Applied Catalysis B: Environmental 267 (2020) 118699

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Applied Catalysis B: Environmental

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

Kinetic study of thermocatalytic degradation of UHMWPE over microporous T

and hierarchical ZSM-23 zeolite
Bruno J.B. Silvaa,*, Lenivaldo V. Sousaa, Lais R.A. Sarmentoa, Soraya L. Alencara,
Paulo H.L. Quintelab, Antonio O.S. Silvaa
a
Federal University of Alagoas, Department of Chemical Engineering, CEP:57072-900, Maceió, AL, Brazil
b
Federal University of Sergipe, Department of Chemical Engineering, CEP:49100-000, São Cristóvão, SE, Brazil

ARTICLE INFO ABSTRACT

Keywords: The catalytic degradation of ultra high molecular weight polyethylene was studied in the presence of micro-
Catalytic degradation porous and hierarchical ZSM-23 zeolites by thermogravimetric analysis. The ZSM-23 was synthesized using
Ultra high molecular weight polyethylene different structure-directing agents and subsequently subjected to post-synthesis treatment. The materials
ZSM-23 zeolite characterization were carried out by dispersive energy X-ray spectrometry, X-ray diffraction, temperature pro-
Post-synthesis treatment
grammed desorption of ammonia and nitrogen adsorption-desorption measurements. The obtained zeolites were
Model-free kinetics
physically mixed with polymer in the proportion of 30 %wt and submitted to thermogravimetric analyses at
heating rates of 5, 10, 20 and 30 °C.min−1. The average activation energy for the process was determined from
the model-free kinetic proposed by Flynn-Wall-Ozawa. The modified zeolites presented a secondary porosity,
which reflected in high values of external surface area and acidity, and demonstrated higher conversion effi-
ciency and lower energy level required in polymer degradation compared to the parent samples.

1. Introduction problems because of chemical inertness and pollutants emissions [5].

Plastics having numerous applications and relatively low cost, are
one of the most widely used materials in our daily lives, with an
average production increase of 10 % each year worldwide since 1950
[1,2]. Within this class of materials is Ultra high molecular weight
polyethylene (UHMWPE), which is a subset of thermoplastic poly-
ethylene. In terms of chemical composition, UHMWPE is a very simple
polymer, composed only by hydrogen and carbon atoms (linear formula
H(CH2CH2)nH, with n greater than 100.000 and density equal to
0.94 g.mL−1 at 25 °C), but its hierarchically organized structure is
complex at a molecular level [3]. UHMWPE is a linear homopolymer
with long molecular chains (molecular mass usually between 3.5 and
7.5 million amu.), all aligned in the same direction, that presents
crystalline (also called crystalline lamellae, with sheet-like form) and
amorphous regions [4]. Due to its wear and impact resistance,
UHMWPE demand is has a growing in industrial applications, including
automotive, bottling and increasingly medical devices [3].
Huge amounts of plastic wastes are generated every year due to the
increasing variety of uses applications of plastics such materials. The
normal methods of disposal of these residues are the landfill and in-
cineration. However, these treatments generate serious environmental
Conventional recycling treatments have limited applicability of re-
cycled for plastic materials due to the their progressive loss of quality or
possible emission of toxic compounds. On the other hand, chemical
treatments appear as a promising alternative, because since high added
value products such as monomers [6–8], chemical feedstocks [9,10] or
fuels [11,12] can be are generated.
The main chemical recycling routes are thermal and catalytic de-
gradation [13]. Thermal degradation requires high processing tem-
peratures (> 500 °C) and have low product selectivity, limiting it’s their
use. Catalytic degradation using a catalyst with adequate properties
provides a solution to these problems, reducing reaction temperature
and restricting improving product selectivity [14].
Several studies describe the application of solid acid catalysts in the
degradation of polymers in fuel production, usually where the most
studied are silica alumina [14,15] and some zeolites [13,16–18]. Cat-
alytic cracking processes over traditional zeolitic catalysts (X, Y, ZSM-5,
Beta, among others) may be restricted, due to the diffusional limitation
imposed on bulky molecules by the microporous structures [19]. One
approach to favor the diffusion of large molecules in the zeolitic
structure is the development of a hierarchical porosity.
Hierarchical zeolites combine typical micropores with the

⁎
Corresponding author.
E-mail address: brunojbarros@gmail.com (B.J.B. Silva).

https://doi.org/10.1016/j.apcatb.2020.118699
Received 10 October 2019; Received in revised form 8 January 2020; Accepted 26 January 2020
Available online 31 January 2020
0926-3373/ © 2020 Elsevier B.V. All rights reserved.
B.J.B. Silva, et al.
occurrence of additional secondary porosity, which is an advantage in
reactions involving large compounds [20]. This is due to a number of
elements: improved diffusion of reagents and products within micro-
porous crystals the pore system due to caused by the presence of wider
mesopores and/or shorter diffusion paths [21,22], improved selectivity
over desired products in some reactions [23,24] and substantial re-
duction in deactivation by coke deposition [25,26].
The catalytic effect of a zeolite on polymer decomposition can be
evaluated using different techniques approachs and reactors, but and
thermogravimetric analysis is one of the most frequently used techni-
ques [27–29]. Thermogravimetric analysis the information provided by
this technique allows to obtain the kinetic data, and evaluate the effect
of the polymer structure, composition and operating variables on the
pyrolysis process to be studied [30]. The isoconversional methods by
thermogravimetry have been extensively used to obtain determine the
activation energy by the for catalytic degradation of polymers [31].
Among these, one of the most used methods is the Flynn-Wall-Ozawa
(FWO) [32–34], which is used to obtain kinetic data, such as degree of
conversion and activation energy (Ea) of chemical reactions.
In this context, the present work aimed, to evaluate the influence of
UHMWPE degradation over microporous and hierarchical ZSM-23
zeolites with different acidity and textural properties. The activation
energy was determined using the non-isothermal kinetic model FWO.
This model allows to determine the activation energy of complex re-
actions, such as polymers degradation, starting from the conversion
data from the reaction obtained by heating the samples with different
heating rates.
2. Experimental
2.1. Synthesis of the catalysts (Z series parent samples)
The following precursor reagents were used to synthesize ZSM-23
zeolite: sodium silicate (Quimesp, 29.6 % SiO2, 9.2 % Na2O), aluminum
sulfate (Merck, 99 %), sulfuric acid (Sigma-Aldrich, 99 %), iso-
propylamine - IPA (Sigma-Aldrich, 99 %), ethylene glycol - ETG
(Dynamic, 99.5 %), N,N-dimethylformamide - DMF (Sigma-Aldrich,
99.8 %), pyrrolidine - PYR (Sigma-Aldrich, 99 %) and distilled water.
The synthesis gel was obtained prepared according to the procedure
described by Silva et al. [35], with the following stoichiometric molar
compositions:
100 IPA : 30 Na2O : 1.0 Al2O3 : 100 SiO2 : 27.6 H2SO4 : 2000 H2O,
666.7 ETG : 30 Na2O : 1.0 Al2O3 : 100 SiO2 : 22.08 H2SO4 : 2000
H2O,
45 PYR : 30 Na2O : 1.0 Al2O3 : 100 SiO2 : 27.58 H2SO4 : 2000 H2O,
67 DMF : 36 Na2O : 1.0 Al2O3 : 100 SiO2 : 3.0 H2SO4 : 3500 H2O
Crystallization occurred at 170 °C in 1 L Parr 4520 reactor, under
stirring at 400 rpm for 20 h. The obtained samples were calcined at
550 °C for 6 h, under 100 mL.min−1 air flow. The acid zeolites were
obtained by ion exchange of a portion of the calcined samples materials,
were performed with a 0.1 M ammonium nitrate solution (Sigma-
Aldrich, 95 %), followed by calcination under the same previous con-
ditions.
2.2. Post-synthesis treatment of the catalysts (AZ series modified samples)
The alkaline treatment of a portion of the calcined samples was
performed in a 300 mL Parr 4560 reactor, using 0.2 M NaOH solution at
65 °C for 2 h under agitation at 200 rpm. In all experiments the ratio of
1 g of zeolite per 50 mL of alkaline solution was used. After the treat-
ment period, the solid was recovered by centrifugation, washed with
distilled water to until pH below 8 and oven dried at 80 °C for 12 h. The
acid wash was then performed with 0.1 M HCl solution at 65 °C for 2 h
under agitation at 200 rpm. The materials were calcined under the
conditions previously described above.
2
Applied Catalysis B: Environmental 267 (2020) 118699
2.3. Catalysts characterization
X-ray diffraction analysis was performed in a Shimadzu XRD-6000
diffractometer, CuKα (λ =0.1542 nm), Ni filter, 40 kV voltage and
30 mA current. The data were as collected in the 2θ range between 3
and 40°, with goniometer velocity speed of 2°.min−1 and step of 0.02°.
Dispersive energy X-ray spectrometry (EDX) was used to determine the
SiO2/Al2O3 ratio of the samples in a Shimadzu – EDX – 7000/8000
spectrometer. Nitrogen adsorption-desorption measurements at
−196 °C were performed on a Micromeritics ASAP 2020 equipment in
the P/P0 range between 0.01 and 0.99. NH3-TPD profiles were de-
termined in a SAMP3 Termolab multipurpose analytical system, where
the samples were initially treated at 500 °C under a 30 mL.min−1 he-
lium flow rate for 1 h, then cooled to 100 °C and subjected to ammonia
adsorption for 1 h, followed by desorption in the temperature range of
100–800 °C, with a heating rate of 10 °C.min−1.
2.4. Thermocatalytic degradation of UHMWPE
Ultra high molecular weight polyethylene (UHMWPE) (Aldrich,
medium Mw 3 × 106 - 6 × 106) was used in the study. Prior to the
preparation of the catalyst and polymer mixtures, these were passed
through a 100 mesh sieve (ensuring particle size less than 150 μm) and
dried at 80 °C for 2 h. The mixing procedure consisted of the following
steps: i) the catalyst and polymer were weighed separately to give 2 g of
mixture (this amount of mixing ensures greater accuracy in the catalyst-
polymer ratio) in a 5-digit analytical balance; (ii) these components
were mixed gently in a agate mortar for 10 min, in the proportion of 30
% catalyst/70 % polymer wt to ensure that a homogeneous mixture is
formed. It is important to observe that this proportion reaches a per-
centage more than enough to evaluate the physicochemical properties
of the catalyst in the process, according to saturating effects described
in the literature for HDPE degradation with ZSM-12 zeolite (uni-
dimensional structure like a ZSM-23) [36].
Polymer degradation experiments were carried out in a termoba-
lance Shimadzu model DTG-60H at temperature range from room
temperature to 600 °C, with nitrogen flow of 50 mL.min−1 and heating
rate of 5, 10, 20 and 30 °C.min−1. For each experiment were used
samples of approximately 10 mg. From the non-isothermal kinetic
model proposed by Flynn-Wall-Ozawa, the activation energy for
UHMWPE degradation reaction with and without catalyst was de-
termined.
In order to verify the catalytic activity of the HZSM-23 zeolites, we
prepared a sample containing 30 % wt. of inert amorphous silica
(Sigma-Aldrich, with particle average diameters of ca. 44 μm), which
was submitted to identical treatments of the samples containing 30 %
wt. of HZSM-23 zeolite. As the silica practically do not present acidity is
expected that the behavior of the mixture silica + UHMWPE be very
similar to UHMWPE without addition of catalyst.
The amount of coke (remaining residue on the catalyst after
polymer degradation at a temperature of 600 °C) was estimated by Eq.
(1):
MFinal MCat
Coke (%) = × 100
MCat (1)
where MFinal is the final mass obtained at a temperature of 600 °C and
MCat is the mass of fresh catalyst added to the polymer.
3. Results and discussion
3.1. Catalysts physicochemical properties
X-ray diffraction patterns of the parent and modified samples are
shown in Fig. 1. Comparing the diffractograms with those reported in
the literature [37,38], all synthesized samples was found to have the
B.J.B. Silva, et al. Applied Catalysis B: Environmental 267 (2020) 118699

Fig. 1. XRD patterns of parent and modified samples, with impurities of ZSM-5 indicated by asterisk.

characteristic peaks of ZSM-23 zeolite. (JCPDS card no 46-057070).
After careful examination of the diffractograms, small impurities re-
lated to the ZSM-5 phase (JCPDS card no 42-0023) were identified in
the XRD of the samples synthesized with IPA and PYR, because the
more representative peaks of both phases overlap, making it difficult to
distinguish them become almost indistinguishable only by X-ray dif-
fraction. It is commonly reported the difficulty in obtaining the pure
ZSM-23 zeolite, due to its synthesis being very sensitive to the experi-
mental conditions [39,40]. After the post-synthesis treatment, there
was a minimum variation in the intensity of the peaks, indicating the
maintenance of the MTT phase crystalline structure.
The textural and acid properties of the zeolites are summarized in
Table 1. EDX results indicated SiO2/Al2O3 ratio values of the parent
zeolites very close to the theoretical (100), demonstrating a significant
insertion of this metal in relation to its stoichiometric chemical com-
position, which proves the efficacy of obtaining the synthesis gel. The
modified samples showed a significant decrease of the SiO2/Al2O3 ratio,
indicating the extraction of silicon atoms from the zeolite structure.
This fact is corroborated by the results of N2 adsorption-desorption,
which show a significant increase in the values of external area and
pore volume, reflecting the partial demetallization of the zeolite
structural lattice promoted by the post-synthesis treatment, generating
defects on the crystal surface, which gradually increase its dimensions
with increasing treatment severity, allowing for create a bimodal por-
osity in the zeolites [41]. Although XRD results indicate the presence of
ZSM-5 phase traces in the Z-IPA sample, the area and volume values
obtained for this material are consistent with those reported for ZSM-23
zeolite [42,43]. In addition, SEM analysis reported in a previous work

Table 1
Textural and acid properties of the zeolites.
Sample SiO2/Al2O3a SEXT/b VTotal/ VMic/c VMeso/d Maximum NH3-TPD
ratio m2. g−1 cm3. g−1 cm3. g−1 cm3. g−1 temperature/e acidity/e
°C μmol. g−1

Weak Strong Total

Z-IPA 97 59 0.16 0.09 0.07 467 237 134 371

AZ-IPA 58 80 0.25 0.08 0.17 472 202 207 409
Z-ETG 91 37 0.13 0.09 0.04 478 370 223 593
AZ-ETG 66 48 0.17 0.09 0.08 469 234 151 385
Z-PYR 90 80 0.31 0.10 0.21 473 281 94 375
AZ-PYR 39 154 0.49 0.08 0.40 486 245 226 471
Z-DMF 93 56 0.16 0.08 0.08 464 281 148 429
AZ-DMF 53 99 0.35 0.09 0.26 459 165 145 311

a
Calculated using the EDX measurements.
b
External area (t-plot method).
c
Micropore volume (t-plot method).
d
Mesopore volume (VTotal - Vmicro).
e
Calculated using the NH3-TPD measurements.

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B.J.B. Silva, et al. Applied Catalysis B: Environmental 267 (2020) 118699

[35] showed that the material synthesized with IPA has the char- Table 2
acteristic morphology of ZSM-23, unlike the sample produced with Thermogravimetric values obtained in the degradation of UHMWPE under
PYR, in which the presence of ZSM-23 and ZSM-5 phases is clear. The heating rate of 10 °C.min−1.
most expressive values of area and volume obtained for PYR samples, as Sample TInitial/a TFinal/a Mass loss/b Coke/c
previously described by Möller and Bein [44], is due to the presence of °C °C mass% mass%
the ZSM-5 observed only by SEM in samples apparently with ZSM-23 as
UHMWPE 426 512 100 —
unique phase through XRD. This which directly influences size and
UHMWPE + SiO2 427 506 99.2 0.6
shape because ZSM-5 has higher surface areas than ZSM-23. Z-IPA 325 428 95.37 4.63
The results obtained from the NH3-TPD analysis indicate that post- AZ-IPA 325 416 98.4 1.6
synthesis treatment promoted a decrease in the density of weak acid Z-ETG 349 449 95.77 4.23
AZ-ETG 349 436 98.28 1.72
sites in all catalysts due to leaching of extra-framework superficial
Z-PYR 328 467 96.64 3.36
aluminum species, such as Al(OH)2+ and Al(OH)2+, characterized as AZ-PYR 328 416 98.6 1.4
weak Lewis acid sites [45,46]. The samples of the IPA and PYR series Z-DMF 335 430 97.25 2.75
showed an increase in the strong and total acid sites densities, conse- AZ-DMF 335 419 98.1 1.9
quently denote an increment in the maximum temperature (acid a
strength), being this attribute to the extraction of Si atoms from the Obtained in DTG curve.
b
In the final temperature of 600 °C (normalized to UHMWPE wt.).
zeolite structure and, therefore, the acidity of these catalysts increases. c
Calculated by the Eq. (1).
Inverse behavior was observed for the samples from the ETG and DMF
series, with a reduction in the strong and total acid sites density, ac-
3.2. Polyethylene catalytic cracking
companied by a decrease in maximum temperatures. This can be at-
tributed, as described by Verboekend et al. [47] for zeolite ZSM-22
The thermogravimetric curves for catalytic degradation of
(structure similar to ZSM-23), to a certain degree of framework Al ex-
UHMWPE under heating rate of 10 °C.min−1 are shown in Fig. 2. The
traction of some materials after the wear and/or partial destruction of
TG and DTG curves indicate that the decomposition of UHMWPE, with
the "needle" crystals promoted by the alkaline treatment, generating Al
and without catalyst, occurs at a single stage of mass loss.
deposits under the external surface and causing the blockage of the
The UHMWPE + SiO2 mixture behaves similarly to the pure
pores. Following the subsequent acid treatment, these Al deposits are
polymer, as indicated by the similar values of the initial and final
leached from the external surface causing a decrease in the acidity.
temperatures of the polymer decomposition reaction (Table 2), con-
These results indicate that for these one-dimensional "needle" mor-
firming the inert character of silica in the polymeric degradation pro-
phology materials, acidity is not only related to the SiO2/Al2O3 ratio of
cess. Furthermore, the degradation of UHMWPE in the presence of
the structure, but possibly also to the coordination of aluminum atoms
amorphous silica produced a small amount of coke, ca. 0.6 % (Table 2),
inside and outside the crystal structure.
demonstrating negligible catalytic activity compared to the zeolites.
The addition of zeolite catalysts had a significant effect on reducing
degradation temperatures compared to pure UHMWPE. In thermal de-
gradation, the random bond cleavage mechanism prevails, while the

Fig. 2. (a) TG and (b) DTG curves obtained in the degradation of UHMWPE under heating rate of 10 °C.min−1.

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B.J.B. Silva, et al. Applied Catalysis B: Environmental 267 (2020) 118699

presence of active sites on the catalyst surface offers many possibilities materials depend on several factors, being the main of them the tem-
for other reaction mechanisms [48]. perature, the type and the amount of catalyst added to the system. The
The thermogravimetric curves of the degradation processes con- reaction rate and others kinetic parameters for each system should be
ducted with the parent and modified catalysts (Fig. 2) show no sig- determined through experimental data, however due to complexity of
nificant differences for the IPA, ETG and DMF series samples. However, the polymers degradation reactions, the conventional methods for de-
in the case of PYR samples, the modified catalyst induced a reduction in termination of the kinetic data are difficult of be applied. The kinetics of
the degradation temperature compared to the parent material. This thermal degradation of polymers is generally expressed by the fol-
difference may be associated with the MFI (zeolite ZSM-5) phase in- lowing typical kinetic Eq. (2) [50–52]:
tergrowth during crystallization of ZSM-23 with pyrrolidine (observed
d
by X-ray diffraction), since ZSM-5 has a three-dimensional structure =k ×f( )
(2)
dt
with pore size greater than ZSM-23. Probably, the regions formed by
the MFI phase are totally or partially surrounded by the MTT phase where α is the conversion degree or the fraction decomposed, calcu-
(ZSM-23) in the parent material, making the polymer molecules ac- lated according to Eq. (3):
cessibility more restricted. = (W0 Wt / W0 Wf ) (3)
After the desilication process, the dissolution of parts of the crystals
generates a secondary porosity with greater accessibility of the polymer being W0, Wt and Wf the initial, time t, and final weights of the polymer,
molecules, causing a decrease in cracking temperature range, as shown f(α) is the kinetic model function, d dt is the rate of conversion, and k is
in Fig. 2. Additionally, the contamination by ZSM- 5 explains the su- the temperature-dependent degradation rate constant which can be
perior textural properties and acidity observed for PYR series samples expressed as the Arrhenius Eq. (4):
compared to the other catalysts. Ea
Table 2 show thermogravimetric values obtained in the degradation k = Aexp
RT (4)
of UHMWPE with zeolites, under heating rate of 10 °C.min−1. It can be
noted that all zeolites caused decomposition effects, considerably re- where A is the pre-exponential factor, Ea is the apparent activation
ducing the initial and final degradation temperature of UHMWPE. energy of the degradation reaction, R is the universal gas constant, and
Comparing the zeolites to each other, it is observed that the modified T is the absolute temperature. The substitution of Eq. (4) into Eq. (2)
zeolites provided the lowest final temperature values in relation to their gives
parents. This fact can be explained by the greater accessibility of d Ea
polymeric macromolecules to the active sites in these materials, as well = Aexp f( )
dt RT (5)
as the reduction of the diffusional pathway of the formed products.
The presence of zeolitic catalysts in the cracking process promotes a Eq. (5) can be considered as a general expression for isothermal
coke deposition on external surface and pore opening, thus blocking the conditions. In the case of non-isothermal conditions where the sample is
diffusional pathway of molecules inside the micropores. Coke formation heated with a constant heating rate, = dT dt , Eq. (5) can be trans-
on the surface of the modified catalysts is reduced in relation to the formed into an equation describing the degradation reaction rate as a
parents, possibly because they are constituted by a bimodal pore system function of temperature and then can be rewritten as follows:
(micro-mesopores), which are effective in suppressing carbon deposits. d A Ea
= exp f( )
Another important parameter obtained from the DTG curves was the dT RT (6)
maximum degradation temperatures (TMax), which are shown in
Table 3. The results show that the addition of zeolites to the polymer Although the polymer degradation is complicated, in many studies,
promotes a significant reduction in the UHMWPE degradation TMax the degradation reaction is assumed to be a simple nth order reaction
values at the different heating rates studied, showing the effectiveness and the kinetic model function, f(α), is expressed as (1-α)n where n is
of the catalysts. DTG peak temperatures were also shifted to lower the order of reaction [51,53]
temperatures depending on the activity of the catalysts. The rising The kinetic model can be obtained in its integral form (g(α)), as
temperatures for different rates can be explained by the increased presented in Eq. (7), by integrating Eq. (6) between the limits α = 0 to
amount of energy supplied in heat form, for the same increment of time α = α that correspond to the degree of conversion, and t = 0 to t = t,
[49]. the time limits required for the conversion to take place [54].
The pattern of thermal and catalytic degradation of polymeric d t
g( ) = = k (T ). dt = k (T ). t
0 f( ) 0 (7)

Table 3 From the substitutions already described in Eqs. (4) to (6), the in-
Thermogravimetric values obtained in the degradation of UHMWPE under tegration of Eq. (7) from an initial temperature T0 to the peak tem-
different heating rates (β). perature Tp and with the degree of conversion varying between α = 0
Sample TMax/a°C
and α = α, leads to Eq. (8) [54,55].
Ea
d A Tp
β=5 β = 10 β = 20 β = 30 g( ) = = . e RT .dT
(°C. min−1) (°C. min−1) (°C. min−1) (°C. min−1)
0 f( ) T0 (8)

UHMWPE 471 484 497 505 If the temperature value (T0) is low enough, it can be assumed that
UHMWPE 467 481 500 508 α = 0, since at low temperatures there would be no conversion, and
+ SiO2 that there is no reaction between 0 and T0, resulting in Eq. (9) [56].
Z-IPA 390 392 401 416
Ea
AZ-IPA 388 390 399 418 A T
Z-ETG 394 405 425 437
g( ) = . e RT .dT
0 (9)
AZ-ETG 383 390 398 411
Z-PYR 389 432 466 487 Kinetic parameters (A, Ea, and n) from isothermal and non-iso-
AZ-PYR 382 395 403 430
thermal TG data can be determined by different methods (model-fitting
Z-DMF 386 400 403 424
AZ-DMF 389 398 406 417 and isoconversion-free model), which involve integration, differentia-
tion or approximation procedures to solve Eqs. (5) and (6) [53,57]. The
a
Obtained in DTG curve. model-fitting methods enable the fitting of various models to

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B.J.B. Silva, et al. Applied Catalysis B: Environmental 267 (2020) 118699

Fig. 3. Conversion data obtained from the TG curves with β = 10 C.min−1.

Table 4 the assumption of a kinetic model (f(α)), being able to assess the type of
Conversion values of the samples at maximum degradation rates (αMax). reaction model and if the kinetic parameters remain constant. For in-
Sample Heating rates (β)
stance, variation in the activation energy with the conversion indicates
(°C. min−1) that the process is complex (multistep reaction); on the other hand, if
the activation energies does not depend on conversion, the process is
β=5 β = 10 β = 20 β = 30 considered simple (single step reaction) [53,58].
UHMWPEa 0.707 0.716 0.622 0.616
The Flynn-Wall-Ozawa method (FWO) [32–34] is a well-known
UHMWPE + SiO2 0.492 0.422 0.479 0.500 representative of model-free approaches, which involves an approx-
Z-IPA 0.586 0.462 0.402 0.368 imation of Eq. (9), allowing the isothermal variation of the heating rate
AZ-IPA 0.644 0.535 0.461 0.457 (β). This method is isoconversional and can be applied to estimate ac-
Z-ETG 0.304 0.302 0.255 0.223
tivation energy of a given chemical reaction as a function of tempera-
AZ-ETG 0.410 0.389 0.380 0.357
Z-PYR 0.553 0.476 0.463 0.455 ture or enthalpy, from mass loss data (at different heating rates).
AZ-PYR 0.574 0.553 0.544 0.523 Bianchi et al. [54] describe that the FWO method is based on Doyle's
Z-DMF 0.484 0.483 0.441 0.430 linear approximation [59] for heterogeneous chemical reactions. Thus,
AZ-DMF 0.573 0.554 0.468 0.439 the mathematical resolution can be obtained according to Eq. (10),
a where g(α) (is the integral form of kinetic model, i.e., g(α) = kt) is a
Self-degradation without catalyst.
relationship as a function of conversion [56].
conversion versus temperature curves and the simultaneous determi-
nation of the activation energy and frequency factor. Model-free ap- AEa 0.45Ea
log( ) = log 2.315
proach allows to estimate Ea values as a function of conversion without Rg ( ) RT (10)

6
B.J.B. Silva, et al.
Fig. 4. log β vs 103T−1 curves for (a) UHMWPE - R2 = 0.99845–0.99995, (b) Z-PYR + UHMWPE – R2 = 0.8984–0.99662 and (c) AZ-PYR + UHMWPE -
R2 = 0.8984–0.9989.
where β is the heating rate, A is the pre-exponential factor, Ea is the
apparent activation energy, R is the gas constant and α is the conversion
(fractional weight loss). In the FWO method it is assumed that the re-
action rate at a given conversion (α) is a function of temperature (T)
only. Therefore, at different heating rates (β), at constant conversion
(α(T)), a linear relationship is observed by plotting a log (β) versus 1/T
plot, and the apparent activation energy (Ea) is obtained from the slope
of the linear fit [32–34]. This calculated activation energy is called the
apparent activation energy because it is the sum of the activation en-
ergies of chemical reactions and physical processes that occur during
conversion [60]. The major advantage of the method proposed by FWO
is that Ea values are easily obtained without knowledge of the reaction
control mechanism [56].
The mass losses determined by thermogravimetric curves were
transformed to conversion data and subjected to kinetic treatment by
the FWO model. Considering that the total mass loss corresponds to 100
% of the conversion, the mass losses at lower temperatures were nor-
malized to the total mass loss. Fig. 3 shown a set of conversion curves,
where it is observed that the samples containing zeolites presents lower
temperatures for UHMWPE degradation, while that the sample con-
taining 30 % wt. of amorphous silica, practically degraded at the same
temperature range of pure polymer.
Conversion values at the temperature of maximum degradation rate,
αMax, are listed in Table 4 for the all heating rates employed. Generally,
this value is accepted as the decisive parameter to distinguish reaction
model for kinetic studies [61,62]. We used it here to compare how the
reaction rate differs over the zeolites during the degradation. The
7
Applied Catalysis B: Environmental 267 (2020) 118699
conversion of UHMWPE at the temperature of maximum degradation
rate is between 0.61 and 0.72 for self-degradation without catalysts.
The modified zeolites have been shown to achieve a higher degree of
conversion in relation to their parents in all studied heating rates, de-
noting the positive impact of post-synthesis treatment on the catalytic
activity of these zeolites in the UHMWPE degradation process.
Fig. 4 presents three examples of the plot of the logarithmics plot of
the heating rates against the reciprocals of the corresponding values of
the absolute temperatures that produce a straight line, whose slope is
proportional to the activation energy.
The Fig. 5 display the values of average activation energy in func-
tion of the conversion for the degradation of pure UHMWPE and of
UHMWPE + 30 % wt. catalysts. UHMWPE + SiO2 (198 kJ.mol−1)
shows average Ea values close to those obtained for pure UHMWPE
(211 kJ.mol−1). The addition of zeolites showed a reduction in average
Ea values in relation to pure polymer, showing the strong influence of
catalyst acidity on the degradation reaction. The modified catalysts had
lower energy level (IPA 159 to 117 kJ.mol−1, ETG 176 to
133 kJ.mol−1, PYR 133 to 74 kJ.mol−1 and DMF 174 to 143 kJ.mol−1
series) compared to their parents. The most expressive result obtained
by the PYR series samples, possibly due to the fact that this material
presents the ZSM-23 one-dimensional and ZSM-5 three-dimensional
phases, simultaneously, providing different pore size and shape, which
are important parameters for the catalytic performance of the zeolites
in the polymer degradation in terms of diffusional effects [63], reflected
in the high area and volume values obtained by these materials.
Thermal self-degradation of polymers consists of many complex
B.J.B. Silva, et al.
Fig. 5. Activation energy versus conversion for UHMWPE degradation reaction.
processes, such as random chain scission, radical transfer, etc., which occurs
simultaneously during degradation. In fact, these steps have their individual
rates and activation energies. TG method is able to the measure overall rate
of degradation and the apparent activation energy of the process. Especially,
in case of catalytic degradation of polymers, it becomes more complex to
discuss the degradation rate depending on the structural properties of cat-
alysts. It has been known that activity of the catalyst is based on the for-
mation of reactive intermediates to reduce the activation energy of the
corresponding partial reactions. This effect reduces the apparent activation
energy of thermal degradation process [64]. The catalysts cannot affect the
enthalpy of CeC bond scission during decomposition.
The results of activation energy, acidity and textural properties
obtained, show that the relatively easy degradation of UHMWPE on the
modified zeolites is influenced not only by the acid character of the
materials, being another preponderant factor, the presence of micro-
mesoporosity in these materials which promotes easier diffusion of
reagents/products to the internal active sites of zeolitic structures
compared to microporous parents.
4. Conclusions
Post-synthesis treatment (desilication and acid washing) of ZSM-23
zeolite synthesized with different structure directing agents generates
materials with greater accessibility due to the dissolution of part of the
structure and formation of secondary porosity in the mesopore range.
Although this type of treatment is advantageous from the point of view
of textural properties (larger external surface area and increased pore
volume), the process removes a portion of aluminum from the zeolite
structure causing a decrease in surface acidity.
The results of UHMWPE degradation reactions in the presence of
parent and modified zeolites indicate that, despite differences in surface
acidity, the catalytic activity measured by thermogravimetry is little
affected. However, the amount of coke formed in the process with the
desilicated materials is considerable lower than in the case of the parent
catalysts. This can be attributed to the more open porous structure
8
Applied Catalysis B: Environmental 267 (2020) 118699
(containing secondary porosity) and the lower external surface acidity
that restrict coke formation reactions.
The addition of 30 % wt. of the microporous and hierarchical ZSM-
23 resulted in a significant decrease in the temperature and average Ea
for the UHMWPE degradation process. The modified zeolites showed
better catalytic activity and lower energy level in polymer degradation
in relation to its parents, highlighting the combined importance of
acidity and presence of bimodal pore system to overcome the diffu-
sional constraints imposed due to the microporous character of zeolites.
This limitation is more accentuated in structures with one-dimensional
pore system such as the parent ZSM-23.
The PYR serie samples presented superior catalytic properties in
comparison to the samples synthesized with IPA, ETG and DMF. This
behavioral difference is associated with the MFI (zeolite ZSM-5) phase
intergrowth in PYR materials.
The results indicate a potential advantage of the use of these hier-
archical catalysts in the catalytic degradation of polymers when com-
pared to conventional zeolites.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors are grateful for the financial support of the
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
(CAPES), through a research grant and Petrobras.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.apcatb.2020.118699.
B.J.B. Silva, et al. Applied Catalysis B: Environmental 267 (2020) 118699

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