Effect of hydrogen fluoride and magnesium oxide on AZ31 Mg alloy/carbon fiber-reinforced plastic composite by thermal laser joining technique

Although hydrofluoric acid(HF)surface treatment is known to enhance the joining of metals with polymers,there is limited information on its effect on the joining of AZ31 alloy and carbon-fiber-reinforced plastics(CFRPs)through laser-assisted metal and plastic direct joining(LAMP).This study uses the LAMP technique to produce AZ31-CFRP joints.The joining process involves as-received AZ31,HFpretreated AZ31,and thermally oxidized HF-pretreated AZ31 alloy sheets.Furthermore,the bonding strength of joints prepared with thermally oxidized AZ31 alloy sheets is examined to ascertain the combined effect of HF treatment and thermal oxidation on bonding strength.The microstructures,surface chemical interactions,and mechanical performances of joints are investigated under tensile shear loading.Various factors,such as bubble formation,CFRP resin decomposition,and mechanical interlocking considerably affect joint strength.Additionally,surface chemical interactions between the active species on metal parts and the polar amide along with carbonyl groups of polymer play a significant role in improving joint strength.Joints prepared with surface-pretreated AZ31 alloy sheets show significant improvements in bonding strength.

Strengthening and toughening styrene-butadiene rubber by mechanically interlocked cross-links

Styrene-butadiene rubber(SBR)is an indispensable material in modern society,and the necessity for enhanced mechanical properties in SBR persists,particularly to withstand the rigors of challenging environmental conditions.To surmount the limitations of conventional cross-linking modes,mechanical bonds stabilized by host-guest recognition are incorporated as the cross-linking points of SBR to form mechanically interlocked networks(MINs).Compared with covalently cross-linked network,the representative MIN exhibits superior mechanical performance in terms of elongation(1392%)and breaking strength(4.6 MPa),whose toughness has surged by 17 times.Dissociation of host-guest recognition and subsequent sliding motion provide an effective energy dissipation mechanism,and the release of hidden length is also beneficial to enhance toughness.Furthermore,the introduction of the rotaxane cross-links made the network more pliable and possess damping and elastic properties,which can return to initial state with one minute rest interval.We aspire that this direct introduction method can serve as a blueprint,offering valuable insights for the enhancement of mechanical properties in conventional commercial polymer materials.

Microstructural formation and mechanical performance of friction stir double-riveting welded Al-Cu joints

A novel friction stir double-riveting welding(FSDRW) technology was proposed in order to realize the high-quality joining of upper aluminum(Al) and lower copper(Cu) plates,and this technology employed a Cu column as a rivet and a specially designed welding tool with a large concave-angle shoulder. The formations, interfacial characteristics, mechanical properties and fracture features of Al/Cu FSDRW joints under different rotational velocities and dwell times were investigated. The results showed that the well-formed FSDRW joint was successfully obtained.The cylindrical Cu column was transformed into a double riveting heads structure with a Cu anchor at the top and an Al anchor at the bottom, thereby providing an excellent mechanical interlocking.The defect-free Cu/Cu interface was formed at the lap interface due to the sufficient metallurgical bonding between the Cu column and the Cu plate, thereby effectively inhibiting the propagation of crack from the intermetallic compound layer at the lap interface between the Al and Cu plates. The tensile shear load of joint was increased first and then decreased when the rotational velocity and dwell time of welding tool increased, and the maximum value was 5.52 k N. The FSDRW joint presented a mixed mode of ductile and brittle fractures.

Bioinspired mechanically interlocking holey graphene@SiO_(2)anode

Mechanically interlocking structures that can enhance adhesion at the interface and regulate the stress distribution have been widely observed in biological systems.Inspired by the biological structures in the wings of beetles,we synthesized a holey graphene@SiO_(2)anode with strong mechanical interlocking,characterized it electrochemically,and explained its performance by finite element analysis and density functional calculations.The mechanically interlocking structure enhances lithium-ion(Li^(+))storage by transmitting the strain from SiO_(2)to the holey graphene and by a mechano-electrochemical coupling effect.The interlocking fit hinders the abscission of SiO_(2)and the distinctive structure reduces the stress and strain of SiO_(2)during(de)lithiation.The positive mechano-electrochemical coupling effect preserves the amount of electrochemically active phase(LixSi)during cycles and facilitates Li+diffusion.Therefore,the capacity shows only a slight attenuation after 8000 cycles(cycling stability),and the specific capacity is~1200 mA h g^(−1)at 5 A/g(rate-performance).This study furnishes a novel way to design high-performance Li^(+)/Na+/K^(+)/Al3^(+)anodes with large volume expansion.

