions increased with the
increase of the amount of cork filler.
Urethane composites are of interest partly because of the wide range of properties
available by appropriately selecting raw materials. The effects of filler contained by the

PUB
% Transmittance (arbitrary unit)

PUH

5000 4000 3000 2000 1000

Wave number (cm–1)

Figure 1. IR spectra of polyurethane samples synthesized with BD and HD.

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Polyurethane Resin-based Polyurethane Elastomeric Bearing Materials 2677

composite on the tensile strength and elongation at break of the sheets are shown in
Figures 2–4. It exhibited a decreased tensile strength and low elongation at break, implying
that filler composition greatly contributed to the toughness of the composites. With an
increase of filler content, the Young modulus increased, whereas the elongation at break

80

70 PUB

60

50
Stress (MPa)

40
PUB10
PUB15
30 PUB5

20 PUB3

10

0
0 50 100 150 200 250 300 350 400 450
Strain (%)

Figure 2. Stress–strain curves of polyurethane and polyurethane composites prepared with BD

and cork 3 mm.

50

45

40

35 PUH

PUH3 PUH1
30
Stress (MPa)

PUH2
PUH4
25

20

15
PUH5
10

5
PUH10
0
0 50 100 150 200 250
Strain (%)

Figure 3. Stress–strain curves of polyurethane and polyurethane composites prepared with HD and cork 1 mm.

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2678 S. OPREA

and tensile strength decreased (Table 3). Figures 2 and 3 presents the stress–strain curves
of PU/cork blends containing 1–15 wt% cork, in which the cross-link density is constant.
The variation in mechanical properties with cork content and chain extender diol type,
reveal substantially different behavioral patterns.
In all cases mechanical properties decreased dramatically with the increase filler content.
This difference is significant at the extremes of the composition range studied.
50

45
PUH
40

35

30
Stress (MPa)

25

PUHb2
20

15 PUHb3

10

0
0 50 100 150 200 250
Strain (%)

Figure 4. Stress–strain curves of polyurethane and polyurethane composites prepared with HD and
carbon black.

Table 3. Tensile properties of polyurethanes obtained with various

fillers and compositions.

Designation
samples E1 (MPa) L1 (%) FR (MPa) AR (%) FM (MPa) AM (%) E (MPa)
PUB 8.5 37.72 86 437 89.7 445 30.8
PUB3 4.2 40 28.7 471 29.6 466 13
PUB5 6.7 27.5 16.8 158.8 19.6 152.7 38
PUB10 7.9 24.8 17.8 131.5 18.1 131.5 56
PUB15 9.6 30 20.6 80 21.6 82.5 57.2
PUH 10.3 37.7 42.1 202.9 42.13 202.9 37.2
PUH1 12.5 29.4 26.7 109.5 27.3 109.5 64
PUH2 13.6 27.2 25.4 72.4 25.5 72.9 79
PUH3 13.5 24.4 24.4 72 24.6 72 94
PUH4 13.9 25 20.8 62 20.9 62 96
PHU5 14.8 25.3 19.7 60 20 61 102
PUH10 13.9 27.4 14.4 42.8 14.5 42.8 108
PUHb2 9.3 36.2 22.1 122.1 22.1 122 35
PUHb3 9 42.9 15.3 96.7 16.6 96.6 47.4

E1 – effective modulus to first transformation of phase; L1 – elongation to first transformation of phase; FR – tensile stress at
break; AR – elongation at break; FM – tensile stress at maximum; AM – elongation at maximum; E – modulus.

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Polyurethane Resin-based Polyurethane Elastomeric Bearing Materials 2679

The results suggest that the accessibility of the PU to the filler wall may play an
important role in determining composite properties.
This impact on interfacial structure and morphology would be clearly represented in the
ultimate properties of the composites. It should not be surprising that a strong correlation
exists between filler content and the mechanical property of interest in virtually all
instances.
When blended with 5–15 wt% cork, the strength and elongation decreased, while the
modulus had improved and the toughness of the blend increased.

Thermal Tests

Thermal degradation curves of the raw materials and of the sheets with fillers are
shown in Figures 5–8. There were three distinct stages of decomposition in the curves.

10

20

30
PUH

40
Weight loss (%)

50 PUH5

PUH10
60

70

80

90

0 100 200 300 400 500 600 700

Temperature (°C)

Figure 5. TG curves of polyurethane and polyurethane composites with HD and cork (1 mm).

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2680 S. OPREA
0

8
Deriv. weight (% min)

10

12 PUH

14

PUH10
PUH5
16

18

0 100 200 300 400 500 600 700

Temperature (°C)

Figure 6. DTG curves for polyurethanes and polyurethane composites with HD and cork (1 mm).

