Acrylate-based Polymer Research Articles

Swelling Behavior of Acrylate-Based Photoresist Polymers Containing Cycloaliphatic Groups of Various Sizes

Photoresist polymers containing cycloaliphatic acrylic monomers have been synthesized for use in the microcircuits of semiconductors. Although cycloaliphatic acrylic monomers exhibit a high etch resistance and excellent thermal properties, their large size increases the distance between the main chains of the resulting polymers. This increased distance facilitates the penetration of a developer between the main chains, which leads to swelling and thus pattern collapse, distortion, and delamination, thereby complicating the fabrication of microcircuits. To solve this problem, various large developers were used in previous studies to reduce the swelling effect. However, these developers could not easily dissolve the unexposed regions of the resist. To overcome this issue, we designed photoresist polymers with smaller functional groups to decrease the degree of swelling. Specifically, ArF photoresist polymers were synthesized from monomers with various sizes of functional groups. We confirmed that the polymer synthesized using cyclohexyl methacrylate (CHMA), which had the smallest functional group, exhibited the shortest distance between the main chains. Consequently, this polymer showed the least swelling, with a swelling ratio of 109%. In contrast, the polymers synthesized using isobornyl acrylate (IBOA) and dicyclopentanyl methacrylate (TCDMA), which have large functional groups, exhibited greater distances between the main chains, resulting in swelling ratios of 114% and 112%, respectively. The polymer with a swelling ratio of 109% showed excellent patterning properties, while those with swelling ratios of 114% and 112% were delaminated by the developer. Our work introduces a novel approach to help reduce the swelling effect and achieve high-quality patterns in negative photoresists.

Solid-State Lithium Batteries with In Situ Polymerized Acrylate-Based Electrolytes Capable of Electrochemically Stable Operation at 100 °C.

Solid polymer electrolytes (SPEs) typically consist of salts with mobile anions that could cause instabilities and parasitic side reactions in solid-state lithium (Li) batteries. To address this challenge, single-Li-ion conducting (SLIC) SPEs, where anions of Li salts are covalently attached to the polymer backbone, have been utilized to reduce the number of mobile anions. This approach improves the cationic transference number but is accompanied by a loss of ionic conductivity. In this work, we investigate a synergetic approach of using both a polymerizable SLIC salt and a conventional Li salt in a polymer matrix by in situ polymerization of the poly(propylene glycol) acrylate (PPGA) monomer. The synthesized hybrid SPEs show a high ionic conductivity of up to ∼2 × 10-4 S cm-1 and a relatively high Li-ion transference number of ∼0.4. With a significantly reduced fraction of mobile anions in the combined salt SPE, in situ polymerized SPE cells with a LiFePO4 (LFP) cathode achieve a stable performance for over 100 cycles at temperatures as high as 100 °C, which is unattainable with conventional Li salts or electrolytes. Furthermore, solid-state nuclear magnetic resonance spectra provide additional insights into differences in Li nucleus environments and emphasize a reduction in activation energy for hybrid SPEs due to their more open structure. This study opens the path for the fabrication of high-performance solid polymer Li batteries capable of operating at high temperatures using commercial battery fabrication equipment, as in situ polymerized acrylate-based polymers provide drop-in compatibility with conventional battery production, ease of acrylate polymerization, and inexpensive, facile SPE chemistry. We expect that further tuning of the acrylate-based SPE composition may allow further increases in its conductivity without sacrificing its electrochemical stability or mechanical properties.

Solid-State Lithium Batteries with in-Situ Polymerized Acrylate-Based Electrolytes Capable of Electrochemically Stable Operation at 100 ℃

