Powder Metallurgy Progress, Vol.11 (2011), No 3-4
290
PREPARATION AND CHARACTERIZATION OF
POLYURETHANE - Fe POWDER COMPOSITES
M. Špírková, R. Bureš, M. Fáberová, M. Trchová, A. Strachota, L. Kaprálková
Abstract
A series of organic-inorganic composites in the form of films was
prepared. The organic polymeric matrix was formed from the commercial
product KRASOL LBH P (linear liquid polybutadiene terminated with
primary
hydroxyl
groups),
aliphatic
diisocyanate
(1,6hexamethylenediisocyanate), and 1,4-butanediol. Powder iron (ASC
100.29) of micrometre size formed the inorganic part of the composite (5
to 80 wt. %). It was found that Fe content considerably influences
mechanical, thermomechanical and surface properties, as detected by
tensile tests, dynamic mechanical thermal analysis and hardness
measurements. While pure organic matrix is typical elastomeric,
qualitatively different mechanical properties were detected for composites
containing more than 30 % of Fe. Bimodal character of Fe area fraction,
hardness and resistivity vs. Fe content dependences were found.
Keywords: polyurethanes, polybutadiene diol, Fe powder, organicinorganic composite
INTRODUCTION
Polyurethane (PU) systems are characterised by extensive range of end-use
properties (e.g., densities, hardness, stiffness). They are used in building, transportation,
furniture (bedding) and footwear in the form of foams (flexible, semi-rigid, rigid), soft solid
elastomers or hard solid plastics [1]. The most common polyurethanes (PUs) are based on
polyether (PE) or polyester (PES) polyols and aromatic di- or poly- isocyanates.
Polybutadiene- (PB) or polycarbonate- (PC) based polyols belong to the group of specialty
polyols due to enhanced end-use properties of PB-PUs and PC-PUs compared with PE-PUs
and PES-PUs [1,2,3]. For example, PB-PUs exhibit superior water-resistant properties, high
elasticity, very good low-temperature characteristics, excellent insulation characteristics
and superior resistance. They are useful mainly in special applications like in encapsulation
of electronic components [1]. PB-PU elastomers exhibit also outstanding resistance to
aggressive aqueous media (acidic and alkaline solutions) [4].
This paper presents our preliminary results of study of novel PU composites made
from PB-based macrodiol, aliphatic diisocyanate, 1,4-butanediol and micrometer-size Fe
powder. Dibutyltin dilaurate was used as a catalyst and one-stage procedure was used in all
cases. As all films were prepared by an identical procedure, the influence of Fe
concentration on structure and surface properties could be tested.
Milena Špírková, Miroslava Trchová, Adam Strachota, Ludmila Kaprálková, Institute of Macromolecular
Chemistry ASCR, Nanostructured Polymers and Composites Department, Prague, Czech Republic
Radovan Bureš, Mária Fáberová, Institute of Materials Research, Slovak Academy of Sciences, Košice, Slovak
Republic
Powder Metallurgy Progress, Vol.11 (2011), No 3-4
291
EXPERIMENTAL
Chemicals
Polybutadiene diol, α,ω-di(2-hydroxyethyl)-polybutadiene [Krasol LBH-P 2000
(LBH-P)], kindly provided by Kaučuk, now Synthos Kralupy), 1,-6 hexamethylene
diisocyanate (HDI; Fluka), butane-1,4-diol (BD, Fluka), dibutyltin dilaurate (DBTDL;
Fluka), and Fe powder (ASC 100.29, Hoganas AB Sweden) were used as received.
Characteristics of LBH-P: Mn 2194; water content: 0.01 wt. %, OH value: 48.98 (0.873
meqiv OH /g), viscosity at 25 o C: 11640 mPa.s.
Polyurethane composite film preparation
As this study is of a preliminary character, all films were prepared without any
solvent by one-step procedure in order to gain basic information about the character of the
organic-inorganic (O-I) composites compared with pure PU matrix. Macrodiol, BD (chain
extender) and Fe powder were mixed and degassed. Finally, HDI and DBTDL (1 %
DBTDL in oil Marcol) were put, the mixture was degassed and spread on modified
polypropylene sheet at constant layer thickness (500 μm) using a ruler. Samples were kept
in the inert milieu at 90 °C for 24 h. Ratios ([OH]macrodiol/[OH]extender = 1.0 and
[NCO]/([OH]macrodiol + [OH]extender) = 1.05) were used in all cases. Catalyst concentration,
cDBTDL, was equal to 0.001 wt. %. Fe powder concentration was up 80 wt. %.
