RESEARCH ARTICLE | DECEMBER 14 2017

Production of PBT/PC particle systems by wet grinding 

Jochen Schmidt; Stefan Romeis; Wolfgang Peukert

AIP Conf. Proc. 1914, 050003 (2017)

https://doi.org/10.1063/1.5016720

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 Production of PBT/PC Particle Systems by Wet Grinding
Jochen Schmidt*, Stefan Romeis and Wolfgang Peukert

Friedrich-Alexander-Universität Erlangen-Nürnberg, Institute of Particle Technology, Cauerstr. 4, D-91058

Erlangen, Germany
*jochen.schmidt@fau.de

Abstract. Comminution of plastic or visco-elastic materials is known to be energy-intensive and costly. Typically impact
mills, cutting mills and jet mills are applied for comminution and the feed material frequently is pre-cooled using liquid
nitrogen or solid carbon dioxide. Therefore, especially the production of fine polymer particles by the aforementioned dry
grinding methods is challenging. We demonstrate that wet grinding of polymers is a feasible approach for production of
fine polymer particles that e.g. may be used as a starting material in a process chain for production of spherical polymer
particles that can be used in in additive manufacturing. Wet comminution of polymers will be discussed for polybutylene
terephthalate (PBT) and polycarbonate (PC). The products are thoroughly characterized by means of vibrational
spectroscopy, X-ray diffraction and dynamic scanning calorimetry. The dependency of the grinding result on
fundamental process parameters like stirrer tip speed, grinding media size, process time, process temperature and system
composition will be discussed. In any case high load conditions, i.e. high stress energies are needed to initiate breakage of
polymer materials. Optimization of the process with respect to process time and energy consumption by appropriate
selection of process temperature and solvent will be addressed. The selection of appropriate solvents allows for
remarkable reduction of mass-specific comminution energy needed.
Keywords: wet comminution, stirred media mill, polybutylene terephthalate, polycarbonate
PACS: 81.05.Lg; 82.35.Lr; 81.20.Wk; 81.15.-z

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INTRODUCTION
In recent years an increasing demand for fine polymer powders that may be used for additive manufacturing
processes, such as selective laser beam melting of polymers (LBM), has been recognized. According to the state of
the art, commercially available LBM powders like e.g. polyamide (PA) are obtained by sophisticated precipitation
methods that cannot be transferred readily to other types of polymers. As a more general method to produce fine
polymer powders, frequently dry grinding has been applied [1-7]. Typically rotor impact mills or cutting mills are
used and the polymer feed material is pre-cooled e.g. with liquid nitrogen or solid carbon dioxide. Thus, the
comminution of materials showing viscous or plastic deformation behavior is costly and energy-intensive.
Moreover, the minimum product particle sizes that are obtained by dry grinding are typically in the range of several
10 micrometers. In this contribution wet grinding [8] is discussed as an alternative and versatile approach to produce
fine micron-sized polymer particles. Dependencies of process parameters are outlined and the applicability of the
wet grinding process to polybutylene terephthalate (PBT), polycarbonate (PC), as well as PBT-PC mixtures is
demonstrated. The products are characterized by means of vibrational spectroscopy, X-ray diffraction and dynamic
scanning calorimetry. No remarkable structural changes occur during size reduction. The wet grinding process may
be employed as the first step in a process chain [9] that allows for production of innovative LBM powders.

METHODS
Particle Sizing

Particle size distributions were determined by laser diffraction particle sizing using a Mastersizer 2000 / Hydro
2000S (Malvern). The product suspensions have been diluted as appropriate prior to measurement. Small amounts of
sodium dodecyl sulphate solution (SDS, 98% (Merck)) have been added to assure dispersion stability. Prior to
measurements ultrasonication of the dispersions has been performed.

Proceedings of PPS-32
AIP Conf. Proc. 1914, 050003-1–050003-5; https://doi.org/10.1063/1.5016720
Published by AIP Publishing. 978-0-7354-1606-2/$30.00

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 Differential Scanning Calorimetry

Differential Scanning Calorimetry (DSC) was performed at a heating rate of 20 K min-1 using a DSC8000
(Perkin Elmer).

X-Ray Diffraction

Structural analysis of the polymers by means of powder X-ray diffraction (XRD) was performed using a Bruker
AXS D8 Advance diffractometer. The device was equipped with a VANTEC-1 detector and a Ni filter. Cu KD
radiation (Ȝ = 154.06 pm) was used. The X-ray diffractograms were recorded in Bragg-Brentano geometry in the
range 20ƒ ˜ 2Ɔ ˜ 80ƒ. The step width was 0.014ƒ and the accumulation time was 1 s for each step.

Infrared Spectroscopy

Infrared (IR) spectra were recorded in transmission (KBR method) in the spectral range from 4800 cm-1 to
400 cm-1 at 2 cm-1 resolution using a FT-IR spectrometer FTS 3100 (Varian). Spectra have been normalized to their
respective maximum absorbance at around 1715 cm-1 (QC=O). Baseline corrections were done manually.

RESULTS

Wet Grinding of PBT

Wet comminution of PBT (Ultradur 4520 HS, BASF) was performed in a custom-made agitator bead mill
equipped with a torque meter which allows for quantification of the mass specific energy Em consumed to obtain a

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certain product particle size x50,3. The feed material for wet grinding was obtained by grinding of the respective
polymer granules in a rotor-impact mill using a 0.5 mm sieve ring. Figure 1 depicts the dependency of the product
particle size on the mass specific energy for different stressing conditions. In the grinding experiments a feed mass
concentration of 12.5% PBT was applied, the process was done at ambient temperature and the solvent was ethanol
and –for SE = 5.4 mJ- also butanol. The variation in stressing conditions is expressed in terms of stress energy SE.
SE equals the maximum kinetic energy of a grinding bead [10]. Variation of the stressing conditions was
accomplished by changing the stirrer tip speed vtip (7.1 m s-1 vs. 10.6 m s-1) and the diameter dGM (1.25 mm, 2.0 mm,
3.0 mm) of the yttrium-stabilized zirconia grinding media of a density of 6050 kg m-3. Obviously, fracture of the
stressed feed material under these conditions only occurs if stress intensities of more than 2 mJ are chosen. In the
case of dGM = 1.25 mm (c.f. red symbols in Figure 1) virtually no fracture has been observed even for the maximum
stirrer tip speed of 10.6 m s-1 for this type of mill. If grinding media of 2.0 mm or 3.0 mm size are used and ethanol
was the solvent, no remarkable differences in the course of x50,3 over the mass specific energy was observed for Em >
10 MJ/kg. For constant stressing conditions of SE = 5.4 mJ the effect of the solvent on the mass specific energy
needed to obtain a certain product particle size was assessed. Obviously, using ethanol as compared to the more
viscous butanol is beneficial with respect to energy consumption: if an energy input of 30 MJ/kg applies, in the
ethanol system product particles of about 10 μm size are obtained, whereas in the butanol system larger particles of
about 17 to 18 microns are produced. The behavior qualitatively may be understood in terms of grinding media
dampening [8]: the energy transferred to a stressed particle is less for higher viscous systems because a higher
portion of energy is dissipated by viscous forces prior to grinding bead collisions. In general low viscous solvents
are advantageous and in certain cases [8] also the reduction of the process temperature (embrittlement of the
polymer) may improve the grinding kinetics and reduce the energy needed to initiate fracture. Compared with
typical mass specific energies needed for polymer grinding and typical minimum product particle size obtainable by
dry grinding [1], one can conclude that the wet grinding process allows for smaller product particles (about one
order of magnitude) at reasonable energy consumption. The wet grinding process is especially superior to dry
grinding, if fine products (x50,3 < 25 μm) are desired. For brittle polymers product particles with x50,3 < 5 μm readily
may be obtained.

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FIGURE 1. Evolution of product particle size x50,3 over process time during wet comminution of PBT in ethanol and butanol at
ambient temperature (for stressing conditions see figure legend).

Wet Grinding of PBT-PC mixtures

The wet grinding process also has been applied to PC (Makrolon 2405, Bayer) and a mixture (1:1 (wt./wt.)) of

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PBT and PC. Figure 2 summarizes the evolution of the particle sizes x90,3, x50,3 and x10,3 of stressed PBT and PC and
x50,3 for the PBT-PC mixture, respectively, over process time for wet comminution in ethanol at 20 °C for a feed
concentration of 18.5 wt.-%. A stress energy SE of 1.9 mJ was applied. PC (filled symbols) shows a narrower
product particle size distribution (c.f. smaller span = (x90,3 – x10,3) / x50,3) as compared to PBT (open symbols) for the
same SE and process time, which reflects differences in mechanical properties and fracture behavior. The grinding
kinetics of PBT-PC mixtures, i.e. the evolution of product particle size over process time, as exemplified for a 1:1
mixture has been found to be a simple (volume-weighted) superposition of the grinding kinetics of PBT and PC at
the respective mass concentration: no interaction between the polymers occurs during grinding and the fracture
mechanism are not influenced by the presence of the respective other polymer. Also no blend formation /
transesterification has been observed in wet grinding even for long process times. Similar grinding kinetics like for
the PBT-PC mixture have been observed for a PBT-PC blend system of the same PBT : PC mass ratio.

FIGURE 2. Evolution of product particle sizes x10,3, x50,3 and x90,3 over process time during wet comminution of PBT, PC and a
PBT-PC mixture (1:1 (wt./wt.)) in ethanol (for stressing conditions see figure legend).

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 Structural Characterization of Grinding Products
The grinding products amongst others have been characterized with DSC, XRD and IR spectroscopy. With
respect to production of powders for an application in LBM [9], it is important that no significant changes of
crystallinity occur during powder production. Table 1 summarizes the melting temperatures of PBT feed material
and product particles obtained after different process times (for stressing conditions see legend of Figure 2) and the
crystallinity of the respective samples. The degree of crystallinity was calculated from the melting enthalpies of the
respective powders, taking the melting enthalpy of fully crystalline D-PBT of 145.5 J/g [11] into account. No
significant change in crystallinity over process time is observed. The determined crystallinities in the range of 34.3
to 36.3 wt.-% of D-PBT, are typical for commercial PBT grades. Therefore, we can conclude that no significant
amorphization of the semi-crystalline polymer occurs during stressing under the chosen conditions.

TABLE (1). Melting temperature and degree of crystallinity (D-PBT) estimated from the heat of fusion of PBT
powders obtained by wet comminution for different process times.
process time / minutes melting temperature / °C degree of crystallinity / wt.-%
0 (feed material) 227.3 35.0
60 226.4 34.3
180 227.9 34.9
240 228.4 36.3
345 228.4 36.1

Also X-ray diffraction and infrared spectroscopy prove that no pronounced structural changes occur: The
diffractograms (Figure 3) of the feed material and wet ground PBT are almost identical. The patterns are typical for
D-PBT [12, 13], no significant changes due to grinding occur. Infrared spectra of polymer powders obtained for
different process times are depicted in Figure 4. For all samples spectral features being typical for PBT [14], i.e. the
C=O vibrational band at around 1715 cm-1, the CH2 bending mode at 1503 cm-1, the symmetric and asymmetric C-

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O-C stretching modes at 1206 cm-1 and 1103 cm-1, and modes assigned to the aromatic ring at 1018 cm-1, 873 cm-1
and 727 cm-1 are found. The spectra are almost identical, no pronounced changes in molecular structure occur during
grinding of PBT under the conditions studied.

FIGURE 3. X-ray diffractograms of PBT feed material and PBT particles obtained by wet comminution in ethanol.

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 FIGURE 4. IR spectra of PBT particles obtained by wet comminution in ethanol in dependency on process time.

CONCLUSIONS
A wet grinding method [8] was successfully applied to produce fine PBT, PC as well as PBT-PC mixed systems
with particle sizes x50,3 below 20 μm. Preservation of the crystallinity and structure of the stressed solids during

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stressing was proven by DSC, IR spectroscopy and X-ray diffraction. No significant amorphization takes place
during wet grinding, which makes the comminution process applicable to successfully produce PBT and PBT-PC
particle systems for additive manufacturing employing a previously proposed process chain [9, 15].

ACKNOWLEDGMENTS
This study has been supported by Deutsche Forschungsgemeinschaft (DFG) in the framework of the
collaborative research center CRC 814 “Additive Manufacturing” (project A1). Financial support is gratefully
acknowledged.

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