Polymer Testing 21 (2002) 665–674

www.elsevier.com/locate/polytest
Material Properties
Correlation between degree of crystallinity, morphology,
glass temperature, mechanical properties and biodegradation
of poly (3-hydroxyalkanoate) PHAs and their blends
A. El-Hadi a, b,*, R. Schnabel a, E. Straube b, G. Müller c, S. Henning d
a
Department of Engineering Science, Institute of Process Engineering, Martin-Luther University of Halle-Wittenberg, Rheologie
Geusaer Strasse, 06217 Merseburg, Germany
b
Department of Physics, Martin-Luther University of Halle-Wittenberg, Halle-Wittenberg, Germany
c
Institute of Macromolecular Chemistry, Martin-Luther University of Halle-Wittenberg, Halle-Wittenberg, Germany
d
Institute of Polymeric Materials, Martin-Luther University of Halle-Wittenberg, Halle-Wittenberg, Germany

Received 18 January 2001; accepted 27 November 2001

Abstract

Bacterial thermoplastic polyesters poly (3-hydroxyalkanoate) PHAs are produced by the fermentation of renewable
materials, such as sugars or molasses. The pure homopolymer, PHB, and pure copolymer (3-HBP-CO-HV) (88:12) are
brittle materials. PHB or PHB/V are mixed with other biodegradable materials to improve their mechanical properties.
The aim is to develop biodegradable polymers of PHB-base with improved mechanical properties, such as fracture
stress (27–18 MPa), strain (400–660%), impact strength and long-term stability, and to compare them with PE, PP and
PET. When nucleating agents are added, smaller spherulites are formed, thus improving the mechanical properties. The
mechanical properties of PHB and its blends are related to processing conditions, morphology, crystallinity and glass
transition. The blends are ductile polymers with plastic deformation (necking). They are biodegraded in aerobic tests,
under compost conditions in soil and water, and many pores are to be found on the surface. The blends are degraded
more easily in the aerobic test, i.e. in the river water and compost, than in the soil.  2002 Elsevier Science Ltd. All
rights reserved.

Keywords: PHB; PHB/PHV; Their blends; Morphology; Stress–strain curves; Biodegradation

1. Introduction poor mechanical properties [4–10]. It exhibits good bar-

Poly-3-hydroxyalkanoate is linear polyester, produced
by many strains of bacteria in fermentation [1–3]. Its
chemical structure is: ⫺[O⫺CH(R)⫺CH2⫺(C ⫽ O)]n⫺,
with R=CH3 for PHB and R=C2H5 for PHV. PHB was
discovered in 1925 in the Lemoigne laboratory [3]. The
polymer is stored in cells of bacteria of up to 80% of its
dry mass and is a partially crystalline material [2]. PHB
is the only polymer from the group of PHAs to be pro-
duced in large quantities. Unfortunately, this polymer has
* Corresponding author. Fax: +49-3461-463-881.
E-mail address: el-hadi@physik.uni-halle.de (A. El-Hadi).
rier properties like PVC and PET [11], and can be used
in the packaging industry [12] as a biodegradable plastic
for solving environmental pollution problems.
There are many references to attempts to mix PHB
with other polymers with the aim of improving its mech-
anical properties — unfortunately with only limited suc-
cess so far [13]. With most polymers chemical incom-
patibility does not permit a good mixture. PHB is
miscible with poly (ethylene oxide) [14], poly
(vinylidene fluoride) [15], poly (vinyl acetate) [16,17],
poly (epichlorohydrin) [18], poly (methyl methacrylate)
[19,20] and poly (cyclohexyl methacrylate) [19]. PHB is
partially miscible with ethylene–propylene rubber [16],
ethylene–vinyl acetate copolymer [21], poly (vinyl