Methods of characterization
ATR FTIR
ATR FTIR spectra were measured using a Thermo Nicolet Nexus 870 FT-IR
spectrometer (Madison, WI, USA) in an H2O-purged environment with MCA detector. The
Golden GateTM single reflection ATR system (Specac Ltd., Orpington, Great Britain) was
used to measure the ATR spectra of samples over a wavelength range of 400–4000 cm–1.
Typical parameters were: 256 sample scans, resolution 4 cm-1, Happ-Genzel apodization,
KBr beamsplitter.
Tensile characterization
Static mechanical properties were measured on an Instron model 5800 (Instron
Limited, UK). Specimens with gauge length 25 mm were tested at 23 °C at a test speed of
0.17 mm.s-1. The reported values are averages obtained from at least five specimens.
Dynamic Mechanical Thermal Analysis (DMTA)
DMTA was carried out on ARES-LS2 from Rheometrics Scientific (now TA
instruments) using an oscillation frequency of 1 Hz, deformation ranging automatically
from 0.01% (glassy state) to 3.5% (maximum deformation allowed), over a temperature
range of – 100 to 120°C, at a heating rate of 3°C/min. The standard specimens dimensions
were 25 mm x 8mm x 0.5 mm. Storage modulus (G‘), loss modulus (G‘‘) and loss factor
(tan δ, tan δ = G‘‘/G‘) were measured. In this work, the glass transition temperature, Tg,
was defined as (tan δ) maximum.
Metallography and image analysis
Inverted metallographic Microscope Olympus GX 71 equipped with the polarizer
was used for qualitative and quantitative metallograhic analysis and 12 Mpix camera
Olympus DP12 for image acquisition. Software ImageJ [5] and Statistica 7 were used for
Image analysis, quantitative metallography and statistics evaluation.
Powder Metallurgy Progress, Vol.11 (2011), No 3-4
292
Hardness
Hardness tester HPO 250 with Vickers indentor was used to measure relative
hardness of the composites. Two values of relative hardness HV5 and HV10 were
measured according to STN EN ISO 6507/1 standard.
Electric properties
Resistivity of composites was measured using Teraohmmeter Sefelec M1501P.
Area of electric contacts was circular with diameter 10 mm. Measurement range from 4 kΩ
to 2.1015 Ω or from 0.01 pA to 20 mA in regime of picoammeter. Measurement voltage was
adjustable volt by volt from 1V to 1500VDC. Measurement speed was selectable from 1 to
10 readings/s.
RESULTS AND DISCUSSION
ATR FTIR
ATR FTIR spectra were measured on the pure PU matrix, and on PU O-I
composites containing 5 to 80 wt. % of Fe powder. ATR FTIR spectra are shown in the
Fig.1, where two distinct dependences (of very similar shape within this type) are very well
visible: one type is detected for the pure PU matrix and for composites with Fe contents up
to 30 wt. %, and the other was distinguished for composites containing 40 to 80 wt. % of
iron. FTIR results strongly support the results of other analytical methods, especially
mechanical analysis; see later.
ATR FTIR
PU_Fe
Absorbance
Fe [%] =
80
70
60
50
40
30
20
10
5
0
4000 3500 3000 2500 2000 1500 1000
-1
Wavenumbers, cm
Fig.1. ATR FTIR spectra of PU-Fe composites (Fe contents is given directly in the Fig.;
left).
Powder Metallurgy Progress, Vol.11 (2011), No 3-4
293
Tensile properties
Tensile properties of the neat PU and PU-Fe films were measured. Stress-at break,
σb, elongation-at break, εb, Young modulus, E, and toughness (expressed as the energy
necessary to break the sample) were measured, and they are given in Table1.
Tab.1. Tensile properties of PU-Fe composites
Code
PU-0Fe
PU-5 Fe
PU-10 Fe
PU -20 Fe
PU-30 Fe
PU- 40 Fe
PU- 50 Fe
PU- 60 Fe
PU- 70 Fe
PU- 80 Fe
Stress-atbreak [MPa]
4.17
3.31
4.55
3.29
3.04
14.8
32.0
24.8
17.8
13.3
Elongation-atbreak [%]
639
597
550
296
225
2.17
3.94
2.64
2.14
1.79
Young modulus E
[MPa]
1.45
1.30
1.66
2.76
3.47
1390
1266
1624
1231
1010
Toughness
[mJ/mm3]
19.84
14.80
16.11
8.89
5.71
0.17
0.79
0.42
0.24
0.14
In accordance with FTIR results, two regions of tensile characteristics are
detectable: (i) PU matrix and samples with Fe content ≤30% exhibiting elastomeric
character of the neat PU and PU composites: εb is of 102 % order, σb or E are of 100 MPa
orders, which leads to toughnes of 100 to 101 mJ/mm3; and (ii) PU composites containing ≥
40 wt.% of Fe are characterised by a dramatic εb decrease, substantial E increase (three
orders of magnitude), ca 5 times σb increase, but at the same time radical εb decrease (two
orders of magnitude) compared with composites containing ≤30% wt.% of Fe.
