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A new straightforward method for measuring xylene soluble for high impact
polypropylene

Article  in  The Canadian Journal of Chemical Engineering · November 2016

DOI: 10.1002/cjce.22735

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A new straightforward method for measuring xylene soluble for high impact

polypropylene

Olivier Boyron*, Aarón J. Cancelas, Manel Taam, Christophe Boisson, Timothy McKenna

–––––––––

O. Boyron, A. J. Cancelas, M. Taam, C. Boisson, T. McKenna C2P2 - LCPP Group, UMR5265

CNRS, Université de Lyon, ESCPE Lyon, Bat 308F, 43 Bd du 11 novembre 1918, F-69616,
Villeurbanne, France
E-mail: olivier.boyron@univ-lyon1.fr
A. J. Cancelas, Dutch Polymer Institute DPI, POBox 902, 5600 AX Eindhoven, the Netherlands

–––––––––

Abstract.
The determination of the xylene soluble fraction in high impact polypropylene is used to estimate
the rubber content in the polymer material. In analytical laboratories, the soluble fraction is
measured by a solvent extraction using gravimetric methods according to ASTM5492 or
ISO6427. These methods require large quantity of polymers, large volume of solvent and long
extraction times. It is therefore highly desirable to develop other laboratory methodologies for
this task; preferably methodologies that employ existing laboratory equipment. It is found that
the SEC method proposed here yields estimates of rubber contents very close to those found
using standardized technics but in much shorter times.
Keywords: polypropylene; high-impact polypropylene; atactic polypropylene; xylene soluble; n-
heptane soluble

1
INTRODUCTION
Polyolefins can be divided into two main families, polyethylene (PE) and isotactic polypropylene
(iPP). Generally speaking, iPP homopolymers have higher stiffness and hardness than PE. These
properties make PP a thermoplastic material suitable for a different range of applications than
PE, and combined with a relatively low cost of production, this explains their widespread use.
However, as an engineering plastic, one of the weak points of iPP homopolymers is their limited
toughness, especially at lower temperatures. This can be overcome, by incorporating of a certain
amount of an amorphous component in situ in the homopolymer phase.

When the second phase is an elastomeric copolymer of ethylene and propylene (often referred to
as ethylene-propylene rubber, or EPR) the final product consisting of a iPP homopolymer matrix
in which EPR nodules are dispersed is called high impact polypropylene (hiPP), or Impact
Copolymer (ICP).[1-4] hiPP is typically made in a two steps process, although different
configurations are possible. In the first step, propylene is polymerized in the gas phase to
produce a highly isotactic homopolymer. Once the initial PP particles have reached a sufficient
size, a second, copolymerization step is used to form a separate elastomeric phase in the still-
reactive homopolymer particles. After processing, the rubber phase that is distributed in the PP
matrix helps to absorb and disperse the energy of any impact, but the overall stiffness is
maintained by the rigid homopolymer matrix.[5-8] Thus hiPP based materials have been widely
used for automobile parts, appliances, and outdoor applications.

The determination of the amount of EPR in the iPP matrix, coupled with the characterization of
the molecular properties is major information in terms of quality control for hiPP batches. One
of the most common ways to characterize hiPP is to measure the xylene solubles (XS). XS is a
term denoting the percentage of soluble species in propylene plastics and is assumed to be
equivalent to the EPR content of the hiPP. Since this value is proportional to the amorphous
content of the materials, it is widely used for product quality control and monitoring physical
properties of the polymer during synthesis and processing. In analytical laboratories, the soluble
fraction is measured by a solvent extraction using a gravimetric method according to
ASTM5492[9] or ISO16152.[10] Malvern Instruments have developed a ViscoGEL FIPA column
(Flow Induced Polymer Analysis) dedicated for XS measurement in polypropylene and for

2
cyclohexane soluble in EPDM elastomers. This method is a fast analytical tool if there is no
requirement for information on the molar mass distribution. An automated analytical technique
for determination of XS (CRYSTEX) have been also developed by Monrabal and co-workers.[11]
Other organic solvents have also been employed. Most common examples are n-octane,[12-16] n-
heptane[17, 18]
and n-hexane.[19] Extraction methods requires several grams of polymers, large
volume of solvent and long extraction times. It is therefore highly desirable to develop other
laboratory methodologies for this task; preferably methodologies that employ existing laboratory
equipment's.

