Superplasticity in an organic crystal

Takamizawa, Satoshi; Takasaki, Yuichi; Sasaki, Toshiyuki; Ozaki, Noriaki

doi:10.1038/s41467-018-06431-7

“…[42] Thec ompound was capable of bearing immense amounts of strain-up to 520 %-along the [100] direction before fracture.T he crystal structure is also maintained by p-p interactions and hydrogen bonding,w hich facilitated the impressive mechanical properties.M ore importantly,t he compound was also analyzed using X-ray diffraction after being strained to 100-150 %and 330 %along the [100] direction. [42] Thec ompound was capable of bearing immense amounts of strain-up to 520 %-along the [100] direction before fracture.T he crystal structure is also maintained by p-p interactions and hydrogen bonding,w hich facilitated the impressive mechanical properties.M ore importantly,t he compound was also analyzed using X-ray diffraction after being strained to 100-150 %and 330 %along the [100] direction.…”

Section: Methodsmentioning

confidence: 99%

Is a Bent Crystal Still a Single Crystal?

Commins

¹

,

Karothu

²

,

Naumov

³

2019

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The mention of the word “crystal” invokes images of minerals, gems, and rocks, all of which are inevitably solid, hard, and durable entities with well‐defined smooth faces and straight edges. With the discovery in the first half of the 20th century that many molecular crystals are soft and can be deformed in a similar way as rubber or plastic, this perception is changing, and both the concept and formal definition of what a crystal is may require reinterpretation. The seemingly naïve question posed in the title of this Minireview does not have a simple answer. Here, we discuss how the effects of the elastic and plastic deformation of molecular crystals on the diffraction signature give primary evidence of their degree of crystallinity. In most cases, the definition of a crystal holds for both elastically and plastically deformed crystals and, unless there is significant or complete physical separation of the crystal during the deformation, they can safely be considered (deformed) single crystals with a high concentration of defects.

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“…

As altering permanent shapes without loss of material function is of practical importance for material molding, especially for elastic materials,s hape-rememorization ability would enhance the utility of elastic crystalline materials.Since diffusionless plastic deformability can preserve the crystallinity of materials,t he interconversion of diffusionless mechanical deformability between superelasticity and ferroelasticity could enable shape rememorization of superelastic single crystals.T his study demonstrates the shape rememorization of an organosuperelastic single crystal of 1,4-dicyanobenzene through time-reversible interconversion of superelasticity-ferroelasticity relaxation by holding the mechanically twinned crystal without heating. Among their properties,s uperelasticity (SE) [18,[28][29][30][31] and ferroelasticity (FE) [19][20][21][22][23][24][25][26] give crystallographically well-regulated deformability while retaining single crystallinity. Practical applications of solid materials demand not only appropriate functions but also appropriate shapes.S ome polycrystalline and amorphous materials,s uch as alloys and polymers,are available in various shapes through molding in ad iffusion manner by thermal processes,i nw hich thermal stability is essential.

…”

mentioning

confidence: 99%

“…Therefore,twinning deformation irrelevant to phase changes basically leads to twinning FE (tFE). [36] tSE has already been found in an umber of organic materials [18,29,37] in the short history of organosuperelasticity since 2014, [23] thus indicating that tSE will also become commonplace in organic crystals.Thes hape-memory effect (SME) of SMAs can be regarded as the interconversion of FE and SE, whereby ferroelastically deformed solids revert to their initial shapes (memorized shapes) by superelastic recovery through aphase transition. [19][20][21][22][23][24][25][26] Furthermore, multiple tFE effects with versatile deformability have been found in a1 ,4-diethoxybenzene crystal.…”

mentioning

confidence: 99%

“…On the other hand, reshaping singlecrystalline materials,i nw hich at hree-dimensional order is kept, is achieved by ac ombination of cutting,f iling, [1] and etching [2,3] according to their physical and chemical characteristics and intended use.R ecently,t he mechanical deformability of organic crystals has attracted great attention. Among their properties,s uperelasticity (SE) [18,[28][29][30][31] and ferroelasticity (FE) [19][20][21][22][23][24][25][26] give crystallographically well-regulated deformability while retaining single crystallinity. SE and FE have been developed in the fields of the materials science of metal alloys and the physics of ferroics, [32] respectively.M echanical deformations through both SE and FE are realized by diffusionless plastic deformability, whereby SE spontaneously recovers from strain and FE leaves permanent strain.…”

mentioning

confidence: 99%

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Shape Rememorization of an Organosuperelastic Crystal through Superelasticity–Ferroelasticity Interconversion

