Polymer Degradation and Stability 95 (2010) 1276e1283

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Polymer Degradation and Stability

journal homepage: www.elsevier.com/locate/polydegstab

Biomass carbon ratio of polymer composites included biomass

or petroleum origin resources
Toru Onishi a, Fumi Ninomiya a, Masao Kunioka a, Masahiro Funabashi a, *, Keiichi Ohara b
a
b

Research Institute for Innovation in Sustainable Chemistry, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
Institute of Accelerator Analysis, Ltd. (IAA), Shirakawa Analysis Center, 6-270 Ichiridan, Shirasaka, Shirakawa, Fukushima 961-0835, Japan

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 30 December 2009
Received in revised form
5 March 2010
Accepted 9 March 2010
Available online 17 March 2010

The biomass carbon ratios of various polymer composites were studied. The biomass carbon ratios of
polymer composites were estimated by the ratios of 14C to 12C measured by accelerator mass spectrometry (AMS) based on ASTM D 6866-08. The pretreatment conditions of the polymer composite of
each constituent for the AMS measurement are described. The repeatability and accuracy of the biomass
carbon ratio evaluation by AMS for the polymer composites with an inorganic ller, which are biomassbased plastics with mineral calcium carbonate and petroleum-based plastics with biobased calcium
carbonate, such as shell powder or an organic ller, are discussed. The standard deviation of the polymer
composite was less than 1%, and it was sufciently lower compared with the limit of the AMS
measurement (0.12%). Also, the biomass carbon ratio of each constituent of the polymer composite
including the inorganic ller was signicant based on the AMS measurement by changing the
pretreatment conditions.
2010 Elsevier Ltd. All rights reserved.

Keywords:
Polymer composite
Calcium carbonate
Cellulose
Biomass carbon ratio
Accelerator mass spectrometry
Repeatability

1. Introduction
The plastics product that we are using is not made from a simple
substance, such as only pure plastics resin. It is because various
additives are added to obtain stability during long-term use. Based on
circumstances, it may be when about 50% of the total weight of the
product is an additive [1]. Many plastics are chiey produced with
petroleum though the plastics product is used in various industrial
elds. A plastics product is difcult to dispose of after its use due to its
resistance to corrosion. Currently, plastics use petroleum for the
feedstock, and also use petroleum for the manufacturing energy. The
use of petroleum is decreased by producing plastics products using
biomass feedstock that has assimilated carbon dioxide, and the total
abatement of carbon dioxide emissions from biomass used in plastics
production is expected.
As for plastics products produced by biomass, various materials
are now reported in the commercial market. Poly(lactic acid)
(PLA) is a typical biodegradable polymer synthesized by using
lactic acid from biomass starch, therefore this polymer is made
from a renewable source. The production of PLA is done at the
mass production plant of NatureWorks in the US [2]. The life cycle
assessment (LCA) of PLA is an analytical tool concerning the
* Corresponding author.
E-mail address: m.funabashi@aist.go.jp (M. Funabashi).
0141-3910/$ e see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2010.03.011

potential decrease in fossil energy use and the emission of greenhouse gases. LCA shows that the processes of PLA production can
become both fossil energy free and a source of more carbon credits
compared to conventional petrochemical based polymers [3].
The trade name TERRAMAC from a Japanese Company is applied
to packaging lms, sheets or bers, such as nonwoven cloths
[4]. The composite of PLA resin with a natural ber has also been
investigated, and the mechanical property of this composite is
promising [5e8]. There is a biodegradable plastics that a microorganism synthesizes called poly(hydroxyl alkanoic acid) (PHA) [9].
Many kinds of monomer units can be produced depending on
the carbon source and fermentation conditions. The composites
mixed with these microbial polyesters and natural bers have
been investigated [10e12]. The mass production of PHA is starting
in the US [13]. The life cycle inventories of energy consumption and
carbon dioxide emission of the biobased PHA are signicantly
lower than those of typical petrochemical plastics [14]. Besides,
bio-polyethylene will be made from the bio-ethanol produced from
sugar cane in Brazil [15]. A lm by ination formed petroleumbased polyolen with old rice powder, which is waste after storage,
and a food grade tray from a compound of polypropylene that
contains rice and wood powder are being made [16]. A composite of
polypropylene or biodegradable plastics (PLA or poly(butylene
succinate)) with scallop shell have been investigated in Hokkaido,
Japan [17,18].

