Next Article in Journal
Experimental Evaluation of Tensile Performance of Aluminate Cement Composite Reinforced with Weft Knitted Fabrics as a Function of Curing Temperature
Previous Article in Journal
Numerical Study of the Effect of Thixotropy on Extrudate Swell
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Polymers
Volume 13
Issue 24
10.3390/polym13244384
polymers-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Dependence on Film Thickness of Guest-Induced c Perpendicular Orientation in PPO Films

by
Baku Nagendra
,
Emanuele Vignola
,
Christophe Daniel
,
Paola Rizzo
and
Gaetano Guerra
*
Dipartimento di Chimica e Biologia, INSTM Research Unit, Università di Salerno, Via Giovanni Paolo II 132, 84084 Fisciano, Italy
*
Author to whom correspondence should be addressed.
Polymers 2021, 13(24), 4384; https://doi.org/10.3390/polym13244384
Submission received: 4 November 2021 / Revised: 30 November 2021 / Accepted: 10 December 2021 / Published: 14 December 2021
(This article belongs to the Topic Polymer Crystallization)
Browse Figures
Versions Notes

Abstract

:
For poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) films exhibiting nanoporous-crystalline (NC) phases, c⊥ orientation (i.e., crystalline polymer chain axes being preferentially perpendicular to the film plane) is obtained by crystallization of amorphous films, as induced by sorption of suitable low-molecular-mass guest molecules. The occurrence of c⊥ orientation is relevant for applications of NC PPO films because it markedly increases film transparency as well as guest diffusivity. Surprisingly, we show that the known crystallization procedures lead to c⊥ oriented thick (50–300 μm) films and to unoriented thin (≤20 μm) films. This absence of crystalline phase orientation for thin films is rationalized by fast guest sorption kinetics, which avoid co-crystallization in confined spaces and hence inhibit formation of flat-on lamellae. For thick films exhibiting c⊥ orientation, sigmoid kinetics of guest sorption and of thickening of PPO films are observed, with inflection points associated with guest-induced film plasticization. Corresponding crystallization kinetics are linear with time and show that co-crystal growth is poorly affected by film plasticization. An additional relevant result of this study is the linear relationship between WAXD crystallinity index and DSC melting enthalpy, which allows evaluation of melting enthalpy of the NC α form of PPO (ΔHmο = 42 ± 2 J/g).

Graphical Abstract

1. Introduction

Orientation of polymer chain axes (c axes) in crystalline lamellae are perpendicular or nearly perpendicular (for monoclinic and triclinic unit cells) to the lamellar planes. Crystalline lamellae can be oriented with respect to the polymer film plane, mainly for films having a thickness lower than 1 μm. Common orientations are the so-called edge-on or flat-on [1,2,3,4,5,6,7], which lead to planar orientations of c axes being preferentially parallel or perpendicular to the film plane, respectively.
Even in the absence of mechanical stresses, different kinds of planar orientations [8,9,10,11,12,13,14] can be easily achieved for polymer films exhibiting co-crystalline (CC) phases, i.e., where a host polymer includes low-molecular-mass guest molecules in crystalline cavities [15,16,17,18,19,20,21]. In fact, even for thickness of several hundredths of microns, different kinds of planar and uniplanar orientations (i.e., preferential orientations of a crystalline axis or of a crystalline plane with respect to the film plane, respectively) have been observed for films exhibiting CC phases of syndiotactic polystyrene [15,16,17], poly-(L-lactic acid) [18,19] and poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) [20,21].
The kind and degree of planar and uniplanar orientations are relevant for properties of CC polymer phases. In fact, in CC films, the orientation of the host polymer can induce orientation of active guest molecules, being fluorescent [22,23,24,25], magnetic [26,27], ferroelectric [28], photo-reactive [29] or chiral-optical [30].
planar and uniplanar orientations of CC phases are also maintained after guest removal procedures leading the nanoporous-crystalline (NC) phases: δ [31,32] and ε [33,34] for sPS, α and β for PPO [35,36,37]. This is mainly relevant for guest sorption kinetics because guest diffusivity can be largely changed by proper selection of the orientation of the NC phase [21,38,39,40,41]. Maximum diffusivity is generally observed for NC films with orientation of chain axes (and molecular channels) [17] preferentially perpendicular to the film plane [21,40,41]. This phenomenon is particularly relevant for NC PPO films with c⊥ orientation, which exhibit diffusivities comparable with those of NC powders and not far from those of NC aerogels [40]. As for PPO, it is also worth noting the much higher diffusivity of NC films with respect to amorphous films, although the latter are well known for their high free volume and fast diffusivities [42,43,44,45,46,47,48,49].
NC PPO films with c⊥ orientation also have the advantage of transparency comparable with those of amorphous PPO films [50]. This high transparency was rationalized on the basis of the positive birefringence of the polymer and of density and refractive index of the NC phases being lower than those of the corresponding amorphous phase [50]. Hence, PPO films with high guest diffusivity and transparency (both relevant for many possible applications) are achieved by using crystallization procedures leading to c⊥ orientation.
For PPO, c⊥ orientation was only obtained by slow guest induced crystallization in amorphous films [21,40,50] and was attributed to formation of flat-on crystalline lamellae in nanoconfined layers [51].
In the present paper, for films as obtained by guest (dibenzyl ether)-induced crystallization of amorphous films, we study the dependence of planar orientation on film thickness. The paper also compares kinetics of guest sorption with corresponding kinetics of crystallization and thickness variation of PPO amorphous films.

