Polymer Microstructure Research Articles

Tubular catalytic polyHIPE reactor with deposited silver nanoplate nanoparticles

Continuously operating heterogeneous catalytic reactors are an important step towards more efficient and controllable processes compared to batch operation. Ideally, reactors should exhibit high permeability with the catalyst having a high surface area to volume ratio to minimize the required amount. An example of such catalyst morphology are nanoparticles with a plate-like morphology. In this work, the catalytic reactor was prepared by depositing plate-like silver nanoparticles on positively charged high internal phase emulsion monoliths by exploiting their negative zeta potential. The silver nanoplates had an edge length of 63 nm and a thickness of 13 nm with a sphericity factor of 0.548. The amount of deposited silver, determined from absorbance measurement and mass difference was 12.5 mg/ml and remained unaffected by the concentration of positively charged groups in the range between 69 and 110 mmol/l, demonstrating the robustness of the proposed approach. The permeability remained unchanged after silver deposition under flow due to the polymer microstructure. The reactor was found to be stable under various elution conditions, even after prolonged catalytic reduction of 4-nitrophenol. The specific catalytic activity of silver nanoplates was 428 min−1 g−1, which is an order of magnitude higher than that of silver nanoparticles with cuboctahedra shape and one of the highest reported. The proposed approach can be applied to various types of catalytic nanoparticles by exploiting a variety of possible interactions.

Evaluation of three pyrolyzer technologies for quantitative pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) of tire tread polymer in an artificial sediment matrix

Transferable and reliable methods for tire and road wear particles (TRWP) environmental mass quantification are needed for environmental risk assessment. The comparative performance of three pyrolysis-gas chromatography-mass spectroscopy (Py-GC-MS) technologies with internal standard was assessed for pure polymers and three cryomilled tire tread (CMTT) samples with or without a standard artificial sediment matrix following ISO Technical Specification (TS) 21396:2017. The pyrolyzer technologies included Curie Point (CP; ferromagnetic induction), microfurnace (MF; ceramic heater), and resistive (R; platinum filament). The dimeric pyrolysis markers for tire tread polymer included: 4-vinylcyclohexene (4-VCH), a marker for styrene-butadiene rubber (SBR) and butadiene rubber (BR); dipentene (DP), a marker for natural rubber (NR) or isoprene; and 4-phenylcyclohexene (4-PCH), a marker specific to SBR not considered in the ISO TS. Comparing the performance of three pyrolysis technologies for quantifying six samples (two tread amount levels for three formulations), the average relative standard deviation in pure-CMTT measured in triplicate using 4-VCH and DP was 6.8% (MF), 26% (CP), and 60% (R) without matrix (100 or 1000 ug CMTT), and 19% (MF), 26% (CP) and 105% (R) with matrix (0.5% or 5% CMTT). The recovery of CMTT was greater than 50% for all MF and CP samples with good separation at the two amount levels. An increased frequency of CMTT recoveries > 150% for MF and CP artificial sediment analysis suggests future consideration of pre-treatment (e.g., thermal desorption or labile organic digestion) in addition to the previously identified importance of polymer microstructure. The magnitude of variability observed with the resistive instrument indicates that further method development may be necessary to optimize thermal transfer. Overall, Curie point and microfurnace were found to be excellent candidate pyrolysis technologies for ongoing quantitative Py-GC-MS of TRWP in environmental method development, capable of a low likelihood of underestimating polymer mass with reasonable replicate precision.

Characterization of a 30 µm pixel size CLIP-based 3D printer and its enhancement through dynamic printing optimization.

Resolving microscopic and complex 3D polymeric structures while maintaining high print speeds in additive manufacturing has been challenging. To achieve print precision at micrometer length scales for polymeric materials, most 3D printing technologies utilize the serial voxel printing approach that has a relatively slow print speed. Here, a 30-µm-resolution continuous liquid interface production (CLIP)-based 3D printing system for printing polymeric microstructures is described. This technology combines the high-resolution from projection microstereolithography and the fast print speed from CLIP, thereby achieving micrometer print resolution at x103 times faster than other high-resolution 3D printing technologies. Print resolutions in both lateral and vertical directions were characterized, and the printability of minimum 30 µm features in 2D and 3D has been demonstrated. Through dynamic printing optimization, a method that varies the print parameters (e.g. exposure time, UV intensity, and dark time) for each print layer, overhanging struts at various thicknesses spanning 1 order of magnitude (25 µm - 200 µm) in a single print are resolvable. Taken together, this work illustrates that the micro-CLIP 3D printing technology, in combination with dynamic printing optimization, has the high resolution needed to enable manufacturing of exquisitely detailed and gradient 3D structures, such as terraced microneedle arrays and micro-lattice structures, while maintaining high print speeds.