In this paper, we describe a new method based on the use of a size exclusion chromatography
(SEC) for characterizing the amount of XS present in commercial hiPP products. The obtained
data are compared to a conventional ASTM testing method. In addition, for each samples the
xylene soluble fraction and xylene insoluble (XI) fraction were extracted, isolated and analyzed
by differential scanning calorimetry (DSC) and nuclear magnetic resonance (13C NMR).

In a similar vein, this new approach was also used to measure atactic fraction in polypropylene
with n-heptane as an alternative soxhlet extraction following ISO6427.[20]

EXPERIMENTAL SECTION
Samples and solvents

Four commercial samples of hiPP (hiPP1, hiPP2, hiPP3 and hiPP4) were provided by a major
producer of polyolefins. In house testing by the producer revealed rubber content of 12, 30, 20
and 17 weight % respectively.

Four addition PP samples were synthesized in our laboratories on a commercial Ziegler-Natta

catalyst as described by Cancelas et al.[21] PP1, PP2 and PP3 were obtained with a Si/Ti molar
ratio of 10 and PP4 with a Si/Ti molar ratio of 0.

Analytical grade solvents were used in all cases. Xylene (a mixture of isomers with less than 1%
ethylbenzene), 1,2,4 trichlorobenzene, tetrahydrofuran, and n-heptane (Biosolve BV, Netherland,
Analytical Reagent grade 99%) were used as received.

Size exclusion chromatography (SEC) in THF

3
SEC in tetrahydrofuran (THF) as eluent was used for measuring the rubber part in hiPP. SEC
measurements were performed with a Viscotek TDAmax system from Malvern Instruments that
consists of an integrated solvent and sample delivery module (GPCmax) and a Tetra Detector
Array (TDA) including a right (90°) and low (7°) angle light scattering (LS) detector
(RALS/LALS), a four-capillary differential viscometer, a differential refractive index detector
(RI), and a diode array UV detector. THF was used as the mobile phase at a flow rate of 1 mL
min–1. All polymers were prepared at a concentration of 20 mg mL–1 and filtrated through a 0.45
µm pore-size membrane before two-fold dilution and injection. The separation was carried out
on three Polymer Standard Service columns (SDVB, 5 µm, 100 000 Å, 300 × 7.5 mm) and a
guard column. Columns and detectors were maintained at 50 °C. The OmniSEC 5.02 software
was used for data acquisition and data analysis. The absolute number-average molar masses were
calculated using the LS and RI signals and xylene soluble content were calculated using RI
signal.

Determination of dn/dc value of xylene soluble fraction

In order to use the SEC method to measure the rubber content of a hiPP powder, it is first
necessary to determine the specific refractive index increment (dn/dc) of the dispersed phase.

This xylene soluble fraction of the polymer were obtained using the standard ASTM5492
method described above. The dn/dc was measured with the online refractive index detector (RI)
using Equation 1. A narrow polystyrene standard (Mn = 99 kg mol-1) with a concentration of 3
mg mL-1 was used to calibrate the detector. An instrumental constant (K) of 148.78 was then
calculated. A solution of the XS of hiPP2 was prepared at a concentration of 10 mg mL-1. Three
different volumes, 10 µL, 30 µL and 45 µL of this solution were injected in SEC. The dn/dc was
calculated by plotting the RI area (integrated from the RI signal) versus the injected volume with
the OmniSEC software. Because the RI area is assumed to be proportional to the refractive index
of the sample (Equation 1),[28] the dn/dc can be calculated from the slope of the straight line. No
adsorption occurs in the column and 100% of the polymer reach the RI detector is assumed. The
dn/dc of the xylene soluble fraction was found to be 0.074 mL g-1.

𝒅𝒏
𝑆"# = 𝐾× ×𝐶+,- ×𝑉+,- (1)
𝒅𝒄

4
SRI: RI signal (mV), K: constant of instrument, dn/dc refractive index increment of xylene soluble
fraction (mL g-1), Cinj: concentration of the injected solution (g mL-1), Vinj: injection volume
(mL).

