Fundamental limits of material toughening in molecularly confined polymers

Isaacson, Scott G.; Lionti, Krystelle; Volksen, Willi; Magbitang, Teddie; Matsuda, Yusuke; Dauskardt, Reinhold H.; Dubois, Géraud

doi:10.1038/nmat4475

Cited by 59 publications

(74 citation statements)

References 25 publications

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“…In the case of polymers, space restriction causes suppression of polymer chains segmental mobility and increases the rigidity of the chains. Toughening of confined polymers extends to a limit of the strength of individual molecules as it was observed for polysterene in 7 nm silica pores [14]. Strong densification of polymer has also been evidenced with gradual suppression of G-actin in phospholipid-stabilized emulsion droplets, which resulted even in cortex formation [1].…”

Section: Introductionmentioning

confidence: 81%

“…The effect is well pronounced for both crystalline and amorphous materials, including polymers [11,12]. As a result, the microstructure of a material changes in response to steric confinement and can be modified by controlling restrictor sizes [13,14]. In the case of polymers, space restriction causes suppression of polymer chains segmental mobility and increases the rigidity of the chains.…”

Section: Introductionmentioning

confidence: 99%

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The effect of geometric confinement on gas separation characteristics of additive poly[3-(trimethylsilyl)tricyclononene-7]

Chernova¹,

Bermeshev²,

Петухов³

et al. 2018

Nanosystems: Phys. Chem. Math.

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Composite membranes based on a hydrophobic glassy poly[3-(trimethylsilyl)tricyclononene-7] (PTCNSi-1) confined in the channels of anodic alumina with different pore diameters are discussed. Formation of continuous polymer film with partial penetration of polymer into the rigid pores of anodic alumina was achieved by spin-coating technique under vacuum suction. Mass-transport characteristics of composite membranes reveal a slight reduction of composite membrane permeability for condensable gases, and many-fold permeability drop for permanent gases as compared to the bulk film. This results in an ideal selectivity rise over 35 for C 4 H 10 /CH 4 pair compared to 12.6 for bulk PTCNSi-1. The effect is attributed to a solubility-controlled mobility of polymer segments confined in the AAO channels and formation of rigid shallow polymer layer at AAO/polymer interface, which suppress transport of gases. The correlation between intrinsic properties of the polymer (hydrophobicity, Kuhn segment) and its transport characteristics in the confined state is discussed. The evolution of the permeance and pure-gas selectivity of the composite membranes during ageing is also reported.

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Section: Introductionmentioning

confidence: 81%

Section: Introductionmentioning

confidence: 99%

The effect of geometric confinement on gas separation characteristics of additive poly[3-(trimethylsilyl)tricyclononene-7]

Chernova¹,

Bermeshev²,

Петухов³

et al. 2018

Nanosystems: Phys. Chem. Math.

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show abstract

“…There is, therefore, the notion that confinement induced by well‐dispersed nanoparticles can induce significant changes to the physical properties of a matrix, and this has been investigated in model systems [ 21 ] in an effort to understand the unusual properties of materials produced by nature. [ 22 ] There is, however, the question of the number of nanoparticles present in the matrix.…”

Section: Introductionmentioning

confidence: 99%

Polyhedral Oligomeric Silsesquioxane Induced Thermomechanical Reinforcement in Polymer Films Using Only Parts‐per‐Million Content