0142-9418/02/$ - see front matter  2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 4 2 - 9 4 1 8 ( 0 1 ) 0 0 1 4 2 - 8
666 A. El-Hadi et al. / Polymer Testing 21 (2002) 665–674
phenol) [22,23], poly (vinyl alcohol) [24,25], poly (L-
lactid) [26,27], synthetic poly (3-hydroxybutyrate) PHB
[28,29], poly (3-hydroxybutyrate) co poly (3-
hydroxyvalerate) [30] and poly (caprolactone) [31,32].
PHB or PHB/V are brittle materials and are not suitable
for technical applications, e.g. as films for deep drawing
articles or injection molding in food industries.
There are many reasons for the brittleness of PHB and
PHB/V. (i) The secondary crystallization of the amorph-
ous phase at ambient temperature takes place during stor-
age at room temperature [33]; (ii) the glass temperature
of PHB being close to room temperature; (iii) PHB has
a low nucleation density, therefore large spherulites exhi-
bit inter-spherulitic cracks.
Many authors [5,12,34] have examined secondary
crystallization, which appears during storage time at
room temperature. By addition of a nucleating agent, the
number of small spherulites increases. On addition of
plasticizers, the molecular motion is enhanced, and the
glass transition is lowered [34]. During processing, the
degradation of the chains may be reduced by the addition
of a lubricant, because PHB is sensitive to high pro-
cessing temperatures. This leads to a decrease in the mol-
ecular weight, as well as a reduction in the melt vis-
cosity. The crystallization temperature shifts to lower
values, and crystallization takes longer. To achieve high
elongation at break and a high degree of flexibility, the
glass temperature must be lower than the testing tem-
perature. The elongation and impact strength depend on
the glass temperature as well as the morphology. An
additive is mixed with the PHB matrix. Therefore, the
blends have a lower glass temperature (from ⫺38°C to
⫺12°C) than pure PHB (5°C), which could be observed
from measurements using DSC, DMA (⫺35°C
to⫺12°C), and DES. The new blends are easy to process
[35], and have a high impact resistance.
The aim of this work is to develop a biodegradable
polymer with a PHB base. The mechanical properties
correlate with the crystallization conditions, i.e., after
quenching from the melt, small-grain spherulites are for-
med, but when cooled slowly spherulites with large
cracks are formed. The influence of the morphology and
glass temperature on mechanical properties (elongation,
stress, impact strength) was investigated and the influ-
ence of aging on the mechanical properties was studied
in pure PHB, PHBV and their blends, after 1, 7, 30, 60,
90 and 120 days aging time, respectively.
2. Experimental
2.1. Materials
PHB in the form of a brown powder has a molar mass
Mw of 220 kg/mol. It has a melting point of about 173°C
and is 55% crystalline. It was supplied by COPERSU-
CAR from Brazil, and was produced by the fermentation
of molasses using Alcaligens euthrophus.
PHB in the form of a white powder has a molecular
weight of 230 kg/mol. It has a melting point of about
175°C, and is 60% crystalline. It was supplied by
BIOMER (Dr Haenggi), Krailling, Germany, and was
produced by the fermentation of sugar also using Alcali-
gens euthrophus.
A copolymer of PHB (88%)/PHV (12%) was supplied
by COPERSUCAR from Brazil. It was produced by the
fermentation of molasses using Alcaligens euthrophus. It
is a brown powder with a molar mass of Mw 240 kg/mol,
a melting point of about 165°C and is 45% crystalline.
2.2. Blend preparation
PHB in powder form was blended with additives by
mixing it in a Brabender (kneader) at 170°C–180°C and
50 rpm for 5 min or in a single screw extruder at a tem-
perature of between 145°C (zone 1), 160°C (zone 2) and
170°C (zone 3) with a 4 mm die and screw speed of 20
rpm. The strand (thread) was cooled in water and cut
with a pelletizer. The mixed material (granulates) was
compression molded in a hydraulically heated press at
170°C–180°C between two Teflon sheets and plates or
plaques of varying radii for 3 min without any pressure
and for 2 min with pressure (50 bar). After melting, the
sample was cooled with water between cold metal plates.
All additives are biodegradable substances. Plasticizers,
glycerol, tributyrin, triacetin, acetyltriethylcitrate, acetyl-
tributylcitrate and nucleation agent, saccharin, were
used. Lubricants were glycerolmonostearate, glyceroltri-
stearate, 12-hydroxystearate and 12-hydroxystearic acid.
The weight ratios of PHB to additives are listed in
Table 1.
2.3. Methods
2.3.1. Tensile testing
Tensile strength measurements, Young’s modulus and
elongation at break were determined with a mechanical
tensile tester (Zwick model 020) under a crossed-head
speed 50 mm min⫺1 at room temperature and at 60°C.
Five samples for each blend composition were tested
with different storage times at ambient temperature. The
correlation between strain (s in Pa) and elongation (e in
%) was determined.
s=E⑀, E=E-modules in MPa, e=(L0⫺L)/L, L0=origin
length, L=length after the elongation.
2.3.2. Impact resistance
The impact strength was determined for PHB and its
blends by using a Charpy test with a 4 J pendulum (ISO
179) at room temperature. The test pieces were in the
form of small injection molded bars with dimensions
length=80 mm, width=10 mm and thickness=4 mm (V-
 A. El-Hadi et al. / Polymer Testing 21 (2002) 665–674 667