In-situ polymerized acrylate-based polymers are very appealing as solid polymer electrolytes (SPEs) in lithium (Li) batteries due to the drop-in compatibility of such in-situ polymerization with conventional battery production, the ease of acrylate polymerization and their inexpensive, facile SPE chemistry. We identified, however, that such SPEs suffer from either a low cationic transference number with dual ion conducting salts (0.12-0.2) or a low ionic conductivity with single Li-ion conducting (SLIC) salts (6·10-6 S cm-1). In this project we overcame these limitations and developed significantly improved SPE with ionic conductivity of up to 2·10-4 Scm-1 and a relatively high Li-ion transference number of 0.4. With a significantly reduced fraction of mobile anions in the hybrid SPE, in-situ polymerized SPE cells with an LiFePO4 (LFP) cathode achieve a stable performance for over 100 cycles at temperatures as high as 100 °C, which is unattainable with conventional Li salts or electrolytes. Furthermore, the motional narrowing observed in the line-shapes of solid-state nuclear magnetic resonance (SS-NMR) spectra provided additional insights of the differences in Li nucleus environments and revealed a reduced activation energy for the hybrid salt SPEs due to their more open structure. This study opens the path for the fabrication of high-performance solid polymer lithium batteries capable of operating at high temperatures using commercial battery fabrication equipment. We expect that further tuning of the acrylate based SPE composition may allow further increases in its conductivity without sacrifices in its electrochemical stability or mechanical properties.

Investigation of thermomechanical behaviors of acrylate-based shape memory polymers by molecular dynamics simulation

Shape memory polymers (SMPs) have received a lot of attention lately due to their potential use as actuators in various applications, including robotics and biomedical device. SMPs are a better choice than other smart materials due to their remarkable ability to recover from significant deformations and their ability to be stimulated remotely. Here, we investigate the mechanical and recovery behaviors of SMPs composed of acrylate-based monomers and crosslinkers with varying crosslink densities, using full-atomistic molecular dynamics (MD) simulations. Physical parameters, such as density and glass transition temperature, are determined for systems with different crosslinking densities. Tensile loading is applied to characterize the mechanical characteristics and shape memory behaviors. Furthermore, the shape-memory behavior of the system with highest crosslinking density is investigated to understand the effects of recovery temperature and deformation temperature on shape recovery. Our findings shed light on the critical structural elements that determine shape recovery ability, giving insights for advanced SMP material design and development. This study adds to our fundamental understanding of SMP behavior and has ramifications for a wide range of technological applications.

Local fluorinated functional units enhance Li+ transport in acrylate-based polymer electrolytes for lithium metal batteries

Fluorinated polymer matrix emerges as a promising candidate owing to their enhanced anti-oxidation ability, but their application is plagued by the relatively low ion conduction ability and the ambiguous ionic conduction mechanism in the fluorinated polymer electrolytes (PEs). Herein, a series of acrylate-based electrolytes with different fluorinated functional units (fluorinated-FUs) of poly(ethyl methacrylate) electrolyte (0F PE), poly(trifluoroethyl methacrylate) electrolyte (3F PE) and poly(hexafluorobutyl methacrylate) electrolyte (6F PE) were investigated. Beneficial from the long fluorinated-FUs in the side chain, the 6F PE exhibits improved both ionic conductivity of 4.0×10−4 S cm−1 and Li+ transference number of 0.65 at 25 °C, which are superior to those of the 0F PE and the 3F PE. The enhanced ion conduction mechanism was clarified via combining the theoretical calculations and experimental data, where the integration of local fluorinated-FUs provides additional coordinating sites for the continuous Li+ migration and regulates the ion transporting pathways. This work demonstrates that the regulation of local fluorinated-FUs can provide a promising strategy for achieving high performance PEs applied in solid-state batteries.

Effect of various reactive diluents on the mechanical properties of the acrylate-based polymers produced by DLP/LCD-type 3D printing

Effect of various reactive diluents on the mechanical properties of the acrylate-based polymers produced by DLP/LCD-type 3D printing

Glycerol Acrylate-Based Photopolymers with Antimicrobial and Shape-Memory Properties.

In this paper, for the first time, photopolymers were synthesized from glycerol acrylates with different numbers of functional groups, 2-hydroxy-3-phenoxypropyl acrylate, glycerol dimethacrylate or glycerol trimethacrylate, without and with the addition of vanillin styrene. The photocuring kinetics were monitored by real-time photorheometry. The mechanical, rheological, thermal, antimicrobial and shape-memory properties of the photopolymers were investigated. All polymers synthesized demonstrated antibacterial activity against Escherichia coli and Staphylococcus aureus, as well as antifungal activity against Aspergillus flavus and Aspergillus niger. 2-Hydroxy-3-phenoxypropyl acrylate-based polymers showed thermoresponsive shape-memory behavior. They were able to maintain their temporary shape below the glass transition temperature and return to their permanent shape above the glass transition temperature. Synthesized photopolymers have potential to be used as sustainable polymers in a wide range of applications such as biomedicine, photonics, electronics, robotics, etc.