High temperature size exclusion chromatography (HT-SEC) in TCB

HT-SEC was used for measuring atactic content in polypropylene. HT-SEC analyses were
performed using a Viscotek system (from Malvern Instruments) equipped with three columns
(Polefin 300 mm x 8 mm I. D. from Polymer Standards Service, porosity of 1 000 Å, 100 000 Å
and 1 000 000 Å). 200 µL of sample solutions with a concentration of 5 mg mL-1 were eluted in
1,2,4-trichlorobenzene (1,2,4 TCB) using a flow rate of 1 mL min-1 at 150°C. The mobile phase
was stabilized with 2,6-di(tert-butyl)-4-methylphenol (200 mg L-1). Online detection was
performed with a differential refractive index detector and a dual light scattering detector (LALS
and RALS) for absolute molar mass measurement. The OmniSEC 5.02 software was used for
calculations.

Differential scanning calorimetry (DSC)

Thermal characterizations were performed with a Mettler Toledo DSC 3+ differential scanning
calorimetry, equipped with an auto-sampler and a 120 thermocouple sensor. The temperature and
the heat flow of the equipment were calibrated with pure water, an indium and a zinc standard.[22]
All samples were accurately weighed (between 5 to 10 mg) and sealed in aluminum pans. They
were heated from -80 °C to 180 °C at 10 °C min-1 with an empty aluminum pan as reference.
Two successive heating and cooling cycle were performed and only the second run was
considered. Dry nitrogen with a flow rate set at 50 mL min-1 was used as the purge gas. Glass
transition temperature (Tg) was measured at the inflexion point while melting temperature (Tm)
was measured at the top of the endothermic peak. The STARe 13.0 thermal analysis software is
used to calculate Tg and Tm and crystallinity of the polymers: X = DHf / DHf0 where DHf (J g-1)
is the melting heat of the sample and DHf0 is the melting enthalpy of 100% crystalline materials
were 207 and 293 J g-1 for polypropylene[23] and polyethylene,[24] respectively.

NMR

5
NMR characterization was performed on a Bruker Avance III 400 spectrometer operating at
100.6 MHz for 13C NMR. 13C NMR spectra were obtained with a 10 mm PA-SEX probe at 393
K. A volume mixture of o-C6H4Cl2 (90%) and p-C6D4Cl2 (10%) was used as solvent.
Chemical shifts were measured in ppm using the resonance of polyethylene as internal reference
at 30.05 ppm.

RESULTS AND DISCUSSION

Rubber content in hiPP by xylene extraction

Rubber content was initially determined by conventional extraction with xylene according to
ASTM5492 method. The samples were then analyzed by a rapid method based on size exclusion
chromatography (SEC) measurements and the results were compared.

Standard test method for determination of xylene solubles in hiPP (ASTM5492)

The samples were weighed exactly (about 2.0 g), dissolved in xylene (200 mL), stabilized with
0.025% w/v of 2, 6-di-tert-butyl-4-methylphenol (BHT), at a reflux temperature of
approximately 145 ºC, for at least 30 minutes under vigorously stirring. After this step the
solution was cooled down to room temperature, at a controlled, constant rate. Then the insoluble
and soluble fractions were separated by filtration at 25 °C. A precise aliquot of 100 mL of the
xylene solution containing the soluble fraction was taken. The solution was evaporated by
heating the mixture up until the residue was almost dried in order to avoid polymer degradation.
The sample was then placed in a vacuum oven at 70 ºC until constant weight was achieved. This
fraction (XS) was identified as an amorphous phase as shown in Figure 1. The measure of the
solid content for each xylene soluble fractions is expressed as the weight % of amorphous part of
hiPP (Table 2).

The insoluble fraction was washed several times with xylene at room temperature, to dissolve
any amorphous material left in this fraction. As shown in Figure 1 insoluble fraction (XI)
contains iPP and a low fraction of crystalline ethylene/propylene copolymer. The thermal
properties of amorphous part and crystalline part are given in Table 1.