Wire-feed laser additive manufacturing of dissimilar metals via dual molten pool interface interlocking mechanism

Intermetallic compounds produced in laser additive manufacturing are the main factors restricting the joint performance of dissimilar metals.To solve this problem,a dual molten pool interface interlocking mechanism was proposed in this study.Based on a dual molten pool interface interlocking mechanism,the dissimilar metals,aluminum alloy and stainless steel,were produced as single-layer and multilayer samples,using the wire-feed laser additive manufacturing directed energy deposition technology.The preferred parameters for the dual molten pool interface interlocking mechanism process of the dissimilar metals,aluminum alloy and stainless steel,were obtained.The matching relationship between the interface connection of dissimilar metals and the process parameters was established.The results demonstrated excellent mechanical occlusion at the connection interface and no apparent intermetallic compound layer.Good feature size and high microhardness were observed under a laser power of 660 W,a wire feeding speed of 55 mm/s,and a platform moving speed of 10 mm/s.Molecular dynamics simulations demonstrated a faster rate of aluminum diffusion in the aluminum alloy substrate to stainless steel under the action of the initial contact force than without the initial contact force.Thus,the dual molten pool interface interlocking mechanism can effectively reduce the intermetallic compound layer when dissimilar metals are connected in the aerospace field.

Improving bonding strength of W/Cu dual metal interface through laser microstructuring method

Selective laser melting(SLM)is a promising technology for fabricating complex components with W/Cu dual metal.To enhance the interfacial bonding of W/Cu dual metal,we propose a novel approach using laser texturing to fabricate micro/nanostructures on the W surface.The micro/nanostructures promoted the spreading of Cu in the liquid,inhibited defects,and considerably increased the contact area between W and Cu by mechanical interlocking.To the best of our knowledge,a W/Cu dual metal was successfully prepared by SLM without a transition layer the first time.The bonding strength of the two materials reached 123 MPa,close to that of a W/Cu dual metal joint prepared by diffusion bonding.

A supramolecular oligo[2]rotaxane constructed by orthogonal platinum(Ⅱ) metallacycle and pillar[5]arene-based host–guest interactions

Oligo[n]rotaxanes are one of the most extensively studied categories of mechanically bonded macromolecules.In this study,a supramolecular oligo[2]rotaxane is successfully constructed driven by platinum(Ⅱ)metallacycle and pillar[5]arene-based host–guest interactions in an orthogonal way.The supramolecular oligo[2]rotaxane is further applied in fabricating a light harvesting system.

Stretchable poly[2]rotaxane elastomers

Mechanically interlocked polymers(MIPs)are promising candidates for the construction of elastomeric materials with desirable mechanical performance on account of their abilities to undergo inherent rotational and translational mechanical movements at the molecular level.However,the investigations on their mechanical properties are lagging far behind their structural fabrication,especially for linear polyrotaxanes in bulk.Herein,we report stretchable poly[2]rotaxane elastomers(PREs)which integrate numerous mechanical bonds in the polymeric backbone to boost macroscopic mechanical properties.Specifically,we have synthesized a hydroxyfunctionalized[2]rotaxane that subsequently participates in the condensation polymerization with diisocyanate to form PREs.Benefitting from the peculiar structural and dynamic characteristics of the poly[2]rotaxane,the representative PRE exhibits favorable mechanical performance in terms of stretchability(∼1200%),Young’s modulus(24.6 MPa),and toughness(49.5 MJ/m^(3)).Moreover,we present our poly[2]rotaxanes as model systems to understand the relationship between mechanical bonds and macroscopic mechanical properties.It is concluded that the mechanical properties of our PREs are mainly determined by the unique topological architectures which possess a consecutive energy dissipation pathway including the dissociation of host−guest interaction and consequential sliding motion of the wheel along the axle in the[2]rotaxane motif.

The New Methods for Characterization of Molecular Weight of Supramolecular Polymers

Supramolecular polymers,as a type of dynamic polymers,are subordinate to the interdisciplinary field of polymer chemistry and supramolecular chemistry,whose development has greatly promoted the prosperity of new materials.Notably,molecular weight is one of the most important parameters of supramolecular polymers,which affects the physical/chemical properties and processing applications of materials.Developing new methods for characterizing the molecular weight of supramolecular polymers is crucial for advancing the development of supramolecular polymers.In this review,we elaborate and summarize three strategies for characterizing the molecular weight of supramolecular polymers that recently reported by our research group according to the characteristics of supramolecular polymers,including(1)the molecular weight distinction corresponding to variable fluorescence colors,(2)matching different molecular weights with different fluorescence lifetime,(3)transforming supramolecular polymers into mechanically interlocked polymers or covalent polymers.Besides,we also discuss the limitations of current methods for characterizing supramolecular polymers.We hope that this review can promote the development of supramolecular polymers and significantly inspire to exploit new methods to characterizing molecular weight of supramolecular polymers.

From Mechanically Interlocked Structures to Host-Guest Chemistry Based on Twisted Dimeric Architectures by Adjusting Space Constraints

Mechanically interlocked molecules(MIMs)and host–guest chemistry have received great attention in the past few decades.However,it remains challenging to design architectures with mechanically interlocked features and construct cavities for guest molecule recognition using similar building blocks.In this study,we designed and constructed a series of novel twisted supramolecular structures by assembling various multitopic terpyridine(tpy)ligands with the same diameter and Zn(II)ions.The obtained complexes exhibited evolutional architectures and showed distinctively different space-constraint effects.Specifically,the assembled dimer SA,SB,and SBH displayed mechanically interlocked phenomena,including[2]catenane and[3]catenane,with an increase in concentration.However,no interlocked structures were observed in complexes SC and SCH constructed by hexatopic tpy ligands due to the significant space constraints.The single-crystal data of complex SCH further proved significant space constraints and illustrated the formation of a relatively closed cavity,which showed excellent host–guest properties for different calixarenes,especially high affinity for calix[6]arene.

Seeing Is Believing:Directly Imaging Contractions of Artificial Molecular Muscles with Platinum Atom Markers

Artificial molecular muscles undergo well-controlled contractile and extensile motions upon external stimulation,leading to remarkable length changes.Evaluating such length changes at the molecular level is essential to the design of integrated artificial molecular muscles that mimic biological muscles.Taking advantage of the strong contrast of platinum(Pt)atoms in high-angle annular dark-field scanning transmission electron microscopy images,we imaged Pt-containing molecular[c2]daisy chains directly by employing metal atom markers.The length changes and associated conformational transformations of these newly developed artificial molecular muscles have been measured experimentally in combination with theoretical calculations.The contraction ratios of these two molecular muscles with the TEMPO or pyrene anchoring group were calculated to be 21.0%or 15.7%respectively,suggesting a substantial anchoring effect.This study demonstrates the experimental measurement of the length changes of artificial molecular muscles and provides a new avenue for investigating the motion of artificial molecular machines.

Applying reticular synthesis to the design of Cu-based MOFs with mechanically interlocked linkers

The concept of“robust dynamics”describes the incorporation of mechanically interlocked molecules(MIMs)into metal-organic framework(MOF)materials such that large amplitude motions(e.g.,rotation or translation of a macrocycle)can occur inside the free volume pore of the MOF.To aid in the preparation of such materials,reticular synthesis was used herein to design rigid molecular building blocks with predetermined ordered structures starting from the well-known MOF NOTT-101.New linkers were synthesized that have a T-shape,based on a triphenylene tetra-carboxylate strut,and their incorporation into Cu(II)-based MOFs was investigated.The single-crystal structures of three new MOFs,UWCM-12(fof),β-UWCM-13(loz),UWCM-14(lil),with naked T-shaped linkers were determined;β-UWCM-13 is the first reported example of the loz topology.A fourth MOF,UWDM-14(lil)is analogous to UWCM-14(lil)but contains a[2]rotaxane linker.Variable-temperature,^(2)H solid-state NMR was used to probe the dynamics of a 24-membered macrocycle threaded onto the MOF skeleton.

Achieving High‑Quality Aluminum to Copper Dissimilar Metals Joint via Friction Stir Double‑Riveting Welding

In order to achieve a high-quality joining of aluminum(Al)and copper(Cu)dissimilar metals,a new friction stir doubleriveting welding(FSDRW)with a Cu rod as the rivet was proposed,and the rotating tool with a large concave angle shoulder was specially designed.The results showed that under the thermal–mechanical effect of rotating tool,the Cu rod was deformed to be a double riveting heads structure with a Cu anchor at the upper surface of Al plate and an Al anchor above the lap interface of joint,and these two anchors greatly enhanced the mechanical interlocking of Al/Cu joint.The effective bonding interfaces were formed among the double riveting heads structure,the upper Al plate and the lower Cu plate,which contained the Cu/Cu interface and the Al/Cu interface.The Cu/Cu interface without the kissing bond and the Al/Cu interface with the rationally thin AlCu and Al_(2)Cu intermetallic compounds(IMCs)layers were beneficial to heightening the joint tensile shear strength.The maximum tensile shear load of the FSDRW joint achieved 5.52 kN,and the joint under different plunging depths of rotating tool presented a mixed mode of ductile fracture and brittle fracture.This novel FSDRW technique owns the advantages of strong mechanical interlocking and superb metallurgical bonding,and provides a new approach to acquiring a high-quality Al/Cu dissimilar metals joint.

Lighting up rotaxanes with AIEgens

Aiming at the construction of novel rotaxanes with desired luminescent properties for practical applications, recently the rapid development of rotaxanes decorated with aggregation-induced emission(AIE) luminogens(i.e., AIEgens) has been witnessed. The combination of AIEgens and rotaxanes leads to the successful construction of a novel type of luminescent rotaxanes with many attractive features. In particular, the unique controllable dynamic feature of rotaxanes endows the resultant AIEgen-based rotaxanes precisely tunable emissions under external stimuli, leading to the construction of a novel type of smart luminescent materials. In this minireview, the recent progress of AIEgen-based rotaxanes has been summarized, with an emphasis on the design strategy and potential applications.

A Bio-inspired Climbing Robot with Flexible Pads and Claws

Many animals exhibit strong mechanical interlocking in order to achieve efficient climbing against rough surfaces by using their claws in the pads. To maximally use the mechanical interlocking, an innovative robot which utilizes flexible pad with claws is designed. The mechanism for attachments of the claws against rough surfaces is further revealed according to the theoretical analysis. Moreover, the effects of the key parameters on the performances of the climbing robots are obtained. It indicates that decreasing the size of the tip of the claws while maintaining its stiffness unchanged can effectively improve the attachment ability. Furthermore, the structure of robot body and two foot trajectories are proposed and the new robot is presented. Using experimental tests, it demonstrates that this robot has high stability and adaptability while climbing on vertical rough surfaces up to a speed of 4.6 cm.s^-1.

Whither Second-Sphere Coordination?

The properties of coordination complexes are dictated by both the metals and the ligands.The use of molecular receptors as second-sphere ligands enables significant modulation of the chemical and physical properties of coordination complexes.In this minireview,we highlight recent advances in functional systems based on molecular receptors as second-sphere coordination ligands,as applied in molecular recognition,synthesis of mechanically interlocked molecules,separation of metals,catalysis,and biomolecular chemistry.These functional systems demonstrate that second-sphere coordination is an emerging and very promising strategy for addressing societal challenges in health,energy,and the environment.

Multistate circularly polarized luminescence switches based on dual stimuli-responsive chiral[2]rotaxanes

Aiming at the construction of novel multistate circularly polarized luminescence(CPL)switches,dual stimuli-responsive chiral[2]rotaxanes towards anions and light have been designed and constructed.Through the light-controlled on/off F?rster resonance energy transfer(FRET)switching between the emissive stoppers and anion-induced controllable motions of the chiral wheel for the precise regulations of chirality information transfer from the chiral wheel to the emissive stoppers,precisely switching between four CPL emission states with varied emission wavelengths and dissymmetry factors has been successfully realized,making them a promising platform for practical uses such as information storage and encryption.This proof-of-concept study not only provides a novel design strategy for multistate CPL switching but also contributes excellent candidates for the construction of novel smart chiral luminescent materials.

Sequence Engineering in Tuning the Circularly Polarized Luminescence of Aggregation-Induced Emission-Active Hetero[3]rotaxanes

Based on a[2]rotaxane precursor with exchangeable pentafluorophenyl ester stoppers,a new wheelassembling approach has been successfully developed for the precise sequence control of hetero[3]rotaxanes,leading to the facile and efficient synthesis of both sequence isomers of hetero[3]rotaxanes.More importantly,taking advantage of the chirality retention along with the wheel-assembling process,corresponding sequence isomers of chiral AIEgenfunctionalized hetero[3]rotaxanes were further precisely synthesized.Impressively,the resultant hetero[3]rotaxanes revealed remarkable sequencedependent aggregation-induced emission(AIE)behavior and circularly polarized luminescence performance with large dissymmetry factors up to 0.012,highlighting the great power of the newly coined sequence engineering concept in developing novel AIE-active chiroptical materials.This proof-ofconcept study lays the foundation for investigation of the structure-property relationships of heterorotaxanes that can further direct the rational design and precise synthesis of sequence-defined heterorotaxanes with desirable properties for practical applications.