Sakamoto

¹

,

Sasaki

²

,

Sato‐Tomita

³

et al. 2019

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As altering permanent shapes without loss of material function is of practical importance for material molding, especially for elastic materials,s hape-rememorization ability would enhance the utility of elastic crystalline materials.Since diffusionless plastic deformability can preserve the crystallinity of materials,t he interconversion of diffusionless mechanical deformability between superelasticity and ferroelasticity could enable shape rememorization of superelastic single crystals.T his study demonstrates the shape rememorization of an organosuperelastic single crystal of 1,4-dicyanobenzene through time-reversible interconversion of superelasticity-ferroelasticity relaxation by holding the mechanically twinned crystal without heating. The shaperememorization ability of the organosuperelastic crystal indicates the compatibility of superelasticity (antiferroelasticity) and ferroelasticity as well as the intrinsic workability of organic crystalline materials capable of recovering their crystal functions under mild conditions. Practical applications of solid materials demand not only appropriate functions but also appropriate shapes.S ome polycrystalline and amorphous materials,s uch as alloys and polymers,are available in various shapes through molding in ad iffusion manner by thermal processes,i nw hich thermal stability is essential. On the other hand, reshaping singlecrystalline materials,i nw hich at hree-dimensional order is kept, is achieved by ac ombination of cutting,f iling, [1] and etching [2,3] according to their physical and chemical characteristics and intended use.R ecently,t he mechanical deformability of organic crystals has attracted great attention. Among their properties,s uperelasticity (SE) [18,[28][29][30][31] and ferroelasticity (FE) [19][20][21][22][23][24][25][26] give crystallographically well-regulated deformability while retaining single crystallinity. SE and FE have been developed in the fields of the materials science of metal alloys and the physics of ferroics, [32] respectively.M echanical deformations through both SE and FE are realized by diffusionless plastic deformability, whereby SE spontaneously recovers from strain and FE leaves permanent strain. In so-called shape-memory alloys (SMAs), [33][34][35] the shape is recovered because of the thermal generation of SE by as olid-state phase transition based on Gibbs free energy gaps,t hat is,m artensitic SE (mSE). Therefore,twinning deformation irrelevant to phase changes basically leads to twinning FE (tFE). Although tFE was claimed in an organic crystal of squaric acid in 1979, [19] tFE has now been identified in an increasing number of organic crystals and become commonplace in organic crystals composed of structurally flexible molecules. [19][20][21][22][23][24][25][26] Furthermore, multiple tFE effects with versatile deformability have been found in a1 ,4-diethoxybenzene crystal. [26] Tw inning deformability is apotential effective reshaping procedure for organic single crystals.Some organic crystals exhibit SE, so-called...

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“…[42] Diese Verbindung war in der Lage,i mmensen Dehnungswerten -b is zu 520 %entlang der [100]-Richtung widerstehen, bis es zum Bruch kam. [42] Diese Verbindung war in der Lage,i mmensen Dehnungswerten -b is zu 520 %entlang der [100]-Richtung widerstehen, bis es zum Bruch kam.…”

Section: Angewandte Chemieunclassified

Ist ein gebogener Kristall immer noch ein Einkristall?

Commins¹,

Karothu²,

Naumov

³

2019

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Die Erwähnung des Wortes “Kristall” ruft beim Betrachter Bilder von Mineralien, Edelsteinen und Gesteinen hervor, die alle unvermeidlich solide, harte und langlebige Objekte mit klar definierten glatten Flächen und geraden Kanten sind. Mit der Entdeckung in der ersten Hälfte des 20. Jahrhunderts, dass viele molekulare Kristalle weich sind und ähnlich wie Gummi oder Kunststoff verformt werden können, entwickelte sich die Auffassung, dass das, was einst als Kristall galt, heute einer neuen formalen Definition bedarf. Die scheinbar naive Frage im Titel dieses Aufsatzes hat keine einfache Antwort. Wir diskutieren die Auswirkungen der elastischen und plastischen Verformung von Molekülkristallen auf die Beugungssignatur als primären Nachweis für den Grad ihrer Kristallinität. In den meisten Fällen gilt die allgemein akzeptierte Definition eines Kristalls auch für elastisch und plastisch verformte Kristalle. Sofern keine signifikante oder vollständige physikalische Trennung des Kristalls während der Verformung vorliegt, können sie sicher als (verformte) Einkristalle mit hoher Fehlerdichte betrachtet werden.

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Superplasticity in an organic crystal

Cited by 104 publications

References 23 publications

Is a Bent Crystal Still a Single Crystal?

Is a Bent Crystal Still a Single Crystal?

Shape Rememorization of an Organosuperelastic Crystal through Superelasticity–Ferroelasticity Interconversion

Ist ein gebogener Kristall immer noch ein Einkristall?

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