2. Materials and Methods

PPO with 350 kg/mol molecular weight (P6130 grade) was supplied by Sabic (Sittard, The Netherlands). Guest molecules: dibenzyl ether (BE) and chloroform (CHCl3) were purchased from Aldrich (Milan, Italy).
Amorphous PPO films with different thickness (~5–300 μm) were prepared by solution casting in chloroform under fast solvent evaporation conditions (atmospheric pressure and T ≈ 60 °C).
PPO CC films were prepared by guest-induced crystallization of amorphous films. Amorphous PPO films were immersed in liquid BE, at ~20 °C for immersion time in the range 5–2800 min. For kinetics studies, these CC PPO films just pulled out of BE liquid were immediately quenched in acetonitrile solvent in order to stop further crystallization.
PPO NC films were obtained from PPO CC films by guest extraction with supercritical carbon dioxide (scCO2) using SFX 200 equipment (ISCO Inc., Austin, TX, USA) at P = 250 bar, T = 40 °C and with extraction time t = 4 h. An alternative method of guest extraction, consisting of liquid acetonitrile sorption at room temperature followed by desorption in air again at room temperature, was also used.
Fourier transform infrared (FTIR) spectra were obtained at a 2.0 cm−1 resolution, with a Vertex 70 Bruker FTIR spectrometer (Bruker, Germany).
Differential Scanning Calorimetry (DSC) was conducted in TA Q2000 equipment from TA Instruments (New Castle, DE, USA). The reported DSC scans were conducted on NC PPO films at heating rate of 10 °C/min under controlled nitrogen gas flow.
Two-dimensional (2D) wide-angle X-ray diffraction (WAXD) patterns were performed in D8 QUEST Bruker diffractometer (CuKα radiation, Bruker, Karlsruhe, Germany) with X-ray beam perpendicular and parallel to the film surface, thus obtaining patterns that are called THROUGH and EDGE, respectively.
Radial profiles were collected (by DIFFRAC.EVA software, Bruker, Karlsruhe, Germany) by averaging the intensities along circles, as a function of the diffraction angle (2θ). Equatorial and meridional profiles were collected along the equatorial and meridional directions of the collected 2D patterns.
Crystallinity indexes were determined by using radial profiles of 2D WAXD THROUGH patterns. In particular, we have applied the classical method of resolving these patterns into two areas corresponding to diffraction halo of the amorphous phase and to diffraction peaks of the crystalline phase, for 3° < 2θ < 30°.
The degree of orientation of the chain axes of the crystalline phase (fc) was evaluated by using the Herman’s orientation function:
f c = ( 3 cos 2 γ ¯ − 1 ) / 2
where cos2γ was determined by azimuthal scan of the 001 reflection of the NC α form, at 2θCuKα = 16.8°. In this framework, fc = 0 corresponds to unoriented crystalline phases, whereas fc = −0.5, corresponds to the limit c⊥ orientation, where chain axes of all crystallites are perpendicular to the film plane.

3. Results and Discussion

3.1. Dependence of Guest-Induced c⊥ Orientation on Film Thickness

2D-WAXD patterns, as taken with the X-ray beam parallel to the film plane (EDGE patterns), of amorphous PPO films of different thickness in the range 20–300 μm, after crystallization induced by equilibrium room-temperature sorption of BE followed by BE desorption by scCO2, are shown in Figure 1. As discussed in [36], BE sorption leads to PPO/BE co-crystalline form, while the subsequent guest desorption leads to the NC α form.
For patterns of thicker films (from 50 μm up to 300 μm, Figure 1b–d), all hk0 reflections are present as arcs centered on the meridian. This clearly indicates, as already described for films of thickness of 50–90 μm [21,40,50], the occurrence of c⊥ orientation. Rather surprisingly, the thinner film (20 μm, Figure 1a) only exhibits diffraction rings, which clearly indicate absence of crystalline phase orientation.
The degree of orientation (fc, also indicated on the top of the patterns of Figure 1) is plotted versus thickness of seven starting amorphous PPO films, in Figure 2. For a better understanding of the plot of Figure 2, it is worth citing that the limit degree of c⊥ orientation, with all polymer chain axes of crystallites being perfectly perpendicular to the film plane, is fc = −0.5. Melting enthalpies of these films are also shown on the right scale in Figure 2. It is apparent that melting enthalpies and hence degrees of crystallinity are poorly dependent on film thickness while, on the contrary, the degree of crystalline phase orientation is maximum for the 150 μm film (fc = −0.3), it is substantially reduced for thicker films (e.g., fc = −0.16 for 300 μm) and it is negligible for thickness ≤ 20 μm.
Results strictly similar to those of Figure 1 and Figure 2 are observed if BE desorption occurs by sorption/desorption of acetonitrile, rather than by scCO2 extraction.

3.2. Kinetics of Be Guest Sorption from Amorphous Films of Different Thickness

This rather unexpected absence of crystalline phase orientation in thinner films can be rationalized in the framework of the recently proposed mechanism, for which c⊥ orientation is favored by slow uptakes of the guest-inducing polymer co-crystallization [51].
BE sorption kinetics from amorphous PPO films of different thickness, based on the absorbance of the BE FTIR peak at 2215 cm−1, are shown in Figure 3. The kinetics of guest sorption of 5 μm and 20 μm film are not reported because they are too fast for the used FTIR method. The BE equilibrium uptake for all the PPO films is in the range 70–75 wt%, nearly independently of the thickness of the starting amorphous film, while it is reached in seconds, minutes and hours for 20 μm, 50 μm and 150 μm films, respectively. The average diffusivity for the kinetics of Figure 3a, as evaluated by the corresponding Fick’s plot up to variation of 30% (Figure 3b), is ~1.3 ± 0.5 × 10−7 cm2 sec−1.
The absence of orientation for guest-induced crystallization of thin films (Figure 2) is possibly associated with their fast guest sorption kinetics. In the framework of our hypothesis [51], fast guest sorption can avoid co-crystallization in confined spaces and hence formation of flat-on lamellae.
This hypothesis is compatible with SEM images of sections of the NC films. For instance, SEM images of 20 μm and 100 μm amorphous films, after BE-induced crystallization followed by BE extraction by scCO2 are reported in Figure 4a–d, respectively. The presence of flat-on lamellae for the thicker film (Figure 4d) is apparent, as is the presence of an unoriented fibrillar morphology for the thinner film (Figure 4b).