Table 1
The blend preparations

Basic polymer Plasticizer Lubricant Nucleation Other polymer

1 PHB (82% wt) 11.5% wt Acetyltriethylcitrate 2% wt glycerolmonostearate 0.5% wt saccharin 4% wt PVAc

2 PHB (80% wt) 9.5%wt glycerol 2% wt glyceroltristearate 0.5% wt saccharin 8% wt PVAc
3 PHB (78% wt) 7.5% wt triacetin 2% wt 12-hydroxystearic acid 0.5% wt saccharin 12% wt PVAc
4 PHB (76% wt) 5.5% wt tributyrin 2% wt 12-hydroxystearate 0.5% wt saccharin 16% wt PVAc
5 PHB (74% wt) 3.5% wt tributyrin 2% wt 12-hydroxystearate 0.5% wt saccharin 20% wt PVAc
6 PHB/V (74% wt) 3.5% tributyrin 2% wt 12-hydroxystearate 0.5% wt saccharin 20% wt PVAc

notch with a notch radius of 0.25 mm and an angle of
45°). Five samples unnotched and five samples with
notches were tested after 120 days preparation (storage
at room temperature).
2.3.3. Differential scanning calorimetry (DSC)
The glass transition and melting temperatures were
recorded by using a Mettler Toledo DSC 820a Calor-
imeter. In the DSC, the samples were heated at a heating
rate of 10°C min⫺1 and cooled at 20°C min⫺1 in N2
atmosphere. The melting temperature and the enthalpy
of fusion were calculated from the maximum and the
area of the endothermic peak. The crystallinity was cal-
culated by
⌬H∗blends
Xc(PHB) ⫽ ⌬H∗PHB / ⌬H0PHB, Xc(blends) ⫽ , influence the size of the spherulites. The maximum strain
⌬H0PHB
⌬H0 (PHB) is the enthalpy of melting per gram of 100%
crystalline 164 J/g [6] and ⌬H∗PHB, ⌬H∗blend the measured
enthalpy of melting for PHB and blends.
2.3.4. Scanning electron microscopy (SEM)
A JEOL 6300 Scanning electron microscopy was used
to investigate the morphology, fractured surfaces and
biodegradation of the blends. The specimens were
sputter coated with gold.
2.3.5. Polarization optic microscopy (POM)
The morphology of PHB and its blends were observed
on thin films using an optical microscope (Jenapol) with
automatic hot stage (Mettler model FP 84), controlled by
a Mettler FP 90 control process. The samples between
two glass covers were heated at 195°C (2 min) with a
heating rate of 2°C min⫺1 from room temperature to
195°C and cooled at 10°C min⫺1 to crystallization tem-
perature.
3. Results and discussion
3.1. Morphology
DSC, POM and SEM were used to investigate the
glass temperature and morphology of PHB and its
blends. The influence of the morphology and glass tem-
perature on the mechanical properties of blends is dis-
cussed.
It is known that PHB is brittle and forms cracks [6,36],
therefore it cannot create necking, and cannot flow. By
adding nucleation agents, the number of large spherulites
is reduced, and the crystallization rate is increased [8].