6
Figure 1. Thermogram obtained by DSC from -70 °C to 190 °C during the second heating step
for the original hiPP1 (A) and its xylene insoluble fraction (B) and xylene soluble fraction (C).

Table 1. Thermal properties of original hiPP and of XI and XS fractions measured by DSC
during the second heating step.

Sample Fraction EPR iPP PE

Tg(°C) Tm(°C) Tm(°C)
hiPP1 original - 48.6 164.5 114.9
XIa - 166.2 117.7
XSb - 42.6 - -
hiPP2 original - 48.7 166.4 114.7
XIa - 166.2 115.8
b
XS - 42.9 - -
hiPP3 original - 49.0 163.6 117.2
XIa - 162.8 120.3
XSb - 43.9 - -
hiPP4 original - 50.1 162.9 119.1
a
XI - 161.8 119.7

7
 XSb - 48.3 - -

a
insoluble fraction in xylene, b soluble fraction in xylene

NMR investigation

13
C NMR was used for investigation of original hiPP, amorphous fraction and insoluble fraction
(Figure 2).

13
Figure 2. C NMR spectrum of original hiPP2 (A) and its xylene insoluble fraction (B) and
xylene soluble fraction (C).

13
C NMR spectra of the XI (Figure 2B) showed that the insoluble fractions are highly isotactic
PP in agreement with the high temperature melting measured by DSC (Figure 1) which contain a
fraction of crystalline ethylene/propylene copolymer. The signals at 21.8, 28.9 and 46.5 ppm are
characteristics of highly isotactic PP.[25] The crystalline ethylene/propylene copolymer is an
ethylene rich material, as shown by the intense signal of ethylene sequence at 30 ppm, with
isolated propylene units (d (ppm) = 37.5, 33.1, 30.4, 27.4, 20.0).[26, 27] In regards to the soluble

8
fraction XS, the NMR spectra showed the resonances for a statistical ethylene/propylene
copolymer (Figure 2C).

Xylene soluble fraction measured by SEC THF

Xylene was stabilized with 0.025% w/v of 2, 6-di-tert-butyl-4-methylphenol (BHT). Solutions of

pure hiPP in xylene were prepared in vials of 40 mL with a concentration of 20 mg mL-1 at a
temperature of 145 ºC, during at least 30 minutes while vigorously stirring. After this step the
solution was cooled down to 25 ºC. Vial was cooled to below 100 ºC, ensuring that the solution
is cooled to within a narrow range of temperature from run to run, and then it was transferred to a
thermostatically controlled water bath at 25 ºC, where it was cooled for additional 30 minutes.
Subsequently the soluble xylene fraction was sampled and filtrated with a PTFE filter with a
porosity of 0.22 µm, and then diluted in THF (two-fold dilution) for SEC analysis. The
integration of the signal of refractive index detector and the use of Equation 2 and 3 provide
xylene soluble content (EPR content) of the sample.

𝑺𝑹𝑰
𝐶/0" = 𝒅𝒏 ×D (2)
𝑲× ×𝑽𝒊𝒏𝒋
𝒅𝒄

=>?@
%𝐸𝑃𝑅 = ×100 (3)
=AB??

where SRI is the RI signal (mV), K the constant of RI detector, dn/dc the refractive index
increment of the xylene soluble fraction (mL g-1), Vinj the injection volume (mL), %EPR the
fraction of ethylene propylene rubber in hiPP, CEPR and ChiPP the concentrations of EPR and
concentration of original hiPP prepared in xylene respectively, and D the dilution factor in THF.

Table 2. Comparison of values for amorphous phase content in hiPP, obtained by various
methods.
Sample Industriala ASTMb SECc Mnd Ðd
(%) (%) (%) (kg mol-1)
hiPP1 12 13 10 48 2.4
hiPP2 30 30 30 27 2.9
hiPP3 20 22 20 27 4.4
hiPP4 17 16 17 24 3.9

9
a b
xylene soluble content determined by industrial, xylene soluble content determined by
ASTM5492 method, xylene soluble content determined by SEC, d number average molar mass
c

Mn and dispersity Ð of the xylene soluble fraction determined by SEC.

As shown in Table 2, the results provided by this faster method are in good agreement with those
provided by the industrial supplier, and with those determined in laboratory by ASTM5492
method. Additionally, this procedure provides simultaneous measurement of the rubber content
and the molecular weight distribution of the soluble fraction. In conclusion, time and energy
consuming filtering, drying and cleaning of larger apparatus is saved, thus, rubber content is
determined in a more efficient way.

Atactic PP (aPP) content in PP by n-heptane extraction

Due to its amorphous nature, aPP is soluble in n-heptane in contrast to the isotactic PP (iPP).
Then during n-heptane extraction we consider that only aPP is soluble. aPP content in 4 PP
samples were determined by conventional extraction and by proposed HT-SEC methodology.

N-heptane fractionation by ISO6427

Atactic PP fraction in PP can be extracted by hot n-heptane using Soxhlet extraction. Five grams
of PP were treated with 300 mL of n-heptane for 16 hours. Between 15-25 reflux cycles per hour
were performed. The extract was then evaporated in a heating vacuum oven in order to measure
the aPP content. This method based on ISO6427 is classically used for determination of the
atactic fraction of PP.

N-heptane fractionation by HT-SEC

The SEC procedure described above can be adapted in order to determine the atactic content in
PP homopolymers. PP samples (400 mg) were stirred in 20 mL of n-heptane, stabilized with
0.025% w/v of 2,6-di-tert-butyl-4-methylphenol (BHT), at a temperature of 95 ºC, during 16
hours while vigorously stirring. After this step the solution was cooled down in a controlled way
to room temperature. The soluble fraction was filtrated for analysis by SEC, the solvent was
evaporated and the polymer was dissolved in 1,2,4 TCB before injection. The refractometer

10
detector permits the accurate quantification of the soluble material. For calculation Equation 1 to
Equation 3 were used and a value of dn/dc for aPP in TCB equal to -0.096 mL g-1[29, 30] was
chosen. This procedure provides simultaneous measurement of atactic content and the molecular
weight distribution of this fraction (Table 3).

Table 3. Heptane soluble content in PP determined by typical ISO6427 and by proposed HT-
SEC methodology.

Sample Tma Crysta ISOb SECc Mnd Ðd

(ºC) (%) (%) (%) kg.mol-1
PP1 169 47 3 2 9.9 2.3
PP2 168 47 2 3 3.6 3.7
PP3 168 47 3 2 8.6 2.1
PP4 160 24 44 48 20.0 5.0
a
Melting temperature and crystallinity determined by DSC, b heptane soluble content determined
c d
by ISO6427 method, heptane soluble content determined by HT-SEC method, number
average molar mass Mn and dispersity Ð of aPP determined by HT-SEC.

Heptane solubility measured with HT-SEC method fit well with the conventional ISO6427
method. In the same injection we obtained also the molecular weight distribution of the soluble
part.

CONCLUSIONS
A rapid method was developed for the determination of the xylene soluble fraction based on SEC
measurements. This method was found to be significantly faster and requiring lower quantity of
material than gravimetric methods.

The results obtained with the new experimental procedure for 4 industrial hiPP compared well
with those of the traditional method (ASTM5492), and with the values supplied by the industrial
partner. Only 2 hours are required using the SEC-based approach to get both the content and the
molecular weight distribution of the soluble fraction, whereas around 8 hours are needed with the

11
standard method. A similar procedure, with n-heptane extraction, was also be used for measuring
the atactic percentage in polypropylene sample. 16 hours of dissolution are required in SEC-
based approach and standard method easier to remove solvent and Mn en plus

to get both the content and the molecular weight distribution of the soluble fraction, whereas
around 8 hours are needed with the standard method. The results obtained compared also very
well with those of the traditional method (ISO6427).

ACKNOWLEDGEMENT
The authors are grateful to the Dutch Polymer Institute for financial and technical support in the
context of DPI Project 785. The authors also thanks Philippe Lievens (Malvern Instruments) and
Julien Lefebvre for SEC experiments and Franck Collas (Mettler Toledo) for support in DSC
analysis.