3.3. Kinetics of Guest-Induced Film Thickening and Polymer Crystallization

Guest uptake in PPO amorphous films induces polymer co-crystallization and leads to remarkable increases (even doubling) of film thickness, which remains essentially unaltered even after complete guest removal).
Kinetics of BE guest sorption (curves a and a’) and kinetics of film thickening (curves b and b’), for films with thickness of 100 μm and 150 μm, are compared in Figure 5A,B, respectively. It is apparent that guest uptake and thickness increase exhibit similar kinetics, with similar sigmoid shapes.
This sigmoid behavior is possibly related to the well-known progressive Tg reduction as a consequence of sorption of plasticizing molecules in amorphous phases [52]. When, for high guest content, Tg becomes close to room temperature, the transformation of the glassy phase in a rubbery phase leads to a jump in guest uptake as well as in film thickness.
Kinetics of crystallization as obtained by WAXD and DSC measurements on the NC films are shown as curves c,c’ and d,d’ in Figure 5A,B, respectively.
2D-WAXD patterns (as taken with the X-ray beam perpendicular to the film plane, THROUGH patterns) of amorphous PPO films, after crystallization induced by BE guest sorption/desorption, only exhibit diffraction rings [21]. Radial diffraction profiles of these 2D-WAXD THROUGH patterns, for a 100 μm film, after different sorption times (in the range 20–2800 min) are shown in Figure 6a. It is clearly apparent that, as a consequence of sorption, diffraction peaks typical of the NC α form (e.g., 100, 010, 210 and 310) [35,36] appear and progressively increase their intensity. Crystallinity indexes (χc) as evaluated on the basis of the WAXD THROUGH patterns for 100 μm and 150 μm films are collected in the third column of Table 1 and Table 2 and plotted in curves c and c’ of Figure 5A,B, respectively.
DSC scans of the NC α form films of Figure 6a are shown in Figure 6b. For the amorphous as well as for the poorly crystallized films (corresponding to sorption time < 100 min), the PPO glass transition temperature (Tg), at nearly 220 °C, is clearly apparent. As the sorption time increases, a melting peak appears, and its area progressively increases up to a melting enthalpy close to 22 J/g. Melting enthalpies as evaluated for films crystallized after different sorption times for 100 μm and 150 μm films are collected in the fourth column of Table 1 and Table 2 and plotted in curves d and d’ of Figure 5A,B, respectively. It is worth noting that for PPO samples, melting enthalpy is an appropriate quantity to evaluate degree of crystallinity, due to the negligible PPO re-crystallization during DSC heating scans [53,54].
For both films with thickness of 100 μm and 150 μm, crystallinity indexes (χc, as evaluated on the basis of the WAXD patterns, like those of Figure 6a) are plotted versus melting enthalpies (ΔHm, as evaluated by DSC scans, like those of Figure 6b) in Figure 7. A linear relationship between χc and ΔHm appears, whose extrapolation to χc = 100% allows a rough evaluation of the melting enthalpy of fully crystalline α form PPO samples (ΔHmο = 42 ± 2 J/g). To reduce the extrapolation error, two additional points, corresponding to the 100 μm film after 2800 min of BE sorption followed by annealing at 40 °C and 60 °C for 12 h (last two rows of Table 1), are added. This ΔHmο value as obtained by the extrapolation procedure of Figure 7 compares well with the value as determined by measuring the depression of melting temperature in mixtures with chloronaphthalene (42 ± 8 J/g) [55].
Plots of Figure 5 show that crystallinity index (plots c) and melting enthalpy (plots d) present similar kinetics, with roughly linear increases before gradual approach to their plateau values, rather than sigmoid increases as observed for guest uptake (plots a) and thickness increase (plots b). This indicates that PPO crystallization, in the co-crystalline form with BE guest, occurs already for low guest concentrations in confined layers imposing formation of flat-on lamellae. By using the terminology of solvent-induced crystallization (often indicated as SINC) of amorphous films [56,57,58,59,60,61], the kinetics of crystallization is controlled by crystal growth rather than by guest diffusion. Kinetics of crystallization being linear with time indicate that co-crystal growth is poorly affected by film plasticization.

4. Conclusions

The planar orientation exhibiting crystalline chain axes preferentially perpendicular to the film plane (c⊥ orientation), which is observed for CC and NC PPO films as obtained by bulky guest (e.g., benzyl ether)-induced crystallization, depends on the thickness of the starting amorphous film. In fact, surprisingly, c⊥ orientation occurs only for thick films (50–300 μm), while it is not observed for films with thickness lower than or equal to 20 μm.
This unexpected behavior can be rationalized in the framework of the mechanism of planar oriented crystallization as proposed in a recent paper [51]. In fact, the absence of orientation for guest-induced crystallization of thin films is associated with fast guest sorption, which avoids co-crystallization in confined spaces and hence hinders formation of flat-on lamellae.
Kinetics of guest uptake and film thickening exhibit sigmoid shapes, which are due to the progressive Tg reduction as a consequence of sorption of plasticizing molecules in amorphous phases [61]. When for high guest content Tg becomes close to room temperature, the transformation of the glassy phase in a rubbery phase leads to a jump in guest uptake as well as in film thickness.
Crystallization kinetics, as measured by WAXD and DSC techniques, show a completely different behavior with degree of crystallinity increasing linearly with sorption time before approaching their plateau values. This indicates that kinetics of PPO guest-induced co-crystallization, leading for thick films to c⊥ orientation, is controlled by crystal growth rather than by guest diffusion.
An additional relevant result of this study is the linear relationship between WAXD crystallinity index and DSC melting enthalpy, which allows for the evaluation of melting enthalpy of a 100% α form PPO sample (ΔHmο = 42 ± 2 J/g).