Dynamic mechanical thermal analysis (DMTA)
Thermomechanical properties were tested by DMTA. Figure 2 shows temperature
dependences of storage shear modulus G’ (Fig.2 a) and tan δ (Fig.2b). Similar to results
given by other methods used for PU-Fe composite characterization, two regions are well
detectable: samples with lower Fe content ( ≤30 wt. %) featuring by Tg between -20 and -30
o
C, while composites with higher Fe contents (up to 50 %) are characteristic by Tg at
temperature over 50 oC, whereas samples contaning 60 and more % of Fe are without any
characteristic (tan δ) peak in the temperature scale from -100 to 120 oC.
Powder Metallurgy Progress, Vol.11 (2011), No 3-4
294
1.E+11
1.E+10
60
shear modulus G'
[Pa]
70
80
50
1.E+09
40
20, 30
1.E+08
10
0
1.E+07
1.E+06
-100
-50
0
50
100
Temperature [°C]
1.2
1
50
tan(delta) [1]
0.8
20,
30
0, 10
40
0.6
60
0.4
70
80
0.2
20,
30
0
-100
-50
0, 10
0
50
100
Temperature [°C]
Fig.2. Storage modulus (a) and tanδ (b) vs. temperature dependences for PU-FE
composites. (Fe content in % is given directly in the Figure).
150
Powder Metallurgy Progress, Vol.11 (2011), No 3-4
295
Microstructure analysis
PU-Fe composites were cut to a cylindrical shape of diameter 10 mm and fixed in
epoxy resin, then ground on SiC and polished using spray with polycrystalline diamond
0.25 μm size.
Samples were observed in normal and polarised light to evaluate planar
distribution of Fe particles and pores. Acquised images in Fig.3 were processed using
image analyzer to remove the noise, image optimisation and measurement. Area fraction,
size and shape characteristics of iron particles were evaluated (Tab.2). Statistic analysis of
measured characteristics in Fig.4 showed that PU-Fe composite exhibits two types of
microstructure- Fe content dependences. Transition between microstructure of ‘PU matrix’
and ‘Fe matrix’ in composites is not smooth. There are two peaks in statistical distribution
of size and shape characteristics. Planar distribution of Fe indicates the same tendency, as
shown by changes in area fraction of Fe on metallographic sample surface. The distribution
of Fe particles in the composites is homogenous up to 30 wt. % Fe. Iron particles are
distributed as aglomerates in the case of high content of Fe 60-80 wt. %. Distribution of Fe
phase is heterogeneous, but distribution of the iron aglomerates is homogeneous. The most
heterogeneous microstructure from the view point of Fe distribution was observed in
composites with content 40-50 wt.% of Fe.
20 % Fe
20 % Fe polarised
30 % Fe
30 % Fe polarised
40 % Fe
40 % Fe polarised
50 % Fe
50 % Fe polarised
60 % Fe
60 % Fe polarised
70 % Fe
70 % Fe polarised
80 % Fe
80 % Fe polarised
PU-matrix
Fig.3. LOM Images of PU-Fe composites observed in normal and polarised light.
Powder Metallurgy Progress, Vol.11 (2011), No 3-4
296
Tab.2. Size, shape and planar distribution characteristics of Fe particles in composite
Sample
PU-20Fe
PU-30Fe
PU-40Fe
PU-50Fe
PU-60Fe
Area Fraction [%]
Feret diameter [μm]
Circularity
Powder Metallurgy Progress, Vol.11 (2011), No 3-4
Sample
Area Fraction [%]
Feret diameter [μm]
297
Circularity
PU-70Fe
PU-80Fe
Hardness
Hardness was measured for fast information about properties of prepared PU-Fe
composites. It is not possible to compare values of hardness with other metallic materials
due to a very high elastic deformation and relaxation of (polymeric) PU matrix. However,
the measurement of the relative hardness is a useful when comparing changes of surface
hardness properties in in relation to Fe content, as shown Table 3. It is evident that values
of relative Vickers hardness increase with increasing Fe content, with two step changes:
between 20 and 30 wt. % of Fe, and between 30 and 40 wt. % of Fe. The values of standard
deviation in Table 3. validate sufficient accuracy of the hardness measurements.