REFERENCES
[1] M. Gahleitner, C. Tranninger, P. Doshev, Journal of Applied Polymer Science 2013, 130, 3028.
[2] J. Jancar, A. DiAnselmo, A. T. DiBenedetto, J. Kucera, Polymer 1993, 34, 1684.
[3] Y. Yokoyama, T. Ricco, Polymer 1998, 39, 3675.
[4] N. Cui, Y. Ke, Z. Lu, C. Wu, Y. Hu, J. Appl. Polym. Sci. 2006, 100, 4804.
[5] F. Ramsteiner, G. Kanig, W. Heckmann, W. Gruber, Polymer 1983, 24, 365.
[6] L. Wang, B. Huang, J. Polym. Sci., Part B: Polym. Phys. 1990, 28, 937.
[7] H. Cai, X. Luo, X. Chen, D. Ma, J. Wang, H. Tan, J. Appl. Polym. Sci. 1999, 71, 103.
[8] H. Cai, X. Luo, D. Ma, J. Wang, H. Tan, J. Appl. Polym. Sci. 1999, 71, 93.
[9] "ASTM D5492-10, Standard Test Method for Determination of Xylene Solubles in Propylene Plastic",
ASTM International, West Conshohocken, PA, 2010, 2010.
[10] "ISO 16152:2005, Plastics - Determination of xylene-soluble matter in polypropylene", ISO
copyright, Geneva, 2005.
[11] L. Romero, A. Ortin, B. Monrabal, J. R. Torres-Lapasio, M. C. Garcia-Alvarez-Coque, Macromol.
Symp. 2012, 312, 157.
[12] R. Mehtarani, Z.-S. Fu, S.-T. Tu, Z.-Q. Fan, Z. Tian, L.-F. Feng, Industrial & Engineering Chemistry
Research 2013, 52, 9775.
[13] Z. Tian, X.-P. Gu, G.-L. Wu, L.-F. Feng, Z.-Q. Fan, G.-H. Hu, Industrial & Engineering Chemistry
Research 2012, 51, 2257.
[14] Z. Fu, J. Xu, Y. Zhang, Z. Fan, Journal of Applied Polymer Science 2005, 97, 640.
[15] Z. Fu, Y. Zhang, Z. Fan, J. Xu, Journal of Applied Polymer Science 2007, 103, 2075.
[16] Q. Dong, X. Wang, Z. Fu, J. Xu, Z. Fan, Polymer 2007, 48, 5905.
[17] H. F. Lie Lua, B.-g. Lia, S.-p. Zhub, 2008.
[18] Y. Zhou, H. Niu, L. Kong, Y. Zhao, J.-Y. Dong, D. Wang, Polymer 2009, 50, 4690.
[19] I. Urdampilleta, A. González, J. J. Iruin, J. C. de la Cal, J. M. Asua, Macromolecules 2005, 38, 2795.
[20] "ISO 6427:2013 - Plastics -- Determination of matter extractable by organic solvents (conventional
methods)", ISO copyright, Geneva, 2013.

12
 [21] A. J. Cancelas, V. Monteil, T. F. L. McKenna, Macromol. Symp. 2016, 360, 133.
[22] E. Gmelin, S. M. Sarge, Pure Appl. Chem. 1995, 67, 1789.
[23] H.-S. Bu, S. Z. D. Cheng, B. Wunderlich, Die Makromolekulare Chemie, Rapid Communications 1988,
9, 75.
[24] V. B. F. Mathot, Polymer 1984, 25, 579.
[25] V. Busico, R. Cipullo, Prog. Polym. Sci. 2001, 26, 443.
[26] T. Hayashi, Y. Inoue, R. Chujo, T. Asakura, Polymer 1988, 29, 1848.
[27] T. Asakura, Y. Nishiyama, Y. Doi, I. Ando, Polym. J. (Tokyo) 1987, 19, 829.
[28] B. Coto, J. M. Escola, I. Suárez, M. J. Caballero, Polymer Testing 2007, 26, 568.
[29] V. Grinshpun, A. Rudin, Journal of Applied Polymer Science 1986, 32, 4303.
[30] J. Horská, J. Stejskal, P. Kratochvíl, Journal of Applied Polymer Science 1983, 28, 3873.

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