Author Contributions

B.N. and G.G.; methodology: B.N. and G.G.; investigation and writing original draft: B.N. and G.G.; Data curation: B.N., C.D., E.V., P.R. and G.G.; supervision and writing—review & editing: G.G., C.D. and P.R. All authors have read and agreed to the published version of the manuscript.

Funding

B.N. was supported by a research grant from MIUR (PON “R&I” 2014–2020; ARS01_01398”INPOS”).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available on request from the corresponding author.

Acknowledgments

The authors are grateful to Ivano Immediata for technical support and useful discussions.

Conflicts of Interest

The authors declare that there are no conflict of interest regarding the publication of this paper.

References

  1. Wegner, G. Ultrathin films of polymers: Architecture, characterization and properties. Thin Solid Film. 1992, 216, 105–116. [Google Scholar] [CrossRef]
  2. Schonherr, H.; Frank, C.W. Ultrathin films of poly(ethylene oxides) on oxidized silicon. 1. Spectroscopic characterization of film structure and crystallization kinetics. Macromolecules 2003, 36, 1188–1198. [Google Scholar] [CrossRef]
  3. Wang, Y.; Chan, C.M.; Ng, K.M.; Li, L. What Controls the Lamellar Orientation at the Surface of Polymer Films during Crystallization? Macromolecules 2008, 41, 2548–2553. [Google Scholar] [CrossRef]
  4. Yang, P.; Han, Y. Crystal Growth Transition from Flat-On to Edge-On Induced by Solvent Evaporation in Ultrathin Films of Polystyrene-b-Poly(ethylene oxide). Langmuir 2009, 25, 9960–9968. [Google Scholar] [CrossRef]
  5. Rueda, D.R.; Hernández, J.J.; García-Gutiérrez, M.C.; Ezquerra, T.A.; Soccio, M.; Lotti, N.; Munari, A.; Perlich, J.; Serna, R. Flat-On Lamellae in Spin-Coated, Stable Films of Poly(propylene azelate). Langmuir 2010, 26, 17540–17545. [Google Scholar] [CrossRef] [Green Version]
  6. Chen, M.S.; Niskala, J.R.; Unruh, D.A.; Chu, C.K.; Lee, O.P.; Frechet, J.M.J. Control of Polymer-Packing Orientation in Thin Films through Synthetic Tailoring of Backbone Coplanarity. Chem. Mater. 2013, 25, 4088–4096. [Google Scholar] [CrossRef]
  7. Hu, R.; Pi, Y.; Wang, N.; Zhang, Q.; Feng, J.; Xu, W.; Dong, X.; Wang, D.; Yang, H. The formation of the S-shaped edge-on lamellae on the thin porous polylactic acid membrane via phase separation induced by water microdroplets. J. Appl. Polym. Sci. 2016, 133, 43355. [Google Scholar] [CrossRef]
  8. Heffelfinger, C.J.; Burton, R.L. X-ray determination of the crystallite orientation distributions of poly(ethylene terephthalate) films. J. Polym. Sci. 1960, 47, 289–306. [Google Scholar] [CrossRef]
  9. Pazur, R.J.; Purd’homme, R.E. X-ray Pole Figure and Small Angle Scattering Measurements on Tubular Blown Low-Density Poly(ethylene) Films. Macromolecules 1996, 29, 119–128. [Google Scholar] [CrossRef]
  10. Shibaev, V.; Bobrovsky, A.; Boiko, N. Photoactive liquid crystalline polymer systems with light-controllable structure and optical properties. Progr. Polym. Sci. 2003, 28, 729–836. [Google Scholar] [CrossRef]
  11. Rao, Y.Q.; Greener, J.; Avila-Orta, C.A.; Hsiao, B.S.; Blanton, T.N. The relationship between microstructure and toughness of biaxially oriented semicrystalline polyester films. Polymer 2008, 49, 2507–2514. [Google Scholar] [CrossRef]
  12. Jariyasakoolroj, P.; Tashiro, K.; Hai, W.; Yamamoto, H.; Chinsirikul, W.; Kerddonfag, N.; Chirachanchai, S. Isotropically small crystalline lamellae induced by high biaxial-stretching rate as a key microstructure for super-tough polylactide film. Polymer 2015, 68, 234–245. [Google Scholar] [CrossRef]
  13. Tatsumi, M.; Teramoto, Y.; Nishio, Y. Different orientation patterns of cellulose nanocrystal films prepared from aqueous suspensions by shearing under evaporation. Cellulose 2015, 22, 2983–2992. [Google Scholar] [CrossRef]
  14. Mueller, C.J.; Gann, E.; Singh, C.R.; Thelakkat, M.; McNeill, C.R. Control of Molecular Orientation in Polydiketopyrrolopyrrole Copolymers via Diffusive Noncovalent Interactions. Chem. Mater. 2016, 28, 7088–7097. [Google Scholar] [CrossRef]
  15. Rizzo, P.; Lamberti, M.; Albunia, A.R.; Ruiz de Ballesteros, O.; Guerra, G. Crystalline orientation in syndiotactic polystyrene cast films. Macromolecules 2002, 35, 5854–5860. [Google Scholar] [CrossRef]
  16. Rizzo, P.; Spatola, A.; De Girolamo Del Mauro, A.; Guerra, G. Polymeric Films with Three Different Uniplanar Crystalline Phase Orientations. Macromolecules 2005, 38, 10089–10094. [Google Scholar] [CrossRef]
  17. Albunia, A.R.; Rizzo, P.; Guerra, G. Polymeric Films with Three Different Orientations of Crystalline-Phase Empty Channels. Chem. Mater. 2009, 21, 3370–3375. [Google Scholar] [CrossRef]