Multiscale modelling of multizone gas phase propylene (co)polymerization reactors—A comprehensive review

AbstractCatalysts and polymerization processes have evolved over the years. Such significant developments have allowed producers to broaden the range of polymer microstructure and process productivity, thereby making it possible to offer a wide range of end‐use properties at a reasonably low cost. However, these advantages in catalyst performance and reactor operation require that we understand as much as possible about reactor operation in the broadest sense. In addition to the fundamental experimental study of polymer chemistry, this means that one needs to develop complete, robust process models. The present paper provides a rapid overview of recent developments in various gas phase propylene (co)polymerization reactors in use today, concentrating on multizone gas phase polypropylene reactors: that is, multizone circulating reactor, fluidized bed reactor with internal circulation, fluidized bed reactor with external circulation, and horizontal stirred bed reactor. We then concentrate on the advances in multiscale modelling of gas phase propylene (co)polymerization reactors, from microscale kinetics at the active sites, to the mesoscale, including physical transport and thermodynamic modelling at the single‐particle level and its boundary layer, up to the macroscale reactor modelling. A systematic guideline used for the selection of appropriate thermodynamic models is proposed for gas phase olefin polymerization processes. Finally, current challenges and remaining issues related with the development of mathematical multiscale modelling are addressed.

Impact of regioregularity on the solubility parameters of poly(3‐hexylthiophene)

The solubilities of four P3HT samples of varying regioregularity (rr = 58%, 86%, 93%, and 96%) are measured in 18 organic solvents, and the solubility data are used to calculate the partial solubility parameters (SPs) (δD, δP, δH) of the samples using the functional solubility parameter (FSP) approach. The FSP results show that the δP and δH parameters increase with increasing regioregularity. The results reveal that the anomalously large δP and δH SPs regioregular P3HT previously reported in the literature are attributable to the microstructure (regioregularity) of the P3HT polymer, and that as that as the regioregularity of P3HT increases the polymer can engage in stronger associative interactions with the solvent. Complementary computational analyses of hexamer model systems using Gaussian16 and AIMll software, reveal variations in electronic characteristics and topological parameters consistent with the regioregular-dependent increases in δP and δH. This research may aid in modifying the fundamental and/or practical framework of SP theory to account for the effects of polymer microstructure and polymorphism.

A computational fluid dynamics model coupled with ethylene polymerization kinetics for fluidized bed polyethylene reactor

This work aims at exploring the effect of macro operating conditions on the distribution of temperature field and chain microstructures of polymer in a gas phase ethylene polymerization fluidized bed reactor (FBR) by coupling polymerization kinetics with computational fluid dynamics (CFD). An ethylene polymerization kinetic model in terms of the method of moments was introduced to CFD model. In the modeling framework, the Flory's distribution and custom field functions were used to predict the molecular weight distribution (MWD). The results show that the average molecular weight decreases with the increasing of reaction temperature, and MWD becomes wider because of the increase of temperature gradient. With the increase of hydrogen concentration, the average molecular weight and MWD becomes smaller and narrower, respectively. Unlike the hydrogen concentration, an increase in the ethylene concentration leads to an increase in the average molecular weight, polydispersity distribution index (PDI), and temperature. An increase of gas velocity improves the heat transfer of FBR but results in a very wide MWD when gas velocity exceeds the optimum fluidizing velocity. This model is helpful to understand how the operating conditions affect the performance of FBR and can provide theoretical guidance for the operation and design of polyolefin FBR.

Brillouin Light Scattering Characterisation of Gray Tone 3D Printed Isotropic Materials.

