Reactive molecular dynamics simulations of thermal and shear-driven oligomerization

Bhuiyan, Fakhrul H.; Kim, Seong H.; Martini, Ashlie

doi:10.1016/j.apsusc.2022.153209

Cited by 16 publications

(38 citation statements)

References 62 publications

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“…Similar observations have been made for other simple organic molecules, including αpinene and allyl alcohol, in both experiments and simulations. 21,23,31,43 Here, interesting observations can be made from the relative reactivity of the three precursors. For methylcyclopentane and cyclohexane at 300 K, very little oxidative chemisorption was observed at any pressure condition tested (Fig.…”

Section: Resultsmentioning

confidence: 99%

“…The number of precursor molecules was chosen to form at least a monolayer on each surface. The amorphous silica slabs were created using a heat and quench method that involved heating a cristobalite slab to 4000 K and then cooling it back to room temperature, with a heating and cooling rate of 0.02 K/fs 23,31 .…”

Section: Simulations Of Cyclohexane Cyclohexene and Methylcyclopentan...mentioning

confidence: 99%

“…39 This force field was used for a similar system previously to study thermal and shear-driven oligomerization of α-pinene. 23,31 The time step for dynamics was 0.25 fs. All simulations were performed using the Large Atomic/Molecular Massively Parallel Simulation (LAMMPS) software.…”

Section: Simulations Of Cyclohexane Cyclohexene and Methylcyclopentan...mentioning

confidence: 99%

“…29,30 ReaxFF-MD simulations of polymerization of allyl alcohol and α-pinene identified shear stress as the key driver of oligomerization reactions and suggested that the mechanochemical activation of the reacting species was caused by shear-induced physical deformation. 21,23,31 A hybrid MD simulation framework integrating a classical force field and ReaxFF captured the physical entanglement between an epoxy network and a cyclobutane-based mechanophore embedded polymer chain, and showed that the intensity of fluorescence was directly proportional to the deformation of the mechanophore. 32 Another study on dimeric anthracene-based mechanophore using the same hybrid MD simulation framework predicted the critical strain for the activation of the mechanophore embedded polymer that was in good agreement with experimental findings.…”

Section: Introductionmentioning

confidence: 99%

“…Previous studies of α-pinene, pinane, and n-decane highlighted the role of ring strain and C=C double bond in shear-driven reactions. 23,24,31 Based on this, we modeled methylcyclopentane, cyclohexane, and cyclohexene to investigate the mechanochemical response of a ring structure, double bond, and methyl side group in cyclic compounds. In the simulations, these precursors were subject to normal and shear stress, and the resulting oxidative chemisorption and oligomerization reactions were tracked.…”

Section: Introductionmentioning

confidence: 99%

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Shear-activated chemisorption and association of cyclic organic molecules

Bhuiyan

Kim

et al. 2023

Faraday Discuss.

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Section: Resultsmentioning

confidence: 99%

Section: Simulations Of Cyclohexane Cyclohexene and Methylcyclopentan...mentioning

confidence: 99%

Section: Simulations Of Cyclohexane Cyclohexene and Methylcyclopentan...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Shear-activated chemisorption and association of cyclic organic molecules

Bhuiyan

Kim

et al. 2023

Faraday Discuss.

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Molecular Structure and Environment Dependence of Shear-Driven Chemical Reactions: Tribopolymerization of Methylcyclopentane, Cyclohexane and Cyclohexene on Stainless Steel

Jang

Bhuiyan

et al. 2023

Tribol Lett

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Tribochemistry, which is another name of mechanochemistry driven by shear, deals with complex and dynamic interfacial processes that can lead to facilitation of surface wear or formation of bene cial tribo lms. For better mechanistic understanding, we investigated the reactivity of tribopolymerization of organic molecules with different internal ring strain energy (methylcyclopentane, cyclohexane, and cyclohexene) on a stainless steel (SS) surface in inert ( N 2 ), oxidizing (O 2 ), and reducing (H 2 ) environments. On the clean SS surface, precursor molecules were found to physisorb with a broad range of molecular orientations. In inert and reducing environments, the strain-free cyclohexane showed the lowest tribochemical activity among the three tested. Compared to the N 2 environment, the tribochemical activity in H 2 was suppressed. In the O 2 environment, only cyclohexene produced tribo lms and methylcyclopentane and cyclohexane did not. When tribo lms were analyzed with Raman spectroscopy, the spectral features of diamond-like carbon (DLC) or amorphous carbon (a-C) were observed due to photochemical degradation of triboproducts. Based on infrared spectroscopy, tribo lms were found to be organic polymers containing oxygenated groups. Whenever polymeric tribro lms were produced, wear volume was suppressed by orders of magnitudes but not completely to zero. These results supported the previously suggested mechanisms which involved surface oxygens as a reactant species of the tribopolymerization process.

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Formation of Wear-Protective Tribofilms on Different Steel Surfaces During Lubricated Sliding

et al. 2023

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We report here the impact of different alloying elements in steels on friction and wear behavior by performing ball-on-at lubricated reciprocating tribotesting experiments on 52100 ball on steel ats with different compositions (52100, 1045, A2, D2, M2, and a specialty Cu-alloyed steel) heat-treated to give similar hardness and microstructure, with polyalphaole n (PAO-4) as the lubricant. There are small variations of coe cient of friction among these alloys. The major observation is that steels containing high concentrations (≥ 10 wt.%) of Cr, Mo, and V gave rise to markedly reduced wear compared with 52100 or plain carbon steels. D2 steel, which contains 11.5 wt.% Cr as the major alloying element was the most wear-resistant. The wear resistance is strongly correlated with the e ciency of formation of carboncontaining oligomeric lms at specimen surfaces as determined by Raman spectroscopy. This correlation holds for steels heat-treated to have higher hardness and with n-dodecane, a much less viscous lubricant compared with PAO-4. Given the strong a nity of chromium to oxygen, chromium should exist as Cr 2 O 3 at the steel surfaces during testing. We have performed molecular dynamics simulation on Cr 2 O 3 and demonstrated its ability to catalyze the formation of carbon-containing oligomeric lms from hydrocarbon molecules, consistent with its known catalytic activity in other hydrocarbon reactions. We believe that chromium-containing alloys, such as D2, and coatings, such as CrN, derive their wear resistance in part from the e cient in-situ formation of wear-protective carbon tribo lms at contacting asperities.

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Reactive molecular dynamics simulations of thermal and shear-driven oligomerization

Cited by 16 publications

References 62 publications

Shear-activated chemisorption and association of cyclic organic molecules

Shear-activated chemisorption and association of cyclic organic molecules

Molecular Structure and Environment Dependence of Shear-Driven Chemical Reactions: Tribopolymerization of Methylcyclopentane, Cyclohexane and Cyclohexene on Stainless Steel

Formation of Wear-Protective Tribofilms on Different Steel Surfaces During Lubricated Sliding

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