  18. Rizzo, P.; Ianniello, G.; Venditto, V.; Tarallo, O.; Guerra, G. Poly(L-lactic acid): Uniplanar Orientation in Cocrystalline Films and Structure of the Cocrystalline Form with Cyclopentanone. Macromolecules 2015, 48, 7513–7520. [Google Scholar] [CrossRef]
  19. Nagendra, B.; Rizzo, P.; Daniel, C.; Baldino, L.; Guerra, G. c-Perpendicular Orientation of Poly(L-lactide) Films. Polymers 2021, 13, 1572. [Google Scholar] [CrossRef] [PubMed]
  20. Rizzo, P.; Ianniello, G.; Longo, S.; Guerra, G. Uniplanar Orientations and Guest Exchange in PPO Cocrystalline Films. Macromocules 2013, 46, 3995–4001. [Google Scholar] [CrossRef]
  21. Rizzo, P.; Gallo, C.; Vitale, V.; Tarallo, O.; Guerra, G. Nanoporous-crystalline films of PPO with parallel and perpendicular polymer chain orientations. Polymer 2019, 167, 193–201. [Google Scholar] [CrossRef]
  22. Venditto, V.; Milano, G.; De Girolamo Del Mauro, A.; Guerra, G.; Mochizuki, J.; Itagaki, H. Orientation and Microenvironment of Naphthalene Guest in the Host Nanoporous Phase of Syndiotactic Polystyrene. Macromolecules 2005, 38, 3696–3702. [Google Scholar] [CrossRef]
  23. Uda, Y.; Kaneko, F.; Tanigaki, N.; Kawaguchi, T. The First Example of a Polymer-Crystal–Organic-Dye Composite Material: The Clathrate Phase of Syndiotactic Polystyrene with Azulene. Adv. Mater. 2005, 17, 1846–1850. [Google Scholar] [CrossRef]
  24. Itagaki, H.; Sago, T.; Uematsu, M.; Yoshioka, G.; Correa, A.; Venditto, V.; Guerra, G. Guest Orientation in Uniplanar-Axial Polymer Host Films and in Co-Crystal Unit-Cell, Determined by Angular Distributions of Polarized Guest Fluorescence. Macromolecules 2008, 41, 9156–9164. [Google Scholar] [CrossRef]
  25. Sano, T.; Uchiyama, A.; Sago, T.; Itagaki, H. Fluorescence behavior of syndiotactic polystyrene and its derivative: Formation of a ground-state dimer in the solid state. Eur. Polym. 2017, 90, 114–121. [Google Scholar] [CrossRef]
  26. Kaneko, F.; Uda, Y.; Kajiwara, A.; Tanigaki, N. Molecular-Complex Formation of Syndiotactic Polystyrene with Stable Radical Molecules. Macromol. Rapid Commun. 2006, 27, 1643–1647. [Google Scholar] [CrossRef]
  27. Albunia, A.R.; D’Aniello, C.; Guerra, G.; Gatteschi, D.; Mannini, M.; Sorace, L. Ordering Magnetic Molecules within Nanoporous Crystalline Polymers. Chem. Mater. 2009, 21, 4750–4752. [Google Scholar] [CrossRef]
  28. Daniel, C.; Rufolo, C.; Bobba, F.; Scarfato, A.; Cucolo, A.; Guerra, G. Ferroelectric co-crystalline polymers. J. Mater. Chem. 2011, 21, 19074–19079. [Google Scholar] [CrossRef]
  29. Stegmaier, P.; De Girolamo Del Mauro, A.; Venditto, V.; Guerra, G. Optical recording materials based on photoisomerization of guest molecules of a polymeric crystalline host phase. Adv. Mater. 2005, 17, 1166–1168. [Google Scholar] [CrossRef]
  30. Rizzo, P.; Abbate, S.; Longhi, G.; Guerra, G. Circularly polarized luminescence of syndiotactic polystyrene. Opt. Mater. 2017, 73, 595–601. [Google Scholar] [CrossRef]
  31. De Rosa, C.; Guerra, G.; Petraccone, V.; Pirozzi, B. Crystal structure of the emptied clathrate form (*e form) of syndiotactic polystyrene. Macromolecules 1997, 30, 4147–4152. [Google Scholar] [CrossRef]
  32. Bhoje Gowd, E.; Shibayama, N.; Tashiro, K. Structural Changes in Thermally Induced Phase Transitions of Uniaxially Oriented δe Form of Syndiotactic Polystyrene Investigated by Temperature-Dependent Measurements of X-ray Fiber Diagrams and Polarized Infrared Spectra. Macromolecules 2006, 39, 8412–8418. [Google Scholar] [CrossRef]
  33. Petraccone, V.; Ruiz de Ballesteros, O.; Tarallo, O.; Rizzo, P.; Guerra, G. Nanoporous Polymer Crystals with Cavities and Channels. Chem. Mater. 2008, 20, 3663–3668. [Google Scholar] [CrossRef]
  34. Itagaki, H.; Sano, T.; Okabe, T.; Sano, S.; Ebihara, H.; Tomono, F.; Dohra, H. Polymerization of Aniline in Tubular Cavities of the Crystalline Phase of Syndiotactic Polystyrene: Proposal of a Preparation Method of Sophisticated Polymer Composites. ACS Macro Lett. 2017, 6, 1099–1103. [Google Scholar] [CrossRef]
  35. Daniel, C.; Longo, S.; Fasano, G.; Vitillo, J.G.; Guerra, G. Nanoporous Crystalline Phases of Poly(2,6-Dimethyl-1,4-phenylene)oxide. Chem. Mater. 2011, 23, 3195–3200. [Google Scholar] [CrossRef]
  36. Nagendra, B.; Cozzolino, A.; Daniel, C.; Rizzo, P.; Guerra, G.; Auriemma, F.; De Rosa, C.; D’Alterio, M.C.; Tarallo, O.; Nuzzo, A. Two nanoporous-crystalline forms of PPO and related co-crystalline forms. Macromolecules 2019, 52, 9646–9656. [Google Scholar] [CrossRef]