Tab.3. Relative Vickers hardness of PU-Fe composites.
Sample
HV5
HV10
PU-0 Fe
30.82
PU-5Fe
31.4
PU-10Fe
19.99
PU-20Fe
27.67
PU-30Fe
64.18
PU-40Fe
140.70
PU-50Fe
141.70
PU-60Fe
181.10
PU-70Fe
190.20
PU-80Fe
248.80
HV5 and HV10 – mean values calculated from 11 measurements
Standard deviation
0.8108
0.5147
0.9279
3.6188
2.2024
5.9451
4.7621
5.4457
1.8135
6.9410
Resistivity
Values of resistivity measured at voltage 10 V, dwell time 600 sec. are shown in
Table 4.
Sample thickness was measured after 600 s after applying pressure to the holder,
because the pressure of the clamp holder on the composite caused thickness changes during
Powder Metallurgy Progress, Vol.11 (2011), No 3-4
298
measurement. Dimensional changes influenced by density and resistivity of composite were
tested. In general, expected could be monotonic decreasing function of resistance on Fe
content. It was found that measured dependence resulted in two maxima, similary as in the
case of metallografic analysis (Fig.4).
Tab.4. Resistivity of PU-Fe composites
Sample
Thickness
[mm]
Resistance
[TΩ]
PU
0.442
2.06
PU-5Fe
0.141
0.224
PU-10Fe
0.413
2.450
PU-20Fe
0.582
0.601
PU-30Fe
0.478
0.594
PU-40Fe
0.389
0.597
PU-50Fe
0.248
1.411
PU-60Fe
0.372
0.978
PU-70Fe
0.399
0.814
PU-80Fe
0.468
0.0342
*
Resistance normalised to thickness 100 μm
*
Normalised
Resistance
[TΩ]
0.466
0.159
0.593
0.103
0.124
0.153
0.569
0.263
0.204
0.007
Specific
Resistivity
[Ωm]
3.659 E11
1.247 E11
4.657 E11
8.106 E10
9.755 E10
1.205 E11
4.466 E11
2.064 E11
1.601 E11
5.737 E9
Fig.4. Trend curves of dependence of evaluated properties on Fe content: area fraction of
Fe(a), hardness (b), resistivity(c).
The tendency to multimodality of relation between selected characteristic of
composite and Fe content is documented in Fig.4. Curves of area fraction of Fe (a),
hardness (b) and resistivity (c) vs. Fe content are bimodal. First peak is related to ‘PUmatrix composite’ and second one corresponds with composition of ‘Fe-matrix composite’.
Powder Metallurgy Progress, Vol.11 (2011), No 3-4
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Transition between the composite structures is not smooth and it is accompanied by step
change of the properties, as evident from tensile, DMTA and microstructure analysis.
CONCLUSIONS
The series of novel PU-Fe composites with content of Fe from 5 to 80 wt. % was
prepared in the form of free-standing films. Analyses of mechanical and electrical
properties indicate two typical combinations of properties of the investigated composite.
Low contents of Fe up to 30 wt.% lead to elastomeric composite with homogeneous
distribution of iron particles and lower content of small bubles (‘PU-matrix composite’).
These composites exhibit high specific resistivity, high ductility, high toughness and
relative low hardness and low tensile strength. Contents about 70 to 80 wt. % of iron lead to
agglomeration of Fe in composites (‘Fe-matrix composite’). Hardness and strength of these
composites are higher, specific resistivity is also high, while ductility and toughness rapidly
decrease. Mixed microstructure with Fe particle and Fe aglomerates was observed in the
range between 30 and 60 wt.% of Fe content, as proved by statistic image analysis of these
composites. Transition microstructure causes anomalous changes in properties of PU-Fe
composites.
Acknowledgement
Presented results were obtained within the work on the projects P108/10/0195
(Grant Agency of the Czech Republic; IMC) and VEGA 2/0149/09 (IMR).
REFERENCES
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vol. 77, 2000, no. 2, p. 381
[3] Špírková, M., Pavličević, J., Strachota, A., Poreba, R., Bera, O., Kaprálková, L.,
Baldrian, J., Šlouf, M., Lazić, N., Budinski-Simendić, J.: J. Eur. Polym. J., vol. 47,
2011, p. 959
[4] Pytela, J., Sufčák, M. In: Proceedings of the International Polyurethane Industry
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http://imagej.nih.gov/ij/, 1997-2011
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