Nucleation agents are small crystalline particles. They
are dispersed in the crystallizing melt and remain solid
at crystallization temperature, so a large number of small
crystals are formed around them. Big spherulitic
material, with the same percentage of crystallinity, is
more brittle than a fine spherulite. The size and number
of the crystalline structures influence the impact strength.
Nucleation agents and crystallization conditions can
decreases with an increase in the average size of the
spherulites. We measured the spherulite size by using
POM before deformation occurred.
The mechanical properties depend on the crystalliz-
ation procedure (quenching or slow cooling down). Dur-
ing fast cooling, the degree of crystallinity is lower, and
smaller crystallites are formed. During slow cooling
from the melt large spherulites are formed. Two types
of break were found in pure PHB spherulites; circular
breaks around the center and splitting [6,8,37]. PHB
forms individual large spherulites [38], which depend on
lower nucleation density but the blends have numerous
small, fine spherulites [8,34]. Figure 1(a) and (b) shows
PHB with large spherulites with cracks, and splitting
around the center. These large spherulites of PHB are
responsible for the poor mechanical properties [6]. Fig-
ure 1 shows isothermal crystallization of blend 4 in the
temperature range: 50°C–120°C. Figure 1(c)–(e) show
non-banded spherulites below 90°C as a fibrous texture
like PP and PEO. Figure 1 (i) shows that blend 4 spheru-
lites grow banded-spherulites above 100°C as a spiral
with twisting lamellae like PE, PPO, and PVDF. Owen
et al. [39] reported that the twist banding in PHB spheru-
lites is due to elastic banding radially oriented lamellae
ribbons, where the folding directions on opposite faces
of the lamellae are orthogonal and inclined in the radial
direction. This leads to the helical formation. Figure 1(h)
shows transcrystalline growth around a cellulose fiber.
668 A. El-Hadi et al. / Polymer Testing 21 (2002) 665–674

Fig. 1. Polarising optical micrographs after isothermal crystallization for PHB at (a) 100°C, (b) 90°C and blend 4 at (c) 50°C, (d)
80°C, (e) 85°C. Scanning electron micrographs of (f) blend 4 in the form of small injection molded bars at tool temperature 80°C,
(g) blend 6 at 40°C, (h) blend 4 with cellulose fibres crystallized at 25°C, (i) blend 4 crystallises at 120°C.
 A. El-Hadi et al. / Polymer Testing 21 (2002) 665–674 669

Figure 1(f) shows scanning electron micrographs of

blend 4 non-banded spherulites. Samples were prepared
in the form of small injection molded bars at tool tem-
perature 80°C.