T. Onishi et al. / Polymer Degradation and Stability 95 (2010) 1276e1283

The product of biomass origin and the product of petroleum

origin are indistinguishable, because it is not possible to
distinguish the physical chemical properties that are different in
biomass-based plastics which have are completely the same
molecular structure from petroleum-based plastics. Therefore, to
attempt improving the general consumers acknowledgment
level and promote for biomass plastics, the Japan Bioplastics
Association (JBPA) is managing the BiomassPla mark certication system as an identication system of products of biomass
origin. Under this system, the products that meet the stipulated
standards are certied as BiomassPla and are permitted to use
the BiomassPla logo shown in Fig. 1. The degree of biomass
plastics in a product shall be a plastics product of 25.0 wt% or
more in one of the authentication conditions of the abovementioned system. The degree of biomass plastics is the ratio of
the biomass origin constituent of the biomass plastics chemical
composition [19].
For measurement of the biomass origin component, there is
a measurement of the biomass carbon ratio by 14C radiocarbon
concentration measuring methods based on ASTM D6866-08 [20].
The 14C concentration is measured by accelerator mass spectrometry (AMS) and a liquid scintillation counter. Measuring of the 14C
radiocarbon concentrations using AMS is based on the age determination used in archeology (carbon dating). 14C is a radioisotope of
carbon atoms with a half-life time of 5730 years. 14C atoms are
continuously generated from 14N because of the interaction with
the cosmic radiation in the modern atmosphere. The carbon in
a biomass made from the atmosphere includes a small amount of
14
C. The ratio of 14C to 12C in modern air is a constant of ca.1
1012
in spite of the time period. In contrast, the carbon from a fossil
contains essentially no radiocarbons. It is then understood that the
ratio of 14C/12C for petroleum carbon is 0. Therefore, the biomass
carbon ratio can be determined by measuring the 14C/12C ratio of
a plastics product. It is applied to the combustion gas measurement
of a boiler, and it can be conrmed by this method that the biomass
waste was burnt [21]. This method can also be applied to a plastics
composite [22e27].
In this study, to separately measure the biomass carbon ratios
of plastics resin and additives in the plastics product, the
pretreatment method of the 14C radiocarbon concentration
measuring methods by the accelerator mass spectrometry was
discussed in detail. The biomass carbon ratio of each constituent
was measured by changing the pretreatment conditions of the
AMS for the composites of the petroleum-based polypropylene
with cellulose or biomass-based calcium carbonate (shell
powder), petroleum-based poly(butylenes succinate) with cellulose, and biomass-based poly(lactic acid) with mineral calcium
carbonate. In addition, the accuracy was conrmed based on the
repetitive measurements under the different conditions to
conrm the adaptation for the International standard (ISO) evaluation method.

1277

2. Experimental
2.1. Materials
Poly(lactic acid) (PLA) (TERRAMAC TE-2000) from Unitika Co.
was used as received. Polypropylene, isotactic (PP) (Mn 67,000) and
poly(1,4-butylene succinate) extended with 1,6-diisocyanatohexane (PBS) were used as received from SigmaeAldrich. Cellulose
microcrystalline powder (Avicel) from Merck KGaA was used as
received. Cellulose (qualitative lter paper) from Whatman was
used as received. Powders of calcium carbonate from shells and
limestone were employed. Calcium carbonate (CaCO3) from shells,
Gofun, which is used as a coloring for Japanese paints, from Matsujirushi, Nakagawa, were used as received. Guaranteed reagent
grade mineral calcium carbonate from Kanto Chemical Co., Inc., was
used as received.
2.2. Crushing of polymer pellets
The polymer pellets were crushed into powders. These samples
were crushed by a mechanical mixer along with crushed dry ice.
One cycle was a 3-min crushing and ten cycles of crushing for each
sample with a 1-min interval. The crushed powders were separated using a 125 mm mesh sieve. The powders under the 125 mm
size were dried in a vacuum oven and used for the sample
preparation.
2.3. Sample preparation of polymer composites
(PP or PBS/cellulose, PP or PLA/CaCO3)
Fig. 2 shows the polymer composite preparation method. The
polymer composites were prepared by the hand mixing of the
polymer and additive powders using a mortar and pestle for
5 min. The determined polymer powders and cellulose or calcium
carbonate llers were mixed. The mixture (ca. 7 g) was then
placed in a stainless mold (10
10
0.05 cm). The mold was
placed on a hot plate and heated. After the temperature of the hot
plate of reached 160e200  C, the mold was pressed at 20 MPa for
5 min.

Polymer pellets
a) Polypropylene (PP) (petroleum origin)
b) Poly(butylene succinate) (PBS) (petroleum origin)
c) Poly(lactic acid) (PLA) (biomass origin)

Crushing
by mechanical mixer along with dry ice

Polymer powder
1. cellulose powder

Filler

2. cellulose (filter paper)

3. calcium carbonate (shell powder)
4. calcium carbonate (mineral)

Mixing
i ) Cellulose powder (biomass origin) with PP
ii ) Filter paper (biomass origin) with PBS
iii ) Calcium carbonate (biomass origin) with PP
iv ) Calcium carbonate (mineral origin) with PLA

Hot press
Hot press at 160 - 200 oC and 20 MPa for 5 min

Sample sheet
Fig. 1. BiomassPla mark in BiomassPla Certication System organized by Japan
BioPlastics Association (JBPA).