Romo-Uribe

Lichtenhan

2020

Macro Materials & Eng

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particle dispersion. The tendency of nano particles to agglomerate has been an unsurpassed hurdle so far. [2,3] The decora tion of nanoparticles surfaces with specific end groups or oligomers to induce homo geneous dispersion and particlepolymer matrix interactions is a cost and time consuming alternative with unconvincing results. [4] Controlling the dispersion of nano particles in a polymeric matrix is key to understand their influence on physical properties. Enabling the dispersion at near unitlevel takes advantage of the high surface area and volume of nano particles and particlelike nanochemicals. Under this condition, recent experimental evidence suggests that only small nano particle content (<5 wt%) is required to produce nanoeffects. [5-10] On the other hand, recent research has shown that when nanoparticles are present in a polymeric matrix, at low con centrations and welldispersed, [7-10] con finement effects can become relevant and the chain dynamics can be modified. [11,12] Therefore, dispersed silica nanoparticles produced entanglement dilation and reduced the melt viscosity of the polymer matrix. [8,13-18] On the other hand, welldispersed layer silicates in polyacrylates and polyelectrolytes significantly attenuated the αrelaxation and increased by orders of magni tude the tensile mechanical modulus by confining the macro molecules between the nanoplatelets. [7,19] There was, however, a penalty on strain at fracture as the nanoparticles acted as stress concentrators thus reducing the extensibility of the nano composite, a result typically seen in reinforced (nano) com posites, i.e., the improvement of tensile mechanical properties degrades performance in extensibility. [7,20] There is, therefore, the notion that confinement induced by welldispersed nanoparticles can induce significant changes to the physical properties of a matrix, and this has been investi gated in model systems [21] in an effort to understand the unu sual properties of materials produced by nature. [22] There is, however, the question of the number of nanoparticles present in the matrix. Recently, the authors reported on a methodology to dis perse untethered polyhedral oligomeric silsesquioxanes (POSS) at a single unit in a lowdensity polyethylene (LDPE) Reinforcement of polymers by nanoparticles has been a challenge due to aggregation and solubility limits, especially at high loads. In this research, a robust and environmentally friendly fabrication approach to produce films reinforced with only parts-per-million (ppm) octamethyl-polyhedral oligomeric silsesquioxane (mePOSS) using conventional extrusion and blow molding processing is demonstrated. The nanocomposites exhibit enhanced thermomechanical properties, and only 160 ppm mePOSS increase the tensile mechanical modulus, E, by ≈120% relative to the neat polymer. Remarkably, there is no penalty on strain at fracture ε f , as usually seen in reinforced (nano) composites. Toughness, yield stress, tear, and puncture resistance are also an increasing function of mePOSS content. F...

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“…Prior to crazing formation, the system undergoes a cavitation process, in which voids preferentially occur at transformation sites with a low local modulus [1][2][3], leading to "cavitation yielding" [4]. Crazing, originating from cavity nucleation, is the phenomenon of forming regional fibrils across the fracture plane [5][6][7]. Drawing of fibrils from the amorphous phase causes active dissipation of energy released from the crack tips, which is important for load-bearing applications [8].…”

Section: Introductionmentioning

confidence: 99%

Atomistic Insights into the Tunable Transition from Cavitation to Crazing in Diamond Nanothread-Reinforced Polymer Composites

Zhang

et al. 2020

Research

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Cavitation and crazing in thermosetting polymers can be sophisticatedly designed for valuable applications in optics, electronics, and biotechnology. It is a great challenge for numerical study to describe the formations of cavity and fibrils in polymer composite due to the complicated interfacial interaction. To explore this challenging task, we exploit a two-phase coarse-grained framework which serves as an efficient atomistic level-consistent approach to expose and predict the transition between cavitation and crazing in a polymeric system. The coarse-grained framework is utilized to transmit the information between single phase and interface in polymer composite, and the learning tasks of force field are fulfilled through parameterization of mechanical performances and structural characterizations. We elaborate on the intrinsic characteristics of the cavitation-crazing transition in diamond nanothread- (DNT-) reinforced polymethyl methacrylate composites, in which DNT plays a specific role of nanomodulator to tune the cavity volume ratio. The transition from cavitation to crazing can be induced through a novel dissipative mechanism of opening an interlocked network, in which case the DNT is stretched to the aligned fibrils and links crazing tightly by interfacial adhesion. The designed computational framework can broaden the scope of theoretical tools for providing better insights into the microstructure design of polymer composites.

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Fundamental limits of material toughening in molecularly confined polymers

Cited by 59 publications

References 25 publications

The effect of geometric confinement on gas separation characteristics of additive poly[3-(trimethylsilyl)tricyclononene-7]

The effect of geometric confinement on gas separation characteristics of additive poly[3-(trimethylsilyl)tricyclononene-7]

Polyhedral Oligomeric Silsesquioxane Induced Thermomechanical Reinforcement in Polymer Films Using Only Parts‐per‐Million Content

Atomistic Insights into the Tunable Transition from Cavitation to Crazing in Diamond Nanothread-Reinforced Polymer Composites

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