3.2. Stress–strain behavior and impact strength

To improve the mechanical properties of products

from PHAs, their glass transition temperature must be
lower than the testing temperature. If the glass tempera-
ture is lower than the testing temperature, the mobility
of the chain segments increases and stress crazing
decreases. PHB has large E modulus (1700 MPa), yield
stress (35 MPa) and elongation (10%) (see Table 2). By
adding plasticizers, the rigidity of PHB is reduced, E-
modulus (743–250 MPa), yield stress (26–18 MPa) is
decreased, but elongation (150–660%) and the impact
strength is increased.
The stress–strain curves in Fig. 2 indicate that the pure
PHB and the pure copolymer are hard, brittle plastics,
but the blends are flexible, tough and ductile. The poly-
mer is designated as brittle, if the elongation, at break,
is ⬍20%. Figure 2(A) shows that the pure PHB/V after
1 h preparation has a high elongation (400%) [7,40], but
after 1-day preparation it has a much smaller elongation
[5,7]. The reason for this is secondary crystallization. Fig. 2. Tensile stress–strain curves for the various samples
During secondary crystallization, new, thin crystallites with strain rate 50 mm/min for (A) PHB/V after storage at room
were being formed in the amorphous region. Density, temperature as indicated. (B) Blend 4 after storage at 20°C for
times indicated.
crystallinity [5,9], stress and E-modulus increase, and
elongation at break decreases and the material becomes
hard and brittle. The maximum stress is always higher PHB/V as a function of storage time at room temperature
and the maximum elongation smaller. Figure 2(B) shows but their blends remain stable.
that the elongation increased from 10% (PHB) to We have examined the two types of PHB from mol-
⬎450% in blend 4. The initial section of the curve is asses and sugar by NMR and FT-IR; both polymers show
linear and the modulus E is determined from the slope. no chemical shifts. They are identical and have the same
As the stress is increased it reaches a maximum (yield peaks of NMR and FT-IR. The only difference is the
point), after which the sample begins to flow so that the colour [34], molasses based PHB is brown and contains
stress remains nearly constant up to high elongations. remains of molasses organic materials, and sugar based
Figure 3(A) shows the changes in elongation of PHB and PHB is white and filtered, but both polymers are brittle.

Table 2
Thermal and mechanical properties of PHB, PHB/V and their blends

Crystallinity % Glass Yield stress Elongation at Impact strength Impact strength E-modulus
temperature °C MPa break % notched without notch MPa
KJ/mm2

PHB 60 5 35 10 3 Break 1700

PHB/V 53 ⫺5 25 20 6 Break 1200
Blend 1 49 ⫺28 26 150 18 No break 743
Blend 2 46 ⫺24 24 230 20 No break 499
Blend 3 44 ⫺18 24 340 22 No break 459
Blend 4 42 ⫺16 25 450 26 No break 432
Blend 5 40 ⫺12 22 660 43 No break 250
Blend 6 36 ⫺25 18 500 25 No break 353
670 A. El-Hadi et al. / Polymer Testing 21 (2002) 665–674

Fig. 3. (A) Strain (%) versus storage time from aging PHB,
PHB/V and their blends. (B) Tensile tested for blend 4 (a)
before and after elongation of PHB-molasses, (b) before and
after elongation of PHB sugar basis.
Figure 3(B) shows tensile test pieces of blend 4 before
and after elongation, (a) molasses based PHB and (b)
sugar based PHB. Blend 4 gives the same values in the
tensile test with either molasses or sugar based PHB.
However, it can be noted that the biodegradation rate in
an aerobic test (see Table 3) is faster for molasses based
PHB because the bacteria feed on the remains of mol-
asses organic materials.
Figure 4(a) and (b) show that blend 4 and blend 6 after
elongation form fibril structures parallel to the stretching
direction. Shear yielding occurs in the form of homo-
geneous and continuous plastic deformation. Figure 4(c)
shows the fracture of blend 4 after breaking in liquid
nitrogen with strongly plastically deformed material
(fibrilled), i.e., the sample is ductile at lower tempera-
tures.
Figure 5(a) and (b) show the force (F) against deflec-
tion (f) curves from the impact tests at room temperature
with velocity of 1.5 ms⫺1 for blend 5 and PHB. PHB
has a small deflection (1.5 mm) but the blend reaches
4.5 mm. PHB is very brittle and the notched impact
strength is 3 kJ/mm2. The blends are ductile, elastic and
characterized by necking with notched impact strength
between 18–43 kJ/mm2. Table 2 also shows that the crys-
tallinity and glass temperature of blends is lower than in
pure PHB.
Ohlberg et al. [41] reported on crystallization studies
in HDPE and found that the impact strength decreased
with an increase in the size of the spherulites. Hummer
et al. [42] found that completely spherulitic films of iPP
cracked, but the smaller spherulites of incomplete
spherulitic films did not. Starkweather et al. [43]
observed that the impact strength decreased with an
increase in the crystallinity. Besselt et al. [44] investi-
gated the effect of structure and morphology on the
mechanical properties of dry nylon 6 (PA6). They found
that the behaviour depends on the degree of crystallinity,
and observed that the samples with higher crystallinity
(40%) were brittle, and the samples with 30% crystal-
linity were ductile. Way and co-workers [45] found that
spherulite size affects the deformation characteristics of
iPP; PP having the largest spherulites (250 µm diameter)
was more brittle than materials with fine spherulites (20
µm diameter). Ragosta and co-workers [46] investigated
the correlation of crystallization conditions, structure,
and impact strength, which decreased linearly with
increasing crystalline lamellae thickness in the case of

Table 3
The aerobic test for PHB and its blends

Type of sample Average BOD end COD end value g O2/g Biodegradation % Degradation time, days
value/mg polymer

PHB based molasses 310 1.1 70 60

PHB based sugar 321 1.2 66.9 60
Blend 1 based molasses 74.4 1.15 16.9 40
Blend 1 based sugar 63.5 2 9.1 40
Blend 2 based molasses 100.2 1.3 19.3 40
Blend 3 based molasses 340.2 1.8 44.8 50
Blend 4 based molasses 460.8 1.5 76.8 60
Blend 4 based sugar 495.1 1.8 68.76 60
 A. El-Hadi et al. / Polymer Testing 21 (2002) 665–674
Fig. 4. Surface structure of a cold drawn film of (a) Blend 4
registered with REM; (b) Blend 6 registered with REM; (c)
Ductile fracture-surface of Blend 4 registered with REM.
both annealed and non-annealed samples. They observed
that the crystallization temperature and lamellae thick-
ness increased by increasing the crystallization tempera-
ture. An increase in the lamellae thickness causes a
decrease in the number of inter-spherulites
3.3. Degradation test
3.3.1. Soil burial and compost condition
Biodegradation is promoted by enzymes and can occur
under aerobic or anaerobic conditions, leading to com-
plete or partial disintegration. Linear polymers are gener-
ally more biodegradable than branched polymers. Biode-
gradability of PHB [47–50] has been examined in
various environments such as in soil, river water and sea-
671
Fig. 5. Dependence load (F)–deflection (f) curves recorded in
the instrument at room temperature in linear elastic unstable
velocity 1.5 ms⫺1 for (a) blend 5, (b) PHB.
water [47]. The rate of enzymatic degradation decreases
with an increase in crystallinity [51], crystal size [52,53]
and glass temperature [54]. Enzymatic degradation of
ductile materials is faster than for higher crystallinity
material [51]. Mixtures of PHB with poly (ε-
caprolactone) PCL are biodegradable [55] as are mix-
tures of PHB with polyethylene oxide PEO [54] and
polyvinylalcohol PVA. PVAc is not water-soluble and
biodegrades slower than polyvinylalcohol [47,56–61] but
it is converted to PVA through hydrolysis.
Doi and his co-workers [55] have found that
PHB/25% PVAc is biodegradable. Biodegradation
depends on the microbes, pH, temperature and moisture
in the environment and on glass temperature [54] and
crystallinity [51] of the plastic. PHB blends will be
degraded in the composting process through micro-
organisms to carbon dioxide and water. The degradation
rates in compost conditions are generally higher than in
natural conditions because of higher temperatures in
compost.
The biodegradation of blend 5 was observed in com-
post. The samples were in the form of thin films about
200 µm thick, prepared by hot pressing at 170°C and
50-bar pressure. After composting, the sample was
washed with distillated water and observed with a scan-
672 A. El-Hadi et al. / Polymer Testing 21 (2002) 665–674

ning electron microscope. Figure 6(e) and (f) shows the
surface of blend 5 film before and after degradation. The
surface of the blend is strongly eroded; only a few areas
of original, non-degraded material was found. Pores of
1–5 µm are formed and the degradation results in a very
rough topography creating larger surface area, which
helps microorganisms to colonize. The specimen was
covered with dirt (EDX spectrum: Si, Al, Na, Mg, Cl,
K, Ca from soil mineral) and soil microorganisms. It
could be the aim of further investigations to identify the
biological items found on the surface. However, in the
densely populated areas we found hypha of fungi, bac-
teria and others. There is evidence that microorganisms
are able to enter larger pores (10 µm, Fig. 6(a) and (c)).
3.3.2. Test in river water
The surfaces of the water-stored specimens were
almost completely covered with organic and inorganic
debris (Fig. 6(d)). The degraded surfaces, where visible,
seem to have undergone degradation very similar to that
in the soil burial test. Pores were found having typical
sizes of several microns. The overall impression is that
the degradation rate is higher than in soil burial tests.
Drying (SEM preparation process) causes shrinkage and
cracks are created. There are densely populated areas
where bacteria formed a layer of organic material cover-
ing the surface completely (Fig. 6(b)). Several non-ident-
ified microorganisms, including algae, were found.

Fig. 6. Scanning electron micrographs of blend 6 film, photos (a), (b) and (c) in the soil after degradation after 5 weeks, (d) water
degradation after 5 weeks, (e) Environment Scanning Electron Microscopy (ESEM) of blend 4 in the compost condition after 3
months, (f) blend 4 before degradation.
 A. El-Hadi et al. / Polymer Testing 21 (2002) 665–674
3.3.3. Aerobic test
We can evaluate the aerobic biodegradability of
organic compounds in an aqueous medium by determi-
nation of oxygen demand in a closed respirometer (ISO
9408:1999). The aqueous medium contains phosphate
buffer (5:1). Bottles were filled with 250 ml of aqueous
medium mixed with PHB or the blends (100 mg) and 10
mg of microbial matter from sewage sludge. We calcu-
lated the degradation rate=BOD/COD×100 from the bio-
chemical oxygen demand (BOD) as a function of theor-
etical oxygen demand (ThOD) or chemical oxygen
demand (COD). Table 3 shows the biodegradability for
PHB and its blends. The degradation after longer time
(60 days) is faster than at shorter time (40 days).
4. Conclusions
1. PHB is a hard and brittle polymer, its elongation at
break is less than 10%, its modulus and fracture stress
are 1.7 GPa and 35 Mpa, respectively. PHB/V is also
brittle, its elongation at break is less than 15%, its
modulus and fracture stress are 1.2 GPa and 25 MPa.
PHB blends or PHB/V blends are ductile, necking,
elastic, flexible and tough polymers, which can
undergo extensive plastic deformation with elong-
ation at break from 400 to 600% and a fracture stress
of 26–18 MPa.
2. The addition of plasticizers and nucleation agents
leads to a lower glass temperature and lower crystal-
linity. Numerous, small and imperfect crystallites are
formed. Therefore, the impact strength and the elong-
ation at break increases and the yield stress is
reduced. This is necessary for applications in the
food industry.
3. The biodegradability of blends was investigated in
composting conditions in river water, the soil and in
an aerobic test. The degradation rate in the aerobic
test, in water and composting conditions is higher
than in the soil. All surfaces are covered in mineral
particles and microorganisms.
Acknowledgements
The authors wish to thank the German Research Coun-
cil (DFG) for their generous financial support in the form
of a Ph.D. grant, and Dr Stoll for the useful discussions.
The authors also wish to thank Dr Trempler and Dr
Hahne for polarization microscopy measurements, and
Mrs Otto for organizing the experiments for degradation
tests with compost conditions, Dr Jank for the aerobic
test and Dr Roeder for ESEM investigations.
673
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