Three-dimensional direct laser writing technology enables one to print polymer microstructures whose size varies from a few hundred nanometers to a few millimeters. It has been shown that, by tuning the laser power during writing, one can adjust continuously the optical and elastic properties with the same base material. This process is referred to as gray-tone lithography. In this paper, we characterize by Brillouin light scattering the complex elastic constant of different reticulated isotropic polymers, at longitudinal phonon frequencies of the order of 16 GHz. We estimate the real part of the constant to vary from 7 to 11 GPa as a function of laser power, whereas its imaginary part varies between 0.25 and 0.6 GPa. The linear elastic properties are further measured at a fixed laser power as a function of temperature, from C to C. Overall, we show that our 3D printed samples have a good elastic quality with high Q factors only ten times smaller than fused silica at hypersonic frequencies.

Ortho-substituent effect on metal coordination geometry, chain microstructure and polymer properties in α-diimine nickel-catalyzed long chain α-Olefin polymerization

The tuning of polyolefin microstructure, including the branching density and branching distribution, through the ligand modification in transition metal-based catalysts has received considerable interest. In this work, we present the synthesis and characterization of a series of α-diimine Ni(II) catalysts containing bulky diarylmethyl moiety and varied steric substituents, and a systematic investigation on the catalytic behavior of these catalyst for 1-octene and 1-decene polymerization. Ni3 with ortho-diisopropyl substituents adopts a common distorted tetrahedral geometry, while a rare square planar geometry is observed for Ni4 with ortho-phenyl substituents. The ortho-substituent effect on the preference of insertion fashion (1,2 or 2,1-insertion) and chain-walking in long chain α-olefin polymerization is also established. Highly branched amorphous polyolefin can be obtained by the unsymmetrical catalyst with ortho-alkyl substituents (H, Me, iPr) in which the major 1,2-insetion pathway was observed, whereas moderate branched semicrystalline polyolefin can be produced by the unsymmetrical catalyst with ortho-phenyl substituents, which showed a significant increase in 2,1-insertion. Most interestingly, the branching distribution analysis through 13C NMR indicated that the polymer obtained by Ni3 gave the higher percentage of long-chain branches relative to methyl branches, while Ni4 afforded the polymer with methyl branches being predominant. These significant differences in coordination geometry and catalytic behavior between Ni3 and Ni4 may be associated with the unique steric congestion of the ortho-phenyl substituents. In particular, the comparative investigation of the mechanical properties of the polymers obtained by Ni3 and Ni4 was also performed.

Hybrid microfabrication of 3D pyrolytic carbon electrodes by photolithography and additive manufacturing

We report a novel hybrid method for fabricating high aspect ratio 3D pyrolytic carbon electrodes combining UV photolithography and additive manufacturing with commercially available SLA 3D printers and materials. By using a 3D printed chip holder, aligned 3D printing on a patterned silicon chip was possible. This allowed for the fabrication of cylindrical polymer micropillars with a height of 2173 ± 26 μm and a width of 316 ± 11 μm on SU-8 precursor structures defining the leads, contact pads and underlying 2D electrode prepared using UV lithography. Microfabrication of 3D structures with these dimensions is impossible to achieve with SU-8 photolithography alone. The hybrid polymer structures were converted into 3D carbon electrodes with high structural integrity using a 3-step pyrolysis process optimized for the specific 3D print resin. During this process, the micropillars shrunk to 30 ± 3% in height and 35 ± 1% in width of the polymer precursor structures, while maintaining the macroscopic shape and microscopic surface roughness. Electrochemical experiments confirmed that the pyrolytic carbon formed a monolithic conductive 3D electrode. The surface roughness contributed to a 17 ± 5% increase in electroactive surface area compared to the geometrical surface area of the micropillars. • · 3D polymer microstructures fabricated by a novel hybrid process combining SU-8 photolithography and additive manufacturing • Optimization of a pyrolysis process converting the 3D polymer structures into 3D pyrolytic carbon electrodes • Electrochemical characterization demonstrating monolithic integration and increased surface area of the 3D electrodes

Coupling Kinetic Modelling with SAOS and LAOS Rheology of Poly(n‐butyl acrylate)

Front Cover: The interplay between reaction conditions of the polymerization process of n-butyl acrylate with the resulting product properties is investigated and quantified in article number 2100620 by Kristina Maria Zentel and co-workers. A detailed kinetic model for the polymerization is validated against model experiments and used to determine the polymeric microstructure—here molar mass distribution and branching densities. They can be directly linked to the rheological behavior in the linear (SAOS) as well as non-linear regime (LAOS).