ZnO Quantum Photoinitiators as an All-in-One Solution for Multifunctional Photopolymer Nanocomposites.

Nanocomposites are constructed from a matrix material combined with dispersed nanosized filler particles. Such a combination yields a powerful ability to tailor the desired mechanical, optical, electrical, thermodynamic, and antimicrobial material properties. Colloidal semiconductor nanocrystals (SCNCs) are exciting potential fillers, as they display size-, shape-, and composition-controlled properties and are easily embedded in diverse matrices. Here we present their role as quantum photoinitiators (QPIs) in acrylate-based polymer, where they act as a catalytic radical initiator and endow the system with mechanical, photocatalytic, and antimicrobial properties. By utilizing ZnO nanorods (NRs) as QPIs, we were able to increase the tensile strength and elongation at break of poly(ethylene glycol) diacrylate (PEGDA) hydrogels by up to 85%, unlike the use of the same ZnO NRs acting merely as fillers. Simultaneously, we endowed the PEGDA hydrogels with post-polymerization photocatalytic and antimicrobial activities and showed their ability to decompose methylene blue and significantly eradicate antibiotic-resistant bacteria and viral pathogens. Moreover, we demonstrate two fabrication showcase methods, traditional molding and digital light processing printing, that can yield hydrogels with complex architectures. These results position SCNC-based systems as promising candidates to act as all-in-one photoinitiators and fillers in nanocomposites for diverse biomedical applications, where specific and purpose-oriented characteristics are required.

Understanding Solid-State Photochemical Energy Storage in Polymers with Azobenzene Side Groups.

Solar thermal fuel (STF) materials store energy through light-induced changes in the structures of photoactive molecular groups, and the stored energy is released as heat when the system undergoes reconversion to the ground-state structure. Solid-state STF devices could be useful for a range of applications; however, the light-induced structural changes required for energy storage are often limited or prevented by dense molecular packing in condensed phases. Recently, polymers have been proposed as effective solid-state STF platforms, as they can offer the bulk properties of solid materials while retaining the molecular-level free volume and/or mobility to enable local structural changes in photoresponsive groups. Light-induced energy storage and macroscopic heat release have been demonstrated for polymers with photoisomerizable azobenzene side groups. However, the mechanism of energy storage and the link between the polymer structure, energy density and storage duration has not yet been explored in detail. In this work, we present a systematic study of methacrylate- and acrylate-based polymers with azobenzene side groups to establish the mechanism of energy storage and release and the factors affecting energy density and reconversion kinetics. For polymers with directly attached azobenzene side groups, the energy storage properties are in line with previous work on similar systems, and the photoisomerization and reconversion properties of the azobenzene side groups mirror those of molecular azobenzene. However, the inclusion of an alkyl linker between the azobenzene side group and the backbone significantly increases the photoswitching efficiency, giving almost quantitative conversion to the Z isomeric state. The presence of the alkyl linker also reduces the glass transition temperature and leads to faster spontaneous thermal reconversion to the E isomeric form, but in all cases, half-lives of more than 4 days are observed in the solid state, which provides scope for applications requiring daily energy storage-release cycles. The maximum gravimetric energy density observed is 143 J g-1, which represents an increase of up to 44% compared to polymers with directly attached azobenzene moieties.

Coupling ATR-FTIR spectroscopy with multivariate analysis for polymers manufacturing and control of polymers’ molecular weight

Acrylate-based polymers are commonly used in the chemical industry. Consistent manufacturing of these polymers with the help of Process Analytical Technology (PAT) is very desirable. The capability of monitoring polymers’ molecular weight in real-time reduces operation time and eliminates the frequent samplings needed for quality control. Herein, molecular weight (Mw) of glycidyl methacrylate-co-methyl methacrylate (GMA-co-MMA) copolymer was monitored in real-time using mid-infrared ATR-FTIR spectroscopy. The Principal Component Analysis (PCA) and Partial Least Square (PLS) models were then utilized to examine, improve the latent space, and select high-quality spectra. We show that acquiring highly correlated spectra enhances the robustness of the regression model. The developed models demonstrate a satisfied R2 correlation up to ∼87%. This study suggests the potential of robust data-driven techniques for the development of predictive Mw analytics tools.

Processing of 3-(Trimethoxysilyl)propyl Methacrylate (TMSPM) Functionalized Barium Titanate/Photopolymer Composites: Functionalization and Process Parameter Investigation

To improve the performance of lead-free piezoelectric composites, the functionalization of the filler particles has been suggested as a successful strategy in several recent reports. The details of the functionalization process, however, are not clear, nor is its influence on the dielectric properties of the composites. This study reports a systematic investigation of the functionalization process parameters of barium titanate nanoparticles (BTONP) with 3-(trimethoxysilyl)propyl methacrylate (TMSPM) used as a linker to an acrylate-based matrix polymer. Functionalization process temperature, time, functionalization agent ratio, solvent, and catalyst influence on the functionalization degree were measured by thermogravimetric analysis (TGA), elemental analysis, and Fourier-transform infrared (FTIR) spectroscopy. Elevated temperature and average functionalization time led to the highest functionalization degree in the form of a TMSPM monolayer on the particle surface. Three solvents, with and without catalysts, were investigated and two types of functionalized BTONP were selected for composite manufacturing. To this end, the functionalized particles were used to manufacture 10 vol.% BTONP/photopolymer UV light-curable composite suspensions. After solidification of the suspensions by exposure to UV light, the microstructure and dielectric properties of the resulting composites were investigated. It was seen that functionalization improves the dispersion of particles, increases suspension viscosity, and decreases the curing depth and dielectric properties.

Tailoring the linear viscoelastic response of industrial double dynamics networks through the interplay of associations

We investigate the linear viscoelastic properties of industrial pressure sensitive adhesives comprising double networks with an entangled acrylate-based polymer and two types of intermolecular associations (crosslinking), permanent (epoxide) and reversible (metal-chelate), having different compositions. A combination of shear rheometry and an appropriately modified version of the Time Marching Algorithm (TMA) allows to probe and analyze the behavior of the different double dynamic networks, in particular, the effects of the type and amount of crosslinks on their linear viscoelastic spectra. To this end, the dynamics of the double networks are compared with the respective individual responses of the polymeric component without crosslinks and the single networks (possessing only physical or only chemical crosslinks), in order to quantify their contributions to the relaxation mechanisms, particularly the interplay between disentanglement and bond association/dissociation processes. With the help of the TMA model, we also examine the respective roles of the lifetime of stickers, polydispersity, and molar mass. Triggered by the good comparison between predictions and experimental data, we propose a framework to tune material parameters in order to obtain a desired viscoelastic behavior.

An acrylate-based quasi-solid polymer electrolyte incorporating a novel dinitrile poly(ethylene glycol) plasticizer for lithium-ion batteries

The performance of solid polymer electrolytes is characterized by lower ionic conductivity than conventional liquid electrolytes but provides advantages in terms of operational safety. A quasi-solid polymer electrolyte (QSPE) based on a new plasticizer 4,7,10,13-tetraoxahexadecane-1,16-dinitrile (bCN-PEG4) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) incorporated into a polyacrylates matrix was successfully prepared via UV-induced copolymerization. The matrix consists of units of trimethylolpropane ethoxylate triacrylate (ETPTA), poly(ethylene glycol) diacrylate (PEGDA), and the monoacrylate poly(ethylene glycol) methyl ether acrylate (mPEGa). The QSPE containing 55 wt% bCN-PEG4 exhibits highly uniform morphology, thermal stability > 200 °C, ionic conductivity of 1.8 × 10−4 S cm−1 at 30 °C, and 1.3 × 10−3 S cm−1 at 80 °C, coupled with very high electrochemical stability (> 5 V vs. Li/Li+) and a low glass transition temperature (− 55.7 °C). A cycling experiment in a Li/QPSE/Li cell setup demonstrated the compatibility toward lithium metal additionally. The bCN-PEG4 offers an overall satisfying performance as a plasticizer in a poly(ethylene oxide)-based solid polymer electrolyte. The new QSPE is an alternative to dinitrile-based (e.g., succinonitrile) or glycol ether-based (e.g., tetraglyme) plasticizers with application potential in high-voltage lithium-ion batteries.Graphical abstract

Growing Strategy for Postmodifying Cross-Linked Polymers' Bulky Size, Shape, and Mechanical Properties.

Living organisms are open systems that can incorporate externally provided nutrients to vary their appearances and properties, while synthetic materials normally have fixed sizes, shapes, and functions. Herein, we report a strategy for enabling cross-linked polymers to continuously grow with programmable bulky structures and properties. The growing strategy involves repeatable processes including swelling of polymerizable components into the cross-linked polymers, in situ polymerization of the components, and homogenization of the original and newborn polymer networks. Using acrylate-based polymers as an example, we demonstrate that homogenization allows the grown polymer materials to further integrate various polymerizable components to alternate their bulky properties. During the growth, the changes from elastomers to organogels and then to hydrogels with updated covalent-linked functions (i.e., photochromism and thermoresponsiveness) are shown. Since this growing strategy is applicable to different acrylate systems, we envision its great potential in the design of next-generation polymers, smartening systems, and postmodification of cross-linked polymer materials.

Raman and scanning probe microscopy for differentiating surface imprints of E. coli and B. cereus.

Molecularly imprinted polymers (MIPs) are artificial recognition materials mimicking biological recognition entities such as antibodies. The general model of imprinting assumes that functional monomers interact with functional groups present on the target species which leads to cavities complementing the template in surface chemistry and shape thus ensuring recognition. However, to date there is little independent experimental evidence supporting that the surface chemistry in the imprints is tailored to analyte recognition and thus differs from the surface chemistry of the surrounding polymer. Herein, we investigate such chemical differences between imprints of Escherichia coli and Bacillus cereus in poly(styrene-co-DVB) and a commercial acrylate-based polymer by the means of confocal Raman microscopy and PLS-DA. The MIPs were generated using a stamping approach. Peak-force QNM measurements were conducted to rule out residues of bacterial cells in the imprints. While imprints of E. coli and B. cereus could be distinguished based on their Raman spectra in the acrylate-based polymer, differentiation in poly(styrene-co-DVB) was not significant. This could be a result of a higher potential of acrylate functional groups for interacting with lipopolysaccharides and peptidoglycans on bacteria surfaces compared to the phenyl groups of poly(styrene-co-DVB) and emphasizes the importance of the right choice of functional monomers for a specific target analyte.

Qualifying the contribution of fiber diameter on the acrylate-based electrospun shape memory polymer nano/microfiber properties.

Fibrous shape memory polymers (SMPs) have received growing interest in various applications, especially in biomedical applications, which offer new structures at the microscopic level and the potential of enhanced shape deformation of SMPs. In this paper, we report on the development and investigation of the properties of acrylate-based shape memory polymer fibers, fabricated by electrospinning technology with the addition of polystyrene (PS). Fibers with different diameters are manufactured using four different PS solution concentrations (25, 30, 35, and 40 wt%) and three flow rates (1.0, 2.5, and 5.0 μL min-1) with a 25 kV applied voltage and 17 cm electrospinning distance. Scanning electron microscope (SEM) images reveal that the average fiber diameter varies with polymer concentration and flow rates, ranging from 0.655 ± 0.376 to 4.975 ± 1.634 μm. Dynamic mechanical analysis (DMA) and stress-strain testing present that the glass transition temperature and tensile values are affected by fiber diameter distribution. The cyclic bending test directly proves that the electrospun SMP fiber webs are able to fully recover; additionally, the recovery speed is also affected by fiber diameter. With the combination of the SMP material and electrospinning technology, this work paves the way in designing and optimizing future SMP fibers properties by adjusting the fiber diameter.

Modeling Three-Dimensional-Printed Polymer Lattice Metamaterial Recovery After Cyclic Large Deformation

Abstract Lattice structure metamaterials generally exhibit better stiffness and/or tunable properties than natural materials. They have important applications in mechatronics and tissue engineering areas. In this work, we demonstrate crystal structure-inspired body-centered cubic (BCC)-lattice architected structures using different acrylate-based polymer materials to study the mechanical response in large deformation. Rigid BCC lattice metamaterials manifest outstanding recovery properties after undergoing multi-cycle compression. With appropriate cell wall thickness, the lattices have the capacity to recover their original shape and maintain a degree of stiffness. In further exploration, we combined mechanical tests and digital image correlation to elaborate on the deformation mechanisms. The digital image correlation (DIC) proves that displacement discrepancy exists in local positions. We propose hourglass and twist models to describe the buckling-induced pattern transformation which occurs during cyclic compressive deformation using simulation.

Organic/Inorganic Hybrid Thin-Film Encapsulation Using Inkjet Printing and PEALD for Industrial Large-Area Process Suitability and Flexible OLED Application.

We present herein the first report of organic/inorganic hybrid thin-film encapsulation (TFE) developed as an encapsulation process for mass production in the display industry. The proposed method was applied to fabricate a top-emitting organic light-emitting device (TEOLED). The organic/inorganic hybrid TFE has a 1.5 dyad structure and was fabricated using plasma-enhanced atomic layer deposition (PEALD) and inkjet printing (IJP) processes that can be applied to mass production operations in the industry. Currently, industries use inorganic thin films such as SiNx and SiOxNy fabricated through plasma-enhanced chemical vapor deposition (PECVD), which results in film thickness >1 μm; however, in the present work, an Al2O3 inorganic thin film with a thickness of 30 nm was successfully fabricated using ALD. Furthermore, to decouple the crack propagation between the adjacent Al2O3 thin films, an acrylate-based polymer layer was printed between these layers using IJP to finally obtain the 1.5 dyad hybrid TFE. The proposed method can be applied to optoelectronic devices with various form factors such as rollables and stretchable displays. The hybrid TFE developed in this study has a transmittance of 95% or more in the entire visible light region and a very low surface roughness of less than 1 nm. In addition, the measurement of water vapor transmission rate (WVTR) using commercial MOCON equipment yielded a value of 5 × 10-5 gm-2 day-1 (37.8 °C and 100% RH) or less, approaching the limit of the measuring equipment. The TFE was applied to TEOLEDs and the improvement in optical properties of the device was demonstrated. The OLED panel was manufactured and operated stably, showing excellent consistency even in the actual display manufacturing process. The panel operated normally even after 363 days in air. The proposed organic/inorganic hybrid encapsulant manufacturing process is applicable to the display industry and this study provides basic guidelines that can serve as a foothold for the development of various technologies in academia and industry alike.

Acrylate-based nanocomposite zirconium-dispersed polymer dielectric for flexible oxide thin-film transistors with a curvature radius of 2 mm

Novel hybrid dielectric film is synthesized at a low temperature of 150 °C using a solution process. Zirconium acrylate (ZrA) and poly(methyl methacrylate) (PMMA) comprise the inorganic and organic components, respectively. The acrylate-based molecular structure of both ingredients allows the facile formation of hybrid ZrA/PMMA dielectric film with neither additional coupling agent nor ultraviolet photon irradiation. The high quality of the hybrid ZrA/PMMA dielectric film is confirmed by its high dielectric constant of 5.5 and low leakage current density of 1.7 × 10−8 A/cm2 at the electric field of 1 MV/cm. The indium gallium tin oxide (IGTO) transistors with the optimal ZrA/PMMA gate insulator layer are fabricated on the polyimide substrate at the maximum high temperature of 150 °C. They exhibit hysteresis-free high performance with high carrier mobility of 24.3 cm2V−1s−1, gate swing of 0.61 V/decade and ION/OFF ratio of 4 × 106. Owing to the intrinsic deformability of hybrid dielectric film, these transistors maintained electrical performance after 100 cycles of mechanical bending to the extremely small radius of curvature of 2 mm.

Adsorbed Water Structure on Acrylate-Based Biocompatible Polymer Surface.

The role of water in the excellent biocompatibility of the acrylate-based polymers widely used for antibiofouling coating material has been realized previously. Here, we report femtosecond mid-infrared pump-probe spectroscopy of the OD stretch band of HOD molecule adsorbed on highly biocompatible poly(2-methoxyethyl) acrylate [PMEA] and poorly biocompatible poly(2-phenoxyethyl) acrylate [PPEA], both of which reveal that there are two water species with significantly different vibrational lifetime. PMEA interacts more strongly with water than PPEA through the H-bonding interaction between carbonyl (C═O) and water. The vibrational lifetime of the OD stretch in PPEA is notably longer by factors of 3 and 7 than those in PMEA and bulk water, respectively. The IR-pump visible-probe photothermal imaging further unravels substantial spatial overlap between polymer CO group and water for hydrated PMEA and a significant difference in surface morphology than those in PPEA, which exhibits the underlying relationships among polymer-water interaction, surface morphology, and biocompatibility.