Fig. 2. Sample sheet preparation method for polymer composites with organic or
inorganic ller.

1278

T. Onishi et al. / Polymer Degradation and Stability 95 (2010) 1276e1283

2.4. Sample preparation of solid materials for biomass

carbon ratio measurement
The sample preparation and AMS measurements were performed at the Institute of Accelerator Analysis, Ltd. (IAA), Japan, as
shown in Fig. 3. All the carbon atoms in the samples were transformed into graphite carbons by serial oxidation and reduction
reactions using a quartz glass tube and a vacuum manifold system.
The composite sample was made into a powder by freeze shattering
in the case of the H3PO4 reaction for a polymer composite with
calcium carbonate to develop the contact between the calcium
carbonate powder and H3PO4 liquid. The sample (ca. 4 g) was
placed in a container (ca. 10 mL) with a stainless cylinder piece,
which is the freeze shattering apparatus. The assembled container
with the sample was then put in liquid nitrogen for about 30 min,
freezing the sample. The container was repetitively hit at the
rubber board, and it was crushed for 15 min. The powder samples
were used without undergoing this powder making process.
Two kinds of pretreatment conditions were applied to the
powder samples. These samples of 3e50 mg were placed in a quartz
glass tube with 1 g of copper oxide (CuO), connected to a vacuum
line system, then the quartz glass tube was closed. The samples in
the tube were oxidized at 500  C for 30 min and at 850  C for 2 h.
Another method was the oxidizing reaction that used the elemental
analysis apparatus at 980  C or 500  C. For the oxidation reaction at
980  C or 500  C, the sample powders of 4e20 mg were oxidized
using the elemental analysis apparatus. Helium gas (He) was the
carrier gas for the elemental analyzer. Oxygen gas (O2) ows only
when the sample is burnt. The element in the sample that is gasied
is separated by the column. The evolved carbon dioxide was then
cold-trapped. The collected carbon dioxide by pretreatment with
ferrous (Fe) powders was reduced to graphite at 650  C in 10 h by
a deoxidization reaction. After these procedures, the pure graphite
with oxidized iron (1 mg) was transferred to a sample holder (small
rod shape; 1 mm hole) for the AMS.
The other pretreatment method is a reaction by acid. In this
study, the separation method for carbonate used the preprocessing
with phosphoric acid (H3PO4). In order to separate the carbon
atoms of carbonate from those of other materials, the carbonate,
such as calcium carbonate (CaCO3), was pretreated with H3PO4.

Sample
Oxidation Reaction
oC

a) With CuO powder at 850

for 2 hours
b) With CuO powder at 500 oC for 2 hours
c) O2/He flow gas at 980 oC
d) O2/He flow gas at 850 oC
e) O2/He flow gas at 500 oC
f) Reacted by H3PO4
Carbon dioxide
Purification of carbon dioxide in vacuum line
Deoxidization
With Fe powder at 650 oC for 10 hours
Graphite
AMS measurement
Fig. 3. Sample pretreatment method for accelerator mass spectrometry (AMS)
measurements.

When it is not necessary to distinguish the carbon atoms from

carbonate, the samples including the carbonates were prepared for
the AMS measurement according to the same procedure for the
solid chemical product as already described. All the carbon atoms
from the CaCO3 were transferred to graphite carbons through serial
vaporization and reduction reactions using a gas-tight glass tube of
clevis with a closing cock which can be connected to a vacuum
manifold system for the AMS measurement of the inorganic ller
(CaCO3). The sample powder including carbonates was placed in
a round-bottom ask on the vacuum manifold system connection
side of the gas-tight glass tube. Liquid H3PO4 (5 ml) was poured into
the other side of the round-bottom portion. This tube was connected to the vacuum manifold line under reduced pressure
(<5
104 mbar) for 10 min with cooling using a cold-trap of
ethanol-dry ice to remove any remaining air in the gas-tight glass
tube. The H3PO4 liquid was slowly transferred to the sample
powder side bottom portion. Additional liquid was added if the
reaction was not active. After all the liquid was transferred, this
tube was heated in a hot water bath (ca. 80  C) for 1 h.
2.5. Measurement of biomass carbon ratio
The measurement of the ratio of the three carbon isotopes (14C,
C, and 12C) using AMS was performed at the IAA. The AMS
measurement procedure has already been reported in our previous
studies [22e29]. The carbon in the graphite, transferred from the
samples, was ionized using a cesium cation beam. The anionized
carbons were accelerated using a 3 MV tandem accelerator. The
accelerated carbon isotopes were separated using an analyzing
magnet based on the different atomic masses. The amounts of 12C
and 13C were detected as a current using multi-Faraday cups. The
14
C atoms were detected using a solid state detector with a semiconductor absorber. The ratio of the 14C to 12C concentrations (14As)
in the composite samples was calculated from the measured
amounts of 14C and 12C. The percentage of modern carbon (pMC) for
an oil-based carbon is 0%. The pMC for the biomass made by the
xation of CO2 in the modern atmosphere through photosynthesis
was 108e110% in 2002. Measurement of the products 14As (14C/12C)
is determined as relative to the modern carbon-based oxalic acid
radiocarbon (Standard Reference Material (SRM) 4990c, National
Institute of Standards and Technology (NIST), USA). D14C can be
calculated using equation (1) and the pMC can be calculated from
D14C by equation (2). The biomass carbon ratio can then be
obtained using equation (3).
13