  37. Yu, A.; Alentiev, I.S.; Levin, M.I.; Buzin, N.A.; Belov, R.Y.; Nikiforov, S.V.; Chirkov, I.V.; Blagodatskikh, A.S.; Kechekyan, P.A.; Kechekyan, V.G.; et al. Gas transport parameters, density and free volume of nanocrystalline poly-2,6-dimethylphenylene oxide. Polymer 2021, 226, 123804. [Google Scholar] [CrossRef]
  38. Venditto, V.; De Girolamo Del Mauro, A.; Mensitieri, G.; Milano, G.; Musto, P.; Rizzo, P.; Guerra, G. Anisotropic Guest Diffusion in the δ Crystalline Host Phase of Syndiotactic Polystyrene: Transport Kinetics in Films with Three Different Uniplanar Orientations of the Host Phase. Chem. Mater. 2006, 18, 2205–2210. [Google Scholar] [CrossRef]
  39. Albunia, A.R.; Rizzo, P.; Guerra, G. Control of guest transport in polymer films by structure and orientation of nanoporous-crystalline phases. Polymers 2013, 54, 1671–1678. [Google Scholar] [CrossRef]
  40. Daniel, C.; Rizzo, P.; Nagendra, B.; Cozzolino, A.; Guerra, G. High guest diffusivity of PPO films with perpendicular orientation of chain axes of nanoporous-crystalline phases. Polymer 2021, 229, 124005. [Google Scholar] [CrossRef]
  41. Cozzolino, A.; Nagendra, B.; Rizzo, P.; Daniel, C.; Guerra, G. Fast uptake of organic pollutants from dilute aqueous solutions by nanoporous-crystalline PPO films with c-perpendicular orientation. J. Eur. Polym. 2021, 161, 110864. [Google Scholar] [CrossRef]
  42. Alentiev, A.; Drioli, E.; Gokzhaev, M.; Golemme, G.; Ilinich, O.; Lapkin, A.; Volkov, V.; Yampolskii, Y. Gas permeation properties of phenylene oxide polymers. J. Membr. Sci. 1998, 138, 99–107. [Google Scholar] [CrossRef]
  43. Chowdhury, G.; Vujosevic, R.; Matsuura, T.; Laverty, B. Effects of polymer molecular weight and chemical modification on the gas transport properties of poly(2,6-dimethyl-1,4-phenylene oxide). J. Appl. Polym. Sci. 2000, 77, 1137–1143. [Google Scholar] [CrossRef]
  44. Tsujita, Y. Gas sorption and permeation of glassy polymers with microvoids. Prog. Polym. Sci. 2003, 28, 1377–1401. [Google Scholar] [CrossRef]
  45. Huang, Y.; Paul, D.R. Physical aging of thin glassy polymer films monitored by gas permeability. Polymer 2004, 45, 8377–8393. [Google Scholar] [CrossRef]
  46. Huang, Y.; Wang, X.; Paul, D.R. Physical aging of thin glassy polymer films: Free volume interpretation. J. Membr. Sci. 2006, 277, 219–229. [Google Scholar] [CrossRef]
  47. Horn, N.R.; Paul, D.R. Carbon Dioxide Sorption and Plasticization of Thin Glassy Polymer Films Tracked by Optical Methods. Macromolecules 2012, 45, 2820–2834. [Google Scholar] [CrossRef]
  48. Minelli, M.; De Angelis, M.G.; Sarti, G.C. Predictive calculations of gas solubility and permeability in glassy polymeric membranes: An overview. Front. Chem. Sci. Eng. 2017, 11, 405–413. [Google Scholar] [CrossRef]
  49. Soniat, M.; Tesfaye, M.; Mafi, A.; Brooks, D.J.; Humphrey, N.D.; Weng, L.-C.; Merinov, B.; Goddard, W.A., III; Weber, A.Z.; Houle, F.A. Permeation of CO2 and N2 through glassy poly(dimethyl phenylene) oxide under steady- and presteady-state conditions. J. Polym. Sci. 2020, 58, 1207–1228. [Google Scholar] [CrossRef] [Green Version]
  50. Nagendra, B.; Rizzo, P.; Daniel, C.; Guerra, G. Planar Orientation and Transparency of Nanoporous-Crystalline Polymer Films. Macromolecules 2021, 54, 6605–6611. [Google Scholar] [CrossRef]
  51. Nagendra, B.; Golla, M.; Gallo, C.; Daniel, C.; Rizzo, P.; Guerra, G.; Baldino, L.; Reverchon, E. Mechanisms Determining Different Planar Orientations in PPO Films Crystallized by Guest Sorption. Polymer 2021, 235, 124242. [Google Scholar] [CrossRef]
  52. Musto, P.; Loianno, V.; Scherillo, G.; La Manna, P.; Galizia, M.; Guerra, G.; Mensitieri, G. Benzene-Induced Crystallization of PPO: A Combined Thermodynamic and Vibrational Spectroscopy Study. Ind. Eng. Chem. Res. 2020, 59, 5402–5411. [Google Scholar] [CrossRef]
  53. Daniel, C.; Zhovner, D.; Guerra, G. Thermal Stability of Nanoporous Crystalline and Amorphous Phases of Poly(2,6-dimethyl-1,4-phenylene) Oxide. Macromolecules 2013, 46, 449–454. [Google Scholar] [CrossRef]
  54. Nagendra, B.; Golla, M.; Daniel, C.; Rizzo, P.; Guerra, G. Melting of nanoporous-crystalline and co-crystalline solution cast films of poly(2,6-dimethyl-1,4-phenylene) oxide. Polymer 2021, 228, 123935. [Google Scholar] [CrossRef]
  55. Karasz, F.E.; Bair, H.E.; O’Reilly, J.M. Thermodynamic properties of poly(2,6-dimethyl-1,4-phenylene ether). J. Polym. Sci. Polym. Phys. Ed. 1968, 6, 1141–1148. [Google Scholar] [CrossRef]
  56. Turska, E.; Benecki, W. Studies of liquid-induced crystallization of bisphenol A polycarbonate. J. Appl. Polym. Sci. 1979, 23, 3489–3500. [Google Scholar] [CrossRef]
  57. Durning, C.J.; Russel, W.B. A mathematical model for diffusion with induced crystallization: 2. Polymer 1985, 26, 131–140. [Google Scholar] [CrossRef]