In the first stage, the temperature ranged from room temperature to 300–3508C, causing
the slow decomposition of the sheets and raw materials. In the second stage, the
sheets decomposed quickly in the temperature range of 300 to 4508C with a weight loss
of 60 to 75%.
In the previous two stages, the thermal stability of PU-cork and PU-carbon black
sheets was higher than that of the raw materials, in good agreement with the result
of DSC.
In the third stage, the weight loss of the sheets was less than that of corresponding raw
materials, yet it increased with the increase of filler content.
The decomposition of pure polyurethane starts at about 2608C.

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Polyurethane Resin-based Polyurethane Elastomeric Bearing Materials 2681
0

10

20

PUHb3

30

PUH

PUHb2
40
Weight loss (%)

50

60

70

80

90

0 100 200 300 400 500 600 700

Temperature (°C)

Figure 7. TG curves of polyurethane and polyurethane composites with HD and carbon black.

Generally, the addition of carbon powder causes the initial decomposition temperature
to slightly increase. Full decomposition takes place at a higher temperature. It has been
shown that the incorporation of filler can improve the thermal stability of some polymer
composites [19,20].
The variation of the quantity of cork added to the resins failed to influence the thermal
characteristics. However, the Tg and Tmax values of these composites that contain cork
were found to be improved compared to those of pure resins.
DSC thermograms and corresponding data for the raw material and composite sheets
are shown in Figures 9 and 10. For pure cross-linked PU, the Tg is about 108C and for
composites it is about 158C.

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2682 S. OPREA
0

8
Deriv. weight (% min)

10

PUH
12

PUHb2
14 PUHb3

16

18

0 100 200 300 400 500 600 700

Temperature (°C)

Figure 8. DTG curves for polyurethanes and polyurethane composites with HD and carbon black.

The mobility of the polymer between the intercalated layers caused the
lowering of the cross-linking density and dispersion of the filler. DSC thermograms
indicate that Tg decreased with the addition of the filler to the polymer matrix. The cork
composite sheets exhibited endothermic peaks in the range of 170–1808C in DSC
thermograms, suggesting that the formation of urethane bonds enhanced the thermal
stability.
It reveals that the glass transition temperature decreases slightly with the increase of the
quantity of carbon powder. A possible explanation is that the added particles change the
kinetics of the glass transition [21].

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Polyurethane Resin-based Polyurethane Elastomeric Bearing Materials 2683
3.852

3
Tg: Half Cp Extrapolated = –9.88°C
Delta Cp = 0.453 J/g*°C
2 PUH

1
Tg: Half Cp Extrapolated = –14.54°C
Heat flow endo up (mW)

PUH5 Delta Cp = 0.414 J/g*°C

0

Tg: Half Cp Extrapolated = –14.04°C

–1 PUH3 Delta Cp = 0.419 J/g*°C

–2 Tg: Half Cp Extrapolated = –14.49°C

PUH1 Delta Cp = 0.402 J/g*°C

–3

Tg: Half Cp Extrapolated = –14.35°C

–4 PUHb2 Delta Cp = 0.480 J/g*°C

–4.512
–59.88 –50 –40 –30 –20 –10 0 10 20 30 40 50
Temperature (°C)

Figure 9. Tg in DSC spectra for PU composite obtained with HD.

4.09

Peak = 176.38 °C
Area = 53.556 mJ
3 PUHb2 Delta H = 7.3365 J/g

Peak = 179.89 °C

2 Area = 32.552 mJ
Delta H = 3.7416 J/g
PUH1
Peak = 180.60 °C
1
Heat flow endo up (mW)

Area = 28.481 mJ
Delta H = 3.7475 J/g

PUH3
0

Peak = 173.21 °C
Area = 32.119 mJ
–1 Delta H = 4.2262 J/g

PUH5

–2

–2.633
102.4 110 120 130 140 150 160 170 180 190

Temperature (°C)

Figure 10. Tm in DSC spectra for PU composites obtained with HD.

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2684 S. OPREA

CONCLUSION

A maximum toughness of PU can be achieved by introducing fillers of a properly

cross-linked polyurethane (having an OH mole ratio of diol to triol of 1 to 1). Optimum
toughness is a result of the compatibility of the cross-linked polyurethane with the
composite fillers.
The cork and carbon black fillers added in these cross-linked polyurethane resins alter
the thermal and mechanical properties of the composites, compared to those of the pure
resins. The polymer’s viscous elastic characteristics changed accordingly to the mass
proportion of filler, showing increased modulus.
Small amount of filler can improve the damping properties without sacrificing the phase
continuity of the lot, but a large amount of filler phase decreases mechanical properties,
indicating large phase separation in the system.

ACKNOWLEDGMENTS

We acknowledge the financial support of this work by the Ministry of Education and
Research, CEEX Program – Grant No. X2C29.

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