High-Temperature Thermal Transport Properties of Multifunctional PTFE/PEEK-Matrix Composite With Short Carbon Fibers and Graphite Flakes

Abstract A combined experimental and theoretical investigation is conducted on elevated-temperature thermal transport properties of a multifunctional polytetrafluoroethylene (PTFE)/polyetheretherketone (PEEK) matrix composite containing short carbon fibers and graphite flakes. In experiments, X-ray diffraction (XRD), scanning electron microscope (SEM), and optical microscopy are used to determine morphologies and microstructure of neat PTFE and PEEK polymers, PTFE/PEEK blend, and individual PTFE and PEEK phases in the carbon fiber (CF)Gr/PTFE/PEEK composite. Microstructure parameters determined are used in subsequent analytical modeling and predictions. Effective heat capacity and thermal conductivities of the composite and its polymer matrix are determined by a modulated differential scanning calorimetry (MDSC) method with temperature up to 225 °C. The results show that thermal transport properties of the composite are significantly affected by temperature and polymer transitions. The carbon fibers and graphite in the composite improve its mechanical and tribological performance and also enhances heat conduction. Thermal diffusivity of the composite, however, is governed by the PTFE/PEEK matrix due to its high thermal capacity. In the theoretical/analytical study, thermodynamic considerations are made at both molecular and micromechanical levels. Theoretical models and micromechanics analyses are used to determine effective thermal transport properties of the composite. The results clarify the roles of individual constituents and temperature effects on the composite thermal transport. Thermal percolation predictions compare well with experimental data; they also reveal that 10% (by volume) graphite lubricant in the carbon fiber-reinforced PTFE/PEEK composite leads to formation of effective thermal conductive networks, which rapidly increases thermal percolation due to their high efficiency of thermal transport.

Miscible polymethyl methacrylate/polylactide blend with enhanced foaming behavior and foam mechanical properties

High-performance foams play significant roles in many industries. Microcellular foaming with carbon dioxide as blowing agents is an advanced and environmentally friendly technology to prepare polymeric foams with significantly refined cellular morphology. The manipulation of polymer microstructure and rheological behavior is the key to tailor its foaming behavior. In this study, polymethyl methacrylate (PMMA) was blended with polylactide (PLA) to improve its foaming behavior in one-step batch foaming with carbon dioxide as blowing agents. It was demonstrated that PMMA and PLA are fully miscible in molecular level. The presence of PLA can lead to decreased glass transition temperature of PMMA, and PMMA can suppress the crystallization of PLA. PLA can enhance the melt elasticity of PMMA at low shear oscillation frequencies but decrease the melt elasticity of PMMA at high shear oscillation frequencies. Thanks to the plasticity effect and heterogeneous nucleation effect of PLA, adding an appropriate amount of PLA can significantly broaden the foaming window of PMMA and refine cellular morphology. Microcellular PMMA/PLA foams with cell sizes less than 10 µm and expansion ratio up to 18.4 were fabricated under a foaming pressure of 17.24 MPa with 10 wt% PLA. Nanocellular PMMA/PLA foam can be achieved with the presence of 25 wt% PLA under a foaming pressure of only 6.90 MPa. The PMMA/PLA blend foams show significantly enhanced compression modulus and strength compared with neat PMMA foams. Moreover, reducing cell sizes can significantly enhance the compression modulus and strength of foams.

A Cocatalyst Strategy to Enhance Ruthenium‐Mediated Metathesis Reactivity towards Electron‐Deficient Substrates

Ruthenium-mediated olefin metathesis has been widely applied for the synthesis of various organic molecules and polymers. Inspired by the cocatalyst strategy for olefin polymerization, here we demonstrate that the abstraction of a chloride ion from various commercially available ruthenium catalysts significantly enhances their reactivity towards electron-deficient internal olefins. This cocatalyst strategy can be implemented in ethenolysis and cross-metathesis reactions of FG-CH=CH-FG type substrates bearing electron-withdrawing groups and the synthesis of telechelic polymers that can be converted to polyethylene-like materials with closed-loop recycling properties. The copolymerization of cyclic substrate with cycloolefins followed by hydrogenation afforded polyolefin materials with in-chain break points. Interestingly, switchable catalysis was achieved in the absence and presence of a cocatalyst, which allowed the polymer microstructure and material properties to be fine-tuned.

A Cocatalyst Strategy to Enhance Ruthenium‐Mediated Metathesis Reactivity towards Electron‐Deficient Substrates

Ruthenium-mediated olefin metathesis has been widely applied for the synthesis of various organic molecules and polymers. Inspired by the cocatalyst strategy for olefin polymerization, here we demonstrate that the abstraction of a chloride ion from various commercially available ruthenium catalysts significantly enhances their reactivity towards electron-deficient internal olefins. This cocatalyst strategy can be implemented in ethenolysis and cross-metathesis reactions of FG-CH=CH-FG type substrates bearing electron-withdrawing groups and the synthesis of telechelic polymers that can be converted to polyethylene-like materials with closed-loop recycling properties. The copolymerization of cyclic substrate with cycloolefins followed by hydrogenation afforded polyolefin materials with in-chain break points. Interestingly, switchable catalysis was achieved in the absence and presence of a cocatalyst, which allowed the polymer microstructure and material properties to be fine-tuned.

Modeling Low‐Density Polyethylene (LDPE) Production in Tubular Reactors: Connecting Polymerization Conditions with Polymer Microstructure and Rheological Behavior

AbstractThe production of low‐density polyethylene (LDPE) in high‐pressure tubular reactors is widely studied due to its extensive use worldwide. Reaction conditions have a crucial impact on the polymer molecular architecture, which, in turn, influences the rheological behavior of the polymer in the molten state, a very important variable during subsequent processing. Up to now, the relationships between reactor polymerization conditions, polymer microstructure, and final rheological properties are not completely established, although they could be a very useful tool for rapid process control and optimization. This work presents an integrated model of the high‐pressure polymerization of ethylene in tubular reactors, consisting of the combination of a deterministic model of the tubular reactor that calculates molecular properties of the polymer and an empirical rheological model for branched molecules. The integrated model predicts conversion, temperature, and average molecular properties, as well as the bivariate molecular weight‐long chain branching distribution, the branching index, and the shear viscosity flow curve for LDPE under different operating conditions. Results compare well with experimental data of an actual industrial reactor. Additionally, the effect of polymerization conditions on molecular and rheological properties is analyzed.

Stereocomplexation of Stereoregular Aliphatic Polyesters: Change from Amorphous to Semicrystalline Polymers with Single Stereocenter Inversion.

Stereocomplexation is a useful strategy for the enhancement of polymer properties by the co-crystallization of polymer strands with opposed chirality. Yet, with the exception of PLA, stereocomplexes of biodegradable polyesters are relatively underexplored and the relationship between polymer microstructure and stereocomplexation remains to be delineated, especially for copolymers comprising two different chiral monomers. In this work, we resolved the two enantiomers of a non-symmetric chiral anhydride (CPCA) and prepared a series of polyesters from different combinations of racemic and enantiopure epoxides and anhydrides, via metal-catalyzed ring-opening copolymerization (ROCOP). Intriguingly, we found that only specific chiral combinations between the epoxide and anhydride building blocks result in the formation of semicrystalline polymers, with a single stereocenter inversion inducing a change from amorphous to semicrystalline copolymers. Stereocomplexes of the latter were prepared by mixing an equimolar amount of the two enantiomeric copolymers, yielding materials with increased melting temperatures (ca. 20 °C higher) compared to their enantiopure constituents. Following polymer structure optimization, the stereocomplex of one specific copolymer combination exhibits a particularly high melting temperature (Tm = 238 °C).

Effect of Highland Barley on Rheological Properties, Textural Properties and Starch Digestibility of Chinese Steamed Bread.

Highland barley has a different composition and structure to other crops. It has higher contents of total polyphenol (TPC), total flavonoid (TFC) and β-glucan, which can be supplemented to improve the nutrition of wheat-flour-based food. In this study, the flours of three different grain-colored highland barley varieties Beiqing 6 (BQ), Dulihuang (DLH), and Heilaoya (HLY), were added to Jimai60 (JM, a wheat variety with medium gluten) wheat flour at different substitution levels to investigate their effects on the unextractable polymeric protein (UPP) content, micro-structure, rheological properties and mixing properties of dough, and the color, texture, flavor, and in vitro digestion of Chinese steam bread (CSB). The results showed that the moderate substitution of highland barley (20%) increased the UPP%, optimized the micro-structure of gluten, and improved its rheological properties by increasing dough viscoelasticity. The CSBs made from the composite flours exhibited a similar specific volume, cohesiveness, springiness and resilience to wheat CSB, while the firmness of composite CSBs (particularly JM-HLY-20) was delayed during storage. Importantly, the addition of highland barley increased the contents of TPC, TFC and β-glucan, but decreased the in vitro starch digestibility of CSBs. A sensory evaluation showed that JM-HLY CSB was the most preferable. Taken together, highland barley can be used as a fine supplement to food products, with health-promoting properties.

