From virgin to recycled bitumen: A microstructural view

In the present work, soft and hard bitumens recovered from unaged, aged and recycled asphalt concrete (AC) mixtures, which in laboratory tests performed mechanically as well as an AC mixture produced with virgin materials, were investigated regarding rheological, thermal and surface microstructural aspects. For comparison purposes, bitumen containing 50 wt% of virgin bitumen and 50 wt% of bitumen recovered from reclaimed asphalt pavement (RAP) was studied. Some properties of the bitumens remained unchanged throughout the preparation of the AC mixture, aging and recycling: Soft and hard bitumens retained their general rheological properties significantly, and their thermal and surface microstructural properties partially. Soft bitumens presented larger “bee” structures and, therefore, higher surface roughness, while hard bitumens presented smaller “bee” structures and, thus, lower surface roughness. Furthermore, soft bitumens seemed to contain higher crystalline-like content than hard bitumens. For the soft cases, the unaged recovered bitumen did not show the same characteristics (rheological and surface microstructure) as the virgin bitumen. Similarly the recovered recycled bitumen did not show the same characteristics (surface microstructure) as the bitumen prepared from the mixture of virgin bitumen and RAP bitumen. Aging of the AC mixture changed the rheological properties of the soft bitumen by increasing the complex modulus and decreasing the phase angle. Similarly, recycling changed the rheological properties by increasing the complex modulus and decreasing the phase angle. Compositional changes occurred during AC mixture preparation (possibly also aging and recycling) for both soft and hard bitumens. Consequently, more “phases” were observed on the surface microstructure for the recovered bitumens as compared with the virgin bitumens. However, no significant trend was found for the surface microstructure characteristics between the unaged, aged and recycled recovered bitumens. Moreover, the nature of the virgin bitumen influenced the properties of the recycled recovered bitumen, e.g. the glass transition temperature.     

Laboratory investigation of bitumen based on round robin DSC and AFM tests

In the past years a wide discussion has been held among asphalt researchers regarding the existence and interpretation of observed microstructures on bitumen surfaces. To investigate this, the RILEM technical committee on nano bituminous materials 231-NBM has conducted a round robin study combining differential scanning calorimetry (DSC) and Atomic Force Microscopy (AFM). From this, methods for performing DSC and AFM tests on bitumen samples and determination of the influence of wax on the observed phases, taking into account thermal history, sample preparation and annealing procedure, are presented and critically discussed. DSC is used to measure various properties and phenomena that indicate physical changes such as glass transition temperature (T _g) and phase transition such as melting and crystallization. In the case of existence of wax, either natural or synthetic, it can further indicate the melting point of wax, that could be used to determine wax content. The results from seven laboratories show that T _g temperatures obtained from the heating scans are more repeatable and easier to obtain in comparison to the cooling scans. No significant difference was noted for T _g’s obtained from the first and second heating scans. AFM is an imaging tool used to characterize the microstructures on a bituminous surface. Using AFM three phases in the materials with wax could be distinguished. The changes in the phases observed with AFM for increases in temperature were correlated with the DSC curve, and it could be established that the so called “Bee” structure disappeared around the melting peak in the DSC curve. Thus, this research has confirmed the relation between the microstructures on a bitumen surface and the wax content.     

Novel test method for accurate characterization of intralaminar fracture toughness in CFRP laminates

A novel initial crack insertion method, “intralaminar film insertion method”, was proposed to investigate the fracture toughness of unidirectional carbon fiber reinforced plastic (CFRP) laminates when the crack propagates inside the ply and not in the interlayer resin-rich area. Here, a release film was inserted inside a single lamina during the resin impregnation process of prepreg manufacturing. Mode I intralaminar fracture toughness tests were carried out for conventional CFRP laminates and interlayer toughened CFRP laminates. For comparison, two conventional methods were used to introduce initial cracks. One is the “interlaminar film method”, where a release film is inserted between two prepreg plies during the lay-up process. The other is the “machined slit method”, where a slit notch is machined in parallel to the layer of CFRP laminates. It was demonstrated that the proposed “intralaminar film method” can correctly evaluate the intralaminar fracture toughness of both conventional CFRP laminate and interlayer toughened CFRP laminate from the initial value to the propagation value. For this range, it was also found that the intralaminar fracture toughness of interlayer toughened CFRP laminate was the same as that of conventional CFRP laminate. Thus, the intralaminar fracture toughness was not influenced by interlayer toughening.     

Impact of maltene and asphaltene fraction on mechanical behavior and microstructure of bitumen

As a widely accepted concept, bitumen consists of four fractions that can be distinguished by their polarity. Highly polar asphaltene micelles are dispersed in a viscous phase of saturates, aromatics and resins (maltene phase). Different concentrations of asphaltenes in the bitumen result in a range of mechanical response properties. In an interdisciplinary study the impact of the maltene phase and asphaltenes on the linear viscoelastic behavior and the microstructure of bitumen were analyzed by creep recovery testing in a DSR and by atomic force microscopy (AFM). Therefore, bitumen was separated into the maltene and asphaltene fractions and artificial bitumen samples with different, pre-defined asphaltene concentrations were produced and investigated. It was found that the artificially produced, precipitated bitumen samples can be regarded as a representative, bitumen-like material in terms of mechanical behavior and microstructure. Asphaltenes play an important role in the typical viscoelastic behavior of bitumen being mainly responsible for stiffness and elasticity. Also, their concentration appears to be correlated to the occurrence and shape of the bee-like inclusions which can be typically observed by AFM.     

Investigation of microstructures and ultraviolet aging properties