  58. Waywood, W.J.; Durning, C.J. Solvent-induced crystallization of a compatible polymer blend. Polym. Eng. Sci. 1987, 27, 1265–1274. [Google Scholar] [CrossRef]
  59. Ouyang, H.; Lee, W.-H.; Shiue, S.-T.; Lin, T.-L. Solvent-induced crystallization in poly(ethylene terephthalate) during mass transport. J. Polym. Sci. Part B Polym. Phys. 2002, 40, 1444–1453. [Google Scholar] [CrossRef]
  60. Tashiro, K.; Yoshioka, A. Molecular mechanism of solvent-induced crystallization of syndiotactic polystyrene glass. 2. Detection of enhanced motion of the amorphous chains in the induction period of crystallization. Macromolecules 2002, 35, 410–414. [Google Scholar] [CrossRef]
  61. Gupper, A.; Chan, K.L.A.; Kazarian, S.G. FT-IR imaging of solvent-indiced crystallization in polymers. Macromolecules 2004, 37, 6498–6503. [Google Scholar] [CrossRef]
Polymers 13 04384 g001 550
Figure 1. 2D-WAXD EDGE patterns of NC PPO films, as obtained by BE induced crystallization in amorphous films with thickness of: (a) ~20 μm, (b) ~50 μm, (c) ~150 μm and (d) ~300 μm, after guest extraction. Degree of orientation (fc) is indicated at top of the patterns. The 001 reflection arc (centered on the equator) and the main hk0 reflection arcs (centered on the meridian), which show the occurrence of c⊥ orientation, are indicated in the pattern (c).
Figure 1. 2D-WAXD EDGE patterns of NC PPO films, as obtained by BE induced crystallization in amorphous films with thickness of: (a) ~20 μm, (b) ~50 μm, (c) ~150 μm and (d) ~300 μm, after guest extraction. Degree of orientation (fc) is indicated at top of the patterns. The 001 reflection arc (centered on the equator) and the main hk0 reflection arcs (centered on the meridian), which show the occurrence of c⊥ orientation, are indicated in the pattern (c).
Polymers 13 04384 g001
Polymers 13 04384 g002 550
Figure 2. Degree of orientation (fc, left scale) and melting enthalpy (right scale) of NC PPO films versus thickness of the starting amorphous films. For fc = −0.5, all polymer chain axes of crystallites are perfectly perpendicular to the film plane.
Figure 2. Degree of orientation (fc, left scale) and melting enthalpy (right scale) of NC PPO films versus thickness of the starting amorphous films. For fc = −0.5, all polymer chain axes of crystallites are perfectly perpendicular to the film plane.
Polymers 13 04384 g002
Polymers 13 04384 g003 550
Figure 3. BE guest sorption kinetics at room temperature (~20 °C) in PPO amorphous films of different thickness (a) and corresponding Fick’s plots (b). The weight uptake for the 100 μm film is shown on the right scale. The inset in (b) shows enlarged Fick’s plot, which have been used to evaluate diffusivity values of BE in amorphous PPO films with different thickness.
Figure 3. BE guest sorption kinetics at room temperature (~20 °C) in PPO amorphous films of different thickness (a) and corresponding Fick’s plots (b). The weight uptake for the 100 μm film is shown on the right scale. The inset in (b) shows enlarged Fick’s plot, which have been used to evaluate diffusivity values of BE in amorphous PPO films with different thickness.
Polymers 13 04384 g003
Polymers 13 04384 g004 550
Figure 4. SEM images of sections of NC α form PPO films, as obtained by BE-induced crystallization on amorphous films, followed by BE extraction by scCO2. The thickness of the starting amorphous films is: (a,b) 20 μm; (c,d) 100 μm. The presence of flat-on lamellae is apparent only for the thicker film (d). The dashed yellow lines indicate the film surface direction.
Figure 4. SEM images of sections of NC α form PPO films, as obtained by BE-induced crystallization on amorphous films, followed by BE extraction by scCO2. The thickness of the starting amorphous films is: (a,b) 20 μm; (c,d) 100 μm. The presence of flat-on lamellae is apparent only for the thicker film (d). The dashed yellow lines indicate the film surface direction.
Polymers 13 04384 g004
Polymers 13 04384 g005 550
Figure 5. Kinetics of phenomena associated with room-temperature guest-induced crystallization of amorphous PPO films, with thickness of 100 μm (A) and 150 μm (B): (a,a’) BE guest sorption; (b,b’) film thickness; (c,c’) crystallinity index by WAXD (χc); (d,d’) melting enthalpy (ΔHm). The blue vertical bar indicates the time of inflection of the S-shaped curve describing guest sorption, which can be taken as a measure of the time needed for film plasticization.
Figure 5. Kinetics of phenomena associated with room-temperature guest-induced crystallization of amorphous PPO films, with thickness of 100 μm (A) and 150 μm (B): (a,a’) BE guest sorption; (b,b’) film thickness; (c,c’) crystallinity index by WAXD (χc); (d,d’) melting enthalpy (ΔHm). The blue vertical bar indicates the time of inflection of the S-shaped curve describing guest sorption, which can be taken as a measure of the time needed for film plasticization.