Suppression of Chain Transfer and Promotion of Chain Propagation in Neutral Anilinotropone Nickel Polymerization Catalysis

Both suppression of chain transfer and promotion of chain propagation are highly important but greatly challenging to enhance desirable turnover frequency (TOF) and molecular weight (MW) in olefin polymerization, which is one of the most important chemical reactions. A transition-metal catalyst is the most important key to controlling these fundamental steps. In this contribution, we report the neutral, single-component anilinotropone nickel catalyst Ni6 via an alternative synthetic pathway, which is the isomer of the milestone salicylaldiminato nickel catalyst Ni6-iso. Compared to the classic Ni6-iso, Ni6 produces polyethylenes with elevated TOF (five times), much higher MW (102 times), narrower molecular weight distribution (PDI = 1.05, living fashion at 40 °C), and lower branching density (substantially linear microstructure) in ethylene polymerization. In particular, in the copolymerization of ethylene with a polar comonomer, Ni6 concurrently gives 4.5 times higher TOF, 34 times higher MW, and 1.6 times higher comonomer incorporation relative to Ni6-iso. Mechanistic insights using density functional theory (DFT) calculation reveal both the suppression of chain transfer and promotion of chain propagation. This evidences the anilinotropone nickel catalyst as a promising candidate.

Adhesion of Oral Bacteria to Commercial d-PTFE Membranes: Polymer Microstructure Makes a Difference.

Bacterial contamination of the membranes used during guided bone regeneration directly influences the outcome of this procedure. In this study, we analyzed the early stages of bacterial adhesion on two commercial dense polytetrafluoroethylene (d-PTFE) membranes in order to identify microstructural features that led to different adhesion strengths. The microstructure was investigated by X-ray diffraction (XRD), differential scanning calorimetry (DSC), and Fourier transform infrared (FTIR). The surface properties were analyzed by atomic force microscopy (AFM), scanning electron microscopy (SEM), and surface free energy (SFE) measurements. Bacterial properties were determined using the microbial adhesion to solvents (MATS) assay, and bacterial surface free energy (SFE) was measured spectrophotometrically. The adhesion of four species of oral bacteria (Streptococcus mutans, Streptococcus oralis, Aggregatibacter actinomycetemcomitas, and Veilonella parvula) was studied on surfaces with or without the artificial saliva coating. The results indicated that the degree of crystallinity (78.6% vs. 34.2%, with average crystallite size 50.54 nm vs. 32.86 nm) is the principal feature promoting the adhesion strength, through lower nanoscale roughness and possibly higher surface stiffness. The spherical crystallites (“warts”), observed on the surface of the highly crystalline sample, were also identified as a contributor. All bacterial species adhered better to a highly crystalline membrane (around 1 log10CFU/mL difference), both with and without artificial saliva coating. Our results show that the changes in polymer microstructure result in different antimicrobial properties even for chemically identical PTFE membranes.

Fabrication of microstructured polymers by a simple biotemplate embossing method and their characterization

AbstractIn this work, microstructures were developed on a polymer surface using an embossing process by utilizing the transverse section of a wood as a biotemplate/mold. Microstructured polymers obtained by the proposed practical method were characterized by optical microscope for rough imaging, by scanning electron microscope for morphological properties and by Fourier transform infrared spectroscopy for surface chemistry. Utilization of a fluoropolymer eliminates the anti-stick surface pre-treatment and facilitates intact demolding of polymer structures from micro-voids of the wood. The height of the polymer microstructures was measured as 4 to 6 μm. Dimensions of the wood micro-voids can be tuned via acid/base treatment process. A drastic increase in heights of polymer microstructures (26 μm) was observed for the sample stamped by the acid/base treated biotemplate. The proposed method, which delivers well-organized microstructure patterns on fluoropolymer surfaces, can be utilized in the production of specialty surfaces, such as antibacterial, stick/anti-stick and water repellent.