D14 C

h14


i
As 14 Ar =14 Ar
1000&

(1)

pMC D14 C=10 100%

(2)

biomass carbon ratio pMC
0:93%

(3)

14
As and 14Ar are the ratios of 14C to 12C for the sample and
reference (SRM 4990c), respectively. The above method is the
measurement procedure of the ratios for the three carbon isotopes
(14C, 13C, and 12C) in the samples at the IAA. Formulas (1) to (3) with
the correction factor of 0.93 are regulated in ASTM D 6866-08. At
the same time, the correction of 14As using the 13C ratio to 12C is also
regulated in ASTM D 6866-08. This correction was used for the
biomass carbon ratio of the Gofun in this study.

3. Results and discussion

The conrmation of a plastics product whose origin is a biomass
or petroleum is difcult, since it is not possible to easily conrm it

T. Onishi et al. / Polymer Degradation and Stability 95 (2010) 1276e1283

in the plastics product. Both resources obtained from a biomass or

petroleum is used in actual plastics products. The evaluation
method of the biomass carbon ratio is necessary for the plastics
product that can be made from both a biomass and petroleum. The
biomass carbon ratios of various polymer composites were
measured by the accelerator mass spectrometry (AMS) method as
described in the experimental section. To conrm the repeatability
and accuracy of the biomass carbon ratios by the AMS measurement, the measurement under different conditions of the polymer
composite was done. The ratio of the 14C atoms to the number of 12C
can be measured by AMS. The difference between the ratio of 14C to
12
C for the reference and that for the sample can be estimated as the
D14C value by equation (1). The percent modern carbon (pMC) can
be calculated from D14C according to equation (2). The biomass
carbon ratios of samples can be derived from the pMC and the
correction factor of 0.93.
3.1. Accuracy of biomass carbon ratio for polymer
composite with organic ller
The objective of this investigation is to develop a biomass
carbon ratio measurement for plastics products by AMS as a new
valuable ISO standard. For this purpose, the accuracy of the AMS
measurement is important. The accuracy was conrmed according
to the measurement under the different pretreatment conditions of
the AMS.
3.2. Polypropylene/cellulose powder composite
The results of the biomass carbon ratios of the petroleum-based
polypropylene (PP)/cellulose powder composite are shown in
Table 1. The materials used for the repetition of the identical ten
samples, shape of the samples, pretreatment conditions, 14C, pMC,
and biomass carbon ratios are shown in Table 1. The 14C atoms were
counted by a semiconductor absorber, since the number of 14C
atoms is very low compared to that of 12C. The measured data 14C by
AMS in IAA is calibrated by a reference. The 14C ratios of this
composite were measured ten times. For each sample, small
specimens were cut from different positions of the sheet sample,
pretreated, then measured. That is to say, a ca. 5 mg sample was
collected from the hot-melt sheet and was pretreated for every
sample. The measurement limit of the biomass carbon ratio by AMS
is 0.12% [29]. The standard deviation of these ten results was
0.78% and is sufciently low compared to the detection limit of

Table 1
Biomass carbon ratio of polypropylene (PP)/cellulose powder composite sheet.
Materiala

Shape

Pretreatment
conditionb

PP cellulose
PP cellulose
PP cellulose
PP cellulose
PP cellulose
PP cellulose
PP cellulose
PP cellulose
PP cellulose
PP cellulose
Average
Standard
deviation

sheet
sheet
sheet
sheet
sheet
sheet
sheet
sheet
sheet
sheet

EA980
EA980
EA980
EA980
EA980
EA980
EA980
EA980
EA980
EA980

C

C

C

C

C

C

C

C

C

C

D14C &

pMC %

Biomass
carbon ratio %

686.17
707.67
709.94
704.24
697.46
682.93
696.48
705.09
703.63
698.95

31.38
29.23
29.01
29.58
30.25
31.71
30.35
29.49
29.64
30.10

29.18
27.18
26.98
27.51
28.13
29.49
28.23
27.43
27.57
27.99
27.97
0.78

a
Heat press sheet of PP/cellulose powder (60/40 wt%). This cellulose is Avicel
powder. The biomass carbon ratio of PP was under 0.12% which was the underlimitation value of AMS. The biomass carbon ratio of the cellulose was 110.87%.
b
Oxidation reaction by O2 gas ow using elemental analysis apparatus at 980  C.

1279

the AMS measurement. The estimated value of the biomass

carbon ratio calculated using the molecular structure of PP and
cellulose is 25.7%. The experimental results (27.97%) are slightly
higher than these values. Possible reason for this result is the
higher biomass carbon ratio (110.87%) of the cellulose powder used
in this study [22].
3.3. Poly(butylene succinate)/cellulose (lter paper) composite
The results of the biomass carbon ratios of the poly(butylene
succinate) (PBS)/lter paper composite are shown in Table 2. The
materials, shape of the samples, pretreatment conditions, 14C, pMC,
and biomass carbon ratios are shown in Table 2. The 14C ratios of
this composite were measured six times. For each sample, small
specimens were cut from different positions in the sheet sample,
pretreated, then measured. That is to say, an ca. 6 mg sample was
collected and every sample was pretreated. The standard deviation
of these six results was 0.63% and is sufciently low compared to
the detection limit of the AMS measurement. The estimated value
of the biomass carbon ratio calculated using the molecular structure of PBS and cellulose is 12.2%. The experimental results
(12.47%) are almost the same as this value (12.2%). It was due to
that the biomass carbon ratio (98.72%) of the lter paper used was
almost 100%.
3.4. Evaluation of biomass carbon ratio for polymer
composite with inorganic ller
The ller and reinforcement including the inorganic carbon are
added to the polymer material to develop the mechanical and
processing properties. It is necessary to measure the biomass
carbon ratio of each constituent because various additives are
contained in an actual plastics product, and to do a more accurate
evaluation. To conrm the repeatability and accuracy of the biomass
carbon ratios by the AMS measurement for these materials, the
measurement under different conditions for the pretreatment of
AMS was done.
3.5. PP/calcium carbonate (biomass origin)
The mixed powder of PP, which is of petroleum origin, and
calcium carbonate (CaCO3), which is of biomass origin, was
measured by AMS. The sample including the inorganic carbon can
be analyzed for a carbon from a separate origin by changing the
pretreatment methods. Table 3 shows the results of the measurement of the biomass carbon ratios of this composite under various
pretreatment conditions. The calcium carbonate derived from the

Table 2
Biomass carbon ratio of poly(butylene succinate) (PBS)/cellulose paper composite
sheet.
Materiala

Shape

Pretreatment
conditionb

PBS cellulose
PBS cellulose
PBS cellulose
PBS cellulose
PBS cellulose
PBS cellulose
Average
Standard deviation

sheet
sheet
sheet
sheet
sheet
sheet

EA980
EA980
EA980
EA980
EA980
EA980

C
C

C

C

C

C


D14C &

pMC %

Biomass
carbon ratio %

873.94
865.19
854.17
870.64
860.88
870.79

12.61
13.48
14.58
12.94
13.91
12.92

11.73
12.54
13.56
12.03
12.94
12.02
12.47
0.63

a
Heat press sheet of PBS/cellulose (85/25 wt%). This cellulose is lter paper. The
biomass carbon ratio of PBS was 0.30% which was the under-limitation value of
AMS. The biomass carbon ratio of the lter paper was 98.72%.
b
Oxidation reaction by O2 gas ow using elemental analysis apparatus at 980  C.

1280

T. Onishi et al. / Polymer Degradation and Stability 95 (2010) 1276e1283

Table 3
Biomass carbon ratio of PP/calcium carbonate (biomass origin) composite under different pretreatment conditions.
Run

1
2
3
4
5
6
7
8
9
10
11
12
13
14

Material

PP CaCO3a
PP CaCO3b
PP CaCO3a
PP CaCO3b
PP CaCO3a
PP CaCO3b
PP CaCO3a
PP CaCO3b
PP CaCO3a
PP CaCO3b
CaCO3c
PP CaCO3a
PP CaCO3b
CaCO3c

Shape

powder
sheet
powder
sheet
powder
sheet
powder
sheet
powder
sheet
powder
powder
powderd
powder

Estimated carbone mg

2.07
2.11
3.59
4.56
1.97
2.01
3.15
3.12
3.29
3.13
3.06
1.95
1.94
3.13

(polymer)
(polymer)
(polymer)
(polymer)
(total)
(total)
(total)
(total)
(total)
(total)
(inorganic)
(inorganic)

Pretreatment
condition

Recovery of CO2
Weight mg

Yield %

CuOf 500  C
CuOf 500  C
EAg 500  C
EAg 500  C
CuOf 850  C
CuOf 850  C
EAg 850  C
EAg 850  C
EAg 980  C
EAg 980  C
EAg 980  C
H3PO4h
H3PO4h
H3PO4h