Polymers 13 04384 g005
Polymers 13 04384 g006 550
Figure 6. NC α form films, as obtained by sorption/desorption of BE in an amorphous 100 μm PPO film for different sorption times: (a) radial profiles of 2D-WAXD THROUGH patterns; (b) DSC scans at h.r. = 10 °C/min.
Figure 6. NC α form films, as obtained by sorption/desorption of BE in an amorphous 100 μm PPO film for different sorption times: (a) radial profiles of 2D-WAXD THROUGH patterns; (b) DSC scans at h.r. = 10 °C/min.
Polymers 13 04384 g006
Polymers 13 04384 g007 550
Figure 7. Crystallinity index (χc, from WAXD patterns) and melting enthalpy (ΔHm, from DSC scans) of NC α form films, obtained by BE guest-induced crystallization of amorphous PPO films of different thickness: (●) 100 μm; (★) 150 μm. The blue circles indicate 100 μm films as crystallized after 2800 min immersion in BE and subsequently annealed at 40 °C and 60 °C. The red line indicated the extrapolation to a fully crystalline α-form PPO sample.
Figure 7. Crystallinity index (χc, from WAXD patterns) and melting enthalpy (ΔHm, from DSC scans) of NC α form films, obtained by BE guest-induced crystallization of amorphous PPO films of different thickness: (●) 100 μm; (★) 150 μm. The blue circles indicate 100 μm films as crystallized after 2800 min immersion in BE and subsequently annealed at 40 °C and 60 °C. The red line indicated the extrapolation to a fully crystalline α-form PPO sample.
Polymers 13 04384 g007
Table
Table 1. BE guest sorption at room temperature in amorphous PPO films, with thickness of ~100 μm, followed by guest removal leading to NC α form: sorption time (min); BE guest uptake (At/At∞); WAXD crystallinity index (%); melting enthalpy (J/g); film thickness (μm).
Table 1. BE guest sorption at room temperature in amorphous PPO films, with thickness of ~100 μm, followed by guest removal leading to NC α form: sorption time (min); BE guest uptake (At/At∞); WAXD crystallinity index (%); melting enthalpy (J/g); film thickness (μm).
Sorption
Time (min)		BE Guest Sorption (At/At∞)Crystallinity Index WAXD (%) (±2)Melting Enthalpy
(ΔHm) in J/g (±0.5)		Film Thickness
(μm) (±4)
0000100
50.0801.5100
200.113.52.3100
400.15134.5100
800.20157.0110
1000.452011.5120
1100.782912.0130
1200.852512.7155
1300.912813.3165
1400.933815.5180
1600.944416.6190
2400.9546.617.8200
32014820.3200
8400.944421.6210
28000.954622.0210
annealed at 40 °C-5223.4210
annealed at 60 °C-6027.1210
Table
Table 2. BE guest sorption at room temperature in amorphous PPO films, with thickness of ~150 μm, followed by guest removal leading to NC α form: sorption time (min); BE guest uptake (At/At∞); WAXD crystallinity index (%); melting enthalpy (J/g); film thickness (μm).
Table 2. BE guest sorption at room temperature in amorphous PPO films, with thickness of ~150 μm, followed by guest removal leading to NC α form: sorption time (min); BE guest uptake (At/At∞); WAXD crystallinity index (%); melting enthalpy (J/g); film thickness (μm).
Guest Sorption
Time (min)		BE Guest Sorption (At/At∞)Crystallinity Index WAXD (%) (±2)Melting Enthalpy
(ΔHm) in J/g (±0.5)		Film Thickness
(μm) (±4)
0000150
50.0100.2150
200.104.21.02150
400.1211.63.5155
800.2219.46.9155
1000.3021.99.1165
1400.4224.311.1180
1600.4827.412.6200
2000.5831.112.8220
2200.8036.914.5250
2400.8639.615.6270
3000.9243.516300
6401.049.817.3315
8400.835118.4325
12800.7349.220345
28000.7350.320.4330
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Nagendra, B.; Vignola, E.; Daniel, C.; Rizzo, P.; Guerra, G. Dependence on Film Thickness of Guest-Induced c Perpendicular Orientation in PPO Films. Polymers 2021, 13, 4384. https://doi.org/10.3390/polym13244384

AMA Style

Nagendra B, Vignola E, Daniel C, Rizzo P, Guerra G. Dependence on Film Thickness of Guest-Induced c Perpendicular Orientation in PPO Films. Polymers. 2021; 13(24):4384. https://doi.org/10.3390/polym13244384

Chicago/Turabian Style

Nagendra, Baku, Emanuele Vignola, Christophe Daniel, Paola Rizzo, and Gaetano Guerra. 2021. "Dependence on Film Thickness of Guest-Induced c Perpendicular Orientation in PPO Films" Polymers 13, no. 24: 4384. https://doi.org/10.3390/polym13244384

APA Style

Nagendra, B., Vignola, E., Daniel, C., Rizzo, P., & Guerra, G. (2021). Dependence on Film Thickness of Guest-Induced c Perpendicular Orientation in PPO Films. Polymers, 13(24), 4384. https://doi.org/10.3390/polym13244384

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop