scholarly journals Thermoset Polymer Matrix Structure and Properties: Coarse-Grained Simulations

Polymers ◽  
2018 ◽  
Vol 11 (1) ◽  
pp. 36 ◽  
Author(s):  
Vladimir Rudyak ◽  
Elizaveta Efimova ◽  
Daria Guseva ◽  
Alexander Chertovich
Keyword(s):  
Network Topology ◽  
Dissipative Particle Dynamics ◽  
Polymer Network ◽  
Polymer Networks ◽  
Covalent Bond ◽  
Mesh Size ◽  
Coarse Grained ◽  
Topological Parameters ◽  
Thermoset Polymer ◽  
Plasticizer Concentration

The formation of a thermoset polymer network is a complex process with great variability. In this study, we used dissipative particle dynamics and graph theory tools to investigate the curing process and network topology of a phthalonitrile thermoset to reveal the influence of initiator and plasticizer concentration on its properties. We also propose a novel way to characterize the network topology on the basis of two independent characteristics: simple cycle length (which is mainly affected by the initiator amount) and the number of simple cycles passing through a single covalent bond (which is determined primarily by plasticizer concentration). These values can be treated in the more familiar terms of network “mesh size” and “sponginess”, correspondingly. The combination of these two topological parameters allows one to characterize any given network in an implicit but precise way and predict the resulting network properties, including the mechanical modulus. We believe that the same approach could be useful for other polymer networks as well, including rubbers and gels.

scholarly journals Slip Spring-Based Mesoscopic Simulations of Polymer Networks: Methodology and the Corresponding Computational Code

Polymers ◽  
2018 ◽  
Vol 10 (10) ◽  
pp. 1156 ◽  
Author(s):  
Grigorios Megariotis ◽  
Georgios Vogiatzis ◽  
Aristotelis Sgouros ◽  
Doros Theodorou
Keyword(s):  
Monte Carlo ◽  
Equation Of State ◽  
Kinetic Monte Carlo ◽  
Polymer Network ◽  
Polymer Networks ◽  
Test System ◽  
Helmholtz Energy ◽  
Coarse Grained ◽  
Crosslinked Polymer ◽  
Mesoscopic Simulations

In previous work by the authors, a new methodology was developed for Brownian dynamics/kinetic Monte Carlo (BD/kMC) simulations of polymer melts. In this study, this methodology is extended for dynamical simulations of crosslinked polymer networks in a coarse-grained representation, wherein chains are modeled as sequences of beads, each bead encompassing a few Kuhn segments. In addition, the C++ code embodying these simulations, entitled Engine for Mesoscopic Simulations for Polymer Networks (EMSIPON) is described in detail. A crosslinked network of cis-1,4-polyisoprene is chosen as a test system. From the thermodynamic point of view, the system is fully described by a Helmholtz energy consisting of three explicit contributions: entropic springs, slip springs and non-bonded interactions. Entanglements between subchains in the network are represented by slip springs. The ends of the slip springs undergo thermally activated hops between adjacent beads along the chain backbones, which are tracked by kinetic Monte Carlo simulation. In addition, creation/destruction processes are included for the slip springs at dangling subchain ends. The Helmholtz energy of non-bonded interactions is derived from the Sanchez–Lacombe equation of state. The isothermal compressibility of the polymer network is predicted from equilibrium density fluctuations in very good agreement with the underlying equation of state and with experiment. Moreover, the methodology and the corresponding C++ code are applied to simulate elongational deformations of polymer rubbers. The shear stress relaxation modulus is predicted from equilibrium simulations of several microseconds of physical time in the undeformed state, as well as from stress-strain curves of the crosslinked polymer networks under deformation.

scholarly journals Light-triggered topological programmability in a dynamic covalent polymer network

2020 ◽  
Vol 6 (13) ◽  
pp. eaaz2362 ◽  
Author(s):  
Weike Zou ◽  
Binjie Jin ◽  
Yi Wu ◽  
Huijie Song ◽  
Yingwu Luo ◽  
...  
Keyword(s):  
Network Topology ◽  
Material Properties ◽  
Polymer Network ◽  
Polymer Networks ◽  
Isomerization Reaction ◽  
Network Polymer ◽  
Robotic Arms ◽  
Practical Applications ◽  
Topological States ◽  
High Degree

Dynamic covalent polymer networks exhibit unusual adaptability while maintaining the robustness of conventional covalent networks. Typically, their network topology is statistically nonchangeable, and their material properties are therefore nonprogrammable. By introducing topological heterogeneity, we demonstrate a concept of topology isomerizable network (TIN) that can be programmed into many topological states. Using a photo-latent catalyst that controls the isomerization reaction, spatiotemporal manipulation of the topology is realized. The overall result is that the network polymer can be programmed into numerous polymers with distinctive and spatially definable (thermo-) mechanical properties. Among many opportunities for practical applications, the unique attributes of TIN can be explored for use as shape-shifting structures, adaptive robotic arms, and fracture-resistant stretchable devices, showing a high degree of design versatility. The TIN concept enriches the design of polymers, with potential expansion into other materials with variations in dynamic covalent chemistries, isomerizable topologies, and programmable macroscopic properties.

Lubricity from Entangled Polymer Networks on Hydrogels

2016 ◽  
Vol 138 (4) ◽  
Author(s):  
Angela A. Pitenis ◽  
Juan Manuel Urueña ◽  
Ryan M. Nixon ◽  
Tapomoy Bhattacharjee ◽  
Brandon A. Krick ◽  
...  
Keyword(s):  
Mechanical Strength ◽  
Polymer Network ◽  
Polymer Networks ◽  
Mesh Size ◽  
Solution Polymerization ◽  
Hydrogel Sample ◽  
Low Friction ◽  
Aqueous Environments ◽  
Surface Measurements ◽  
Entangled Polymer

Structural hydrogel materials are being considered and investigated for a wide variety of biotribological applications. Unfortunately, most of the mechanical strength and rigidity of these materials comes from high polymer concentrations and correspondingly low polymer mesh size, which results in high friction coefficients in aqueous environments. Recent measurements have revealed that soft, flexible, and large mesh size hydrogels can provide ultra low friction, but this comes at the expense of mechanical strength. In this paper, we have prepared a low friction structural hydrogel sample of polyhydroxyethylmethacrylate (pHEMA) by polymerizing an entangled polymer network on the surface through a solution polymerization route. The entangled polymer network was made entirely from uncrosslinked polyacrylamide (pAAm) that was polymerized from an aqueous solution and had integral entanglement with the pHEMA surface. Measurements revealed that these entangled polymer networks could extend up to ∼200 μm from the surface, and these entangled polymer networks can provide reductions in friction coefficient of almost two orders of magnitude (μ > 0.7 to μ < 0.01).

Investigation of the Microscopic Viscoelastic Property for Cross-linked Polymer Network by Molecular Dynamics Simulation

2011 ◽  
Vol 39 (1) ◽  
pp. 44-58 ◽  
Author(s):  
Y. Masumoto ◽  
Y. Iida
Keyword(s):  
Molecular Dynamics ◽  
Molecular Dynamics Simulation ◽  
Analytical Method ◽  
Viscoelastic Properties ◽  
Polymer Network ◽  
Dynamics Simulation ◽  
Coarse Grained ◽  
The Cross ◽  
Microscopic Dynamic ◽  
Coarse Grained Molecular Dynamics

Abstract The purpose of this work is to develop a new analytical method for simulating the microscopic mechanical property of the cross-linked polymer system using the coarse-grained molecular dynamics simulation. This new analytical method will be utilized for the molecular designing of the tire rubber compound to improve the tire performances such as rolling resistance and wet traction. First, we evaluate the microscopic dynamic viscoelastic properties of the cross-linked polymer using coarse-grained molecular dynamics simulation. This simulation has been conducted by the coarse-grained molecular dynamics program in the OCTA) (http://octa.jp/). To simplify the problem, we employ the bead-spring model, in which a sequence of beads connected by springs denotes a polymer chain. The linear polymer chains that are cross-linked by the cross-linking agents express the three-dimensional cross-linked polymer network. In order to obtain the microscopic dynamic viscoelastic properties, oscillatory deformation is applied to the simulation cell. By applying the time-temperature reduction law to this simulation result, we can evaluate the dynamic viscoelastic properties in the wide deformational frequency range including the rubbery state. Then, the stress is separated into the nonbonding stress and the bonding stress. We confirm that the contribution of the nonbonding stress is larger at lower temperatures. On the other hand, the contribution of the bonding stress is larger at higher temperatures. Finally, analyzing a change of microscopic structure in dynamic oscillatory deformation, we determine that the temperature/frequency dependence of bond stress response to a dynamic oscillatory deformation depends on the temperature dependence of the average bond length in the equilibrium structure and the temperature/frequency dependence of bond orientation. We show that our simulation is a useful tool for studying the microscopic properties of a cross-linked polymer.

scholarly journals Solubilization of Charged Porphyrins in Interpolyelectrolyte Complexes: A Computer Study

Polymers ◽  
2021 ◽  
Vol 13 (4) ◽  
pp. 502
Author(s):  
Karel Šindelka ◽  
Zuzana Limpouchová ◽  
Karel Procházka
Keyword(s):  
Dissipative Particle Dynamics ◽  
Water Soluble ◽  
Coarse Grained ◽  
Core Shell ◽  
Computer Study ◽  
Interpolyelectrolyte Complex ◽  
The Core ◽  
Porphyrin Derivatives ◽  
Oppositely Charged ◽  
Positively Charged

Using coarse-grained dissipative particle dynamics (DPD) with explicit electrostatics, we performed (i) an extensive series of simulations of the electrostatic co-assembly of asymmetric oppositely charged copolymers composed of one (either positively or negatively charged) polyelectrolyte (PE) block A and one water-soluble block B and (ii) studied the solubilization of positively charged porphyrin derivatives (P+) in the interpolyelectrolyte complex (IPEC) cores of co-assembled nanoparticles. We studied the stoichiometric mixtures of 137 A10+B25 and 137 A10−B25 chains with moderately hydrophobic A blocks (DPD interaction parameter aAS=35) and hydrophilic B blocks (aBS=25) with 10 to 120 P+ added (aPS=39). The P+ interactions with other components were set to match literature information on their limited solubility and aggregation behavior. The study shows that the moderately soluble P+ molecules easily solubilize in IPEC cores, where they partly replace PE+ and electrostatically crosslink PE− blocks. As the large P+ rings are apt to aggregate, P+ molecules aggregate in IPEC cores. The aggregation, which starts at very low loadings, is promoted by increasing the number of P+ in the mixture. The positively charged copolymers repelled from the central part of IPEC core partially concentrate at the core-shell interface and partially escape into bulk solvent depending on the amount of P+ in the mixture and on their association number, AS. If AS is lower than the ensemble average ⟨AS⟩n, the copolymer chains released from IPEC preferentially concentrate at the core-shell interface, thus increasing AS, which approaches ⟨AS⟩n. If AS>⟨AS⟩n, they escape into the bulk solvent.

THE SIMULATION OF POLYSTYRENE/NANOPARTICLES COMPOSITE MICROSPHERES USING DISSIPATIVE PARTICLE DYNAMICS

2013 ◽  
Vol 12 (02) ◽  
pp. 1250111 ◽  
Author(s):  
HAILONG XU ◽  
QIUYU ZHANG ◽  
HEPENG ZHANG ◽  
BAOLIANG ZHANG ◽  
CHANGJIE YIN
Keyword(s):  
Dissipative Particle Dynamics ◽  
Sodium Dodecyl ◽  
Coarse Graining ◽  
Particle Dynamics ◽  
Coarse Grained ◽  
Polystyrene Nanoparticles ◽  
Coarse Grained Model ◽  
Composite Microspheres ◽  
Polystyrene Matrix ◽  
Materials Studio

Dissipative particle dynamics (DPD) was initially used to simulate the polystyrene/nanoparticle composite microspheres (PNCM) in this paper. The coarse graining model of PNCM was established. And the DPD parameterization of the model was represented in detail. The DPD repulsion parameters were calculated from the cohesive energy density which could be calculated by amorphous modules in Materials Studio. The equilibrium configuration of the simulated PNCM shows that the nanoparticles were actually "modified" with oleic acid and the modified nanoparticles were embedded in the bulk of polystyrene. As sodium dodecyl sulfate (SDS) was located in the interface between water and polystyrene, the hydrophilic head of SDS stretched into water while the hydrophobic tailed into polystyrene. All simulated phenomena were consistent with the experimental results in preparation of polystyrene/nanoparticles composite microspheres. The effect of surface modification of nanoparticles on its dispersion in polystyrene matrix was also studied by adjusting the interaction parameters between the OA and NP beads. The final results indicated that the nanoparticles removed from the core of composite microsphere to the surface with increase of a OA-NP . All the simulated results demonstrated that our coarse–grained model was reasonable.

scholarly journals Small Oligonucleotides Detection in Three-Dimensional Polymer Network of DNA-PEG Hydrogels

2021 ◽  
Author(s):  
Alessia Mazzarotta ◽  
Tania Maristella Caputo ◽  
Luca Raiola ◽  
Edmondo Battista ◽  
Paolo Antonio Netti ◽  
...  
Keyword(s):  
Polymer Network ◽  
Three Dimensional ◽  
Mesh Size ◽  
Short Oligonucleotide ◽  
Dna Oligonucleotides ◽  
Hydrogel Network ◽  
Displacement Assay ◽  
Oligonucleotide Detection ◽  
Biomolecules Detection ◽  
And Diffusion

The control of the three-dimensional (3D) polymer network structure is important for permselective materials when specific biomolecules detection is needed. Here we investigate conditions to obtain a tailored hydrogel network that combine both molecular filtering and molecular capture capabilities for biosensing applications. Along this line short oligonucleotide detection in a displacement assay is set within PEGDA hydrogels synthetized by UV radical photopolymerization. To provide insights on the molecular filter capability, diffusion studies of several probes (sulforhodamine G and dextrans) with different hydrodynamic radii were carried out using NMR technique. Moreover, fluorometric analyses of hybridization of DNA oligonucleotides inside PEGDA-hydrogels shed light on the mechanisms of recognition in 3D, highlighting that mesh size and crowding effect greatly impact of hybridization mechanism onto polymer network. Finally, we found the best probe density and diffusion transport conditions to allow the specific oligonucleotide capture and detection inside PEGDA-hydrogels for oligonucleotide detection and the filtering out of higher molecular weight molecules.

scholarly journals Single-Macromolecular Level Imaging of a Hydrogel Structure

2021 ◽  
Author(s):  
Ryuji Kiyama ◽  
Takayuki Nonoyama ◽  
Sedlacik Tomas ◽  
Hiroshi Jinnai ◽  
Jian Ping Gong
Keyword(s):  
Polymer Network ◽  
Mesh Size ◽  
Fixation Method ◽  
Gel Properties ◽  
Cell Scaffolds ◽  
Transmission Electron ◽  
Hydrogel Network ◽  
Network Observation ◽  
Surface Network ◽  
First Time

Hydrogels are promising materials for several applications, including cell scaffolds and artificial load-bearing substitutes (cartilages, ligaments, tendons, etc.). Direct observation of the nanoscale polymer network of hydrogels is essential in understanding its properties. However, imaging of individual network strands at the molecular level is not achieved yet due to the lack of suitable methods. Herein, for the first time, we developed a novel mineral-staining method and network fixation method for transmission electron microscopy observation to visualize the hydrogel network in its unperturbed conformation with nanometer resolution. Surface network observation indicates that the length of surface dangling chains, which play a major role in friction and wetting, can be estimated from the gel mesh size. Moreover, bulk observations reveals a hierarchical formation mechanism of gel heterogeneity. These observations have the great potential to advance gel science by providing comprehensive perspective that link bulk gel properties with nanoscale.

scholarly journals A Generic Force Field for Simulating Native Protein Structures Using Dissipative Particle Dynamics

Soft Matter ◽  
2021 ◽  
Author(s):  
Rakesh K Vaiwala ◽  
Ganapathy Ayappa
Keyword(s):  
Molecular Dynamics ◽  
Force Field ◽  
Molecular Dynamics Simulations ◽  
Dissipative Particle Dynamics ◽  
Protein Structures ◽  
Particle Dynamics ◽  
Coarse Grained ◽  
Native Protein ◽  
Dynamics Simulations

A coarse-grained force field for molecular dynamics simulations of native structures of proteins in a dissipative particle dynamics (DPD) framework is developed. The parameters for bonded interactions are derived by...

The effect of blob size in polymer networks on nanoparticle-mediated adhesion of hydrogels

Soft Matter ◽  
2019 ◽  
Vol 15 (48) ◽  
pp. 9942-9948
Author(s):  
Sohyun Kim ◽  
Tae Hui Kang ◽  
Gi-Ra Yi
Keyword(s):  
Mesoporous Silica ◽  
Silica Nanoparticles ◽  
Pore Diameter ◽  
Physical Adsorption ◽  
Mesoporous Silica Nanoparticles ◽  
Polymer Networks ◽  
Mesh Size ◽  
Adhesion Energy ◽  
Polymer Chains

Mesoporous silica nanoparticles can be used as an adhesive for hydrogels due to their physical adsorption to polymer chains, in which adhesion energy can be affected by the ratio of mesh size and pore diameter.

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