2.14
2.16
2.53
4.29
1.71
1.75
3.03
3.06
3.20
3.06
3.05
1.82
1.09
3.00

104
103
70.6
94.1
86.7
87.3
96.3
98.0
97.2
97.8
99.8
93.2
56.3
96.0

D14Ci &

pMCi %

Biomass
carbon ratio %

980.82
976.08
996.08
995.79
907.54
904.45
904.12
906.96
905.54
907.36
82.67
73.78
89.37
82.99

1.92
2.39
0.39
0.42
9.25
9.56
9.59
9.30
9.49
9.26
108.27
107.38
108.94
108.30

1.79
2.22
0.36
0.39
8.60
8.89
8.92
8.65
8.83
8.61
100.69
99.86
101.31
100.72

Mixed powder of PP/CaCO3 (60/40 wt%).

Heat press sheet of PP/CaCO3 (60/40 wt%).
c
Biobased calcium carbonate (shell powder).
d
Freeze shattering from PP/CaCO3 composite sheet.
e
The (total) estimated carbon was calculated from the carbon of PP and CaCO3, and distinguished by the polymer and inorganic. The estimated carbon was calculated from
the carbon of PP as the indication (polymer). The estimated carbon was calculated from the carbon of CaCO3 as the indication (inorganic).
f
Oxidation reaction with CuO in a quartz tube.
g
Oxidation reaction by O2 gas ow using elemental analysis apparatus.
h
Reaction by phosphoric acid (H3PO4).
i
Corrected value using for shell samples for AMS.
b

biomass is Gofun, which is a coloring used in Japanese paints and is

made of sea shells. It is thought that there are some amounts of
other materials rather than calcium carbonate in Gofun, since
Gofun is not a chemical product and is not pure calcium carbonate.
These organic materials have a higher pMC due to the bomb effect
on carbon derived from phytoplankton growing near surface of the
sea. In this study, the pMC of samples including shells was corrected using the ratio of 13C to 12C.
The biomass carbon ratios for the pretreatment condition in the
oxidizing reaction by owing O2 gas using the elemental analysis
apparatus at 980  C (runs 9, 10) and 850  C (runs 7, 8) are shown in
Table 3. These values (8.61e8.92%) are almost same as the value
(8.61%) which is the estimated value of the biomass carbon ratio
calculated using the molecular structure of PP and calcium
carbonate with the correction by the biomass carbon ratio of the
shell powder (runs 11, 14). Also, when all the carbon atoms in the
composites were converted into carbon dioxide by the pretreatment condition for the oxidation reaction at 850  C or higher, the
recovery yields of these samples were over 96%. It is similar to
processing using the copper oxide at 850  C (runs 5, 6). The biomass
carbon ratio for the elemental analysis condition at 500  C (runs 3,
4) is about 0%, because PP in this sample is of petroleum origin and
the CO2 is produced from only PP. It is thought that the carbon atom

of polymer origin without any inorganic carbon can be measured by

this elemental analysis condition at 500  C. However, an increase in
the biomass carbon ratio from the inorganic carbon of biomass
origin when processing by the copper oxide at 500  C (runs 1, 2)
was observed. It is thought that even calcium carbonate was
oxidized because it is an oxidation reaction in the closed system for
a long time. The biomass carbon ratio in the reaction by phosphoric
acid (runs 12, 13) was almost 100%, because the calcium carbonate
ller in this sample is of biomass origin, and CO2 was produced
from only calcium carbonate. In the reaction with phosphoric acid,
a decrease in the biomass carbon ratio with the ca0rbon of petroleum origin was not observed. Because the oxidizing reaction of
polymer is not done in the reaction with phosphoric acid.
The recovery of yield is a ratio of the carbon weight in the
recovered CO2 to the estimated carbon weight in PP and/or CaCO3.
The recovery of yield was not affected by difference in the shape of
the sample under the elemental analysis conditions at 850  C or
higher (runs 7, 8, 9, 10). However, the recovery of yield was affected
by difference in the shape of the sample under the elemental
analysis conditions at 500  C (runs 3, 4). The yield of the sample
whose from is a powder during processing by the copper oxide at
850  C (runs 5, 6) increases with the increasing reaction temperature. When processing with phosphoric acid, the yield (56.3% in

Table 4
Biomass carbon ratio of poly (lactic acid) (PLA)/calcium carbonate (mineral origin) composite using an elemental analysis apparatus at 980  C.
Materiala

Shape

Estimated carbon
(total)b mg

Pretreatment
conditionc

PLA CaCO3
PLA CaCO3
PLA CaCO3
PLA CaCO3
PLA CaCO3
Average
Standard deviation

sheet
sheet
sheet
sheet
sheet

3.07
3.01
3.04
2.99
3.03

EA980
EA980
EA980
EA980
EA980

a
b
c

C

C

C

C

C

Recovery of CO2
Weight mg

Yield %

3.08
3.03
3.09
3.04
3.06

100
101
102
102
101
101
0.60

Heat press sheet of PLA/CaCO3 (80/20 carbon %). The biomass carbon ratio of CaCO3 was 0.20%.
The estimated carbon is calculated from all carbons in the PLA and CaCO3.
Oxidation reaction by O2 gas ow using elemental analysis apparatus at 980  C.

D14C &

pMC %

Biomass
carbon ratio %

125.46
118.34
126.52
120.69
118.87

87.45
88.17
87.35
87.93
88.11

81.33
82.00
81.24
81.77
81.94
81.66
0.32

T. Onishi et al. / Polymer Degradation and Stability 95 (2010) 1276e1283

1281

Table 5
Biomass carbon ratio of PLA/calcium carbonate (mineral origin) composite using an elemental analysis apparatus at 500  C.
Materiala

PLA CaCO3
PLA CaCO3
PLA CaCO3
PLA CaCO3
PLA CaCO3
Average
Standard deviation
a
b
c

Shape

sheet
sheet
sheet
sheet
sheet

Estimated carbon
(polymer)b mg

Pretreatment
conditionc

2.42
2.44
2.46
3.00
3.00

EA500
EA500
EA500
EA500
EA500

C
C

C

C

C


Recovery of CO2
Weight mg

Yield %

2.31
2.21
2.18
2.52
2.46

95.1
90.4
88.5
84.1
82.2
88.0
4.60

D14C &

pMC %

Biomass
carbon ratio %

92.80
82.15
92.23
83.57
81.55

109.28
108.22
109.22
108.36
108.15

101.63
100.64
101.57
100.77
100.58
101.04
0.46

Heat press sheet of PLA/CaCO3 (80/20 carbon %). The biomass carbon ratio of CaCO3 was 0.20%.
The estimated carbon amount is calculated from the carbons in PLA. This value does not include the carbon in CaCO3.
Oxidation reaction by O2 gas ow using elemental analysis apparatus at 500  C.

run 13) of the composite sample is lower than that (93.2% in run 12)
of powder sample even if both are powders. This is thought to be
dare rotes low value of the yield because of wrapping the inorganic
ller by polymers in the case of run 13. Also, it is thought that the
yield increases when the sample size becomes smaller.
3.6. Poly(lactic acid) (PLA)/calcium carbonate (mineral origin)
The possibility of AMS to separate a plastics part and the inorganic carbon is shown from the result in Table 3 for a plastics
composite. The PLA composite with an inorganic ller was
conrmed by the same method. The composite of PLA, which is of
biomass origin, with the calcium carbonate (CaCO3), which is of
mineral origin, was made, and the biomass carbon ratio of the
composite was measured by AMS. The results of the measurements
under different conditions for the pretreatment of the biomass
carbon ratios are shown in Tables 4e6. The 14C ratios of this
composite were measured ve times under different pretreatment
conditions. Table 4 shows the biomass carbon ratios in which the
PLA/CaCO3 composite is processed at 980  C that is the usual
pretreatment condition for carbon dating by the AMS method.
Under this condition, both the polymer and the inorganic carbon
become carbon dioxides. The biomass carbon ratio of PLA was the
same as the value in Table 5. The estimate of the biomass carbon
ratios calculated using the molecular structure of PLA and CaCO3 is
80%, the measured averaged value is 81.66%, and it is almost the
same as the average (81.66) in Table 4. The standard deviation of
these ve results is 0.32% and is sufciently low compared to the
detection limit of the AMS measurement. This value is lower than
the value in Tables 1 and 2. This suggests the better dispersion of
calcium carbonate with the ner powder. It was possible to
measure with a better repeatability. The recovery factor of the
carbon dioxide of the composite under the pretreatment conditions
for the oxidation reaction at 980  C is almost 100%. It was found

that all carbon atoms in the composite were converted into carbon
dioxide.
Table 5 shows the result of the measurement under the different
conditions for the biomass carbon ratio at 500  C. For the preprocessing condition at 500  C, the carbon atoms of polymer origin
can be measured, since the inorganic carbon does not become
carbon dioxide under this condition. The biomass carbon ratio of
the composite for the pretreatment condition during the oxidation
reaction at 500  C was 101.04%. The standard deviation of these
results was able to be measured at 0.46% which is very low with
a good repeatability. The recovery yield factor of carbon dioxide is
lower than that of the sample for the pretreatment condition
during the oxidizing reaction at 980  C.
Table 6 shows the results of the measurement under the
different conditions of the biomass carbon ratios for the reaction
with phosphoric acid (H3PO4). For the pretreatment by H3PO4, the
carbon atoms of inorganic ller origin can be measured, since PLA
is not oxidized to CO2 by the acid reaction. It oured by the freeze
shattering from the PLA/CaCO3 composite sheet and used the for
AMS measurement. The reaction of CaCO3 with the acid hardly
occurs in the sheet state. CaCO3 in the PLA matrix cannot contact
the H3PO4 liquid. The biomass carbon ratio is 0.29% under the
pretreatment condition for the reaction with H3PO4 of the
composite and is almost 0%. The biomass carbon ratio of calcium
carbonate (mineral origin) used in this study is 0.20%. The biomass
carbon ratio of calcium carbonate (mineral origin) is not 0%,
because calcium carbonate is obtained from limestone by
a chemical treatment such as combustion. It is thought that some
of the carbon atoms in the calcium carbonates exchanged with the
biomass carbon atoms during the combustion process, since
a small biomass waste amount is mixed as a fuel for combustion.
It is thought that the lower recovery (77.6%) of carbon dioxide was
not able to react using phosphoric acid as the calcium carbonate
was covered with a polymer. The biomass carbon ratio of each

Table 6
Biomass carbon ratio of PLA/calcium carbonate (mineral origin) composite using reaction by H3PO4 at 80  C for 1 h.
Materiala

Shapeb

Estimated carbon
(inorganic)c mg

Pretreatment
conditiond

Recovery of CO2
Weight mg

Yield %

PLA CaCO3
PLA CaCO3
PLA CaCO3
PLA CaCO3
PLA CaCO3
Average
Standard deviation

powder
powder
powder
powder
powder

2.01
2.11
2.07
2.02
2.03

H3PO4
H3PO4
H3PO4
H3PO4
H3PO4

1.52
1.65
1.63
1.61
1.54

75.4
78.1
78.7
79.7
76.0
77.6
1.61

a
b
c
d

Heat press sheet of PLA/CaCO3 (80/20 carbon %). The biomass carbon ratio of CaCO3 was 0.20%.
Freeze shattering from PLA/CaCO3 composite sheet.
Estimated carbon amount is calculated from carbon in CaCO3. This value does not include the carbons in PLA.
Reaction by phosphoric acid (H3PO4).

D14C &

pMC %

Biomass
carbon ratio %

997.12
996.77
996.87
996.78
996.73

0.29
0.32
0.31
0.32
0.33

0.27
0.30
0.29
0.30
0.31
0.29
0.01

1282

T. Onishi et al. / Polymer Degradation and Stability 95 (2010) 1276e1283

Polymer/Inorganic filler composite sample

Pretreatment

Reaction by H3PO4 at 80 oC

Oxidation reaction at 980 oC

Oxidation reaction at 500 oC

Carbon dioxide

Carbon dioxide

Carbon dioxide

Deoxidization

Deoxidization

Deoxidization

Graphite

Graphite

Graphite

AMS measurement

AMS measurement

AMS measurement

Total biomass carbon ratio

for all components

Biomass carbon ratio for

polymer component

Biomass carbon ratio for

inorganic filler component

(polymer + Inorganic filler)

Fig. 4. Biomass carbon ratio measured by AMS for each component of polymer composite sample by pretreatment condition.

constituent can be measured from the above-mentioned result

by changing the pretreatment conditions of sample as shown in
Fig. 4.
4. Conclusion
The biomass carbon ratio of a polymer composite mixed with an
organic or inorganic ller was investigated by the accelerator mass
spectrometry method (AMS). The repeatability and accuracy of the
biomass carbon ratio of the polymer composite were conrmed by
the measurement under the different conditions used for the AMS
pretreatment method. As a result, the repeatability and accuracy of
the biomass carbon ratio of plastics composites are sufcient for the
biomass certication system. Accordingly, the AMS method is an
evaluation method with an acceptable biomass carbon ratio of the
plastics composite for the new ISO standard. Each biomass carbon
ratio of the polymer/calcium carbonate composite was appreciable
by AMS method under different pretreatment conditions. The
standard deviation of the result under the different pretreatment
conditions is sufciently lower compared to the detection limit of
the of AMS measurement. It was thought that the biomass carbon
ratio of each constituent of the plastics products that are mixed
with an actual inorganic ller is appreciable as described in this
investigation. The product including biomass plastics and the
biomass additive is appreciable using this method. It is necessary to
develop this evaluation method in order to adapt the ISO standard
for biomass plastics products. More studies are necessary for this
purpose.
Acknowledgements
The authors are grateful for the nancial support from the New
Energy and Industrial Technology Development Organization
(NEDO) to Research Project entitled Development of Preparatory
Basic Bioenergy Technologies: Accelerated Technology Development for Biofuel: R&D of Method to Measure Biomass Carbon Ratio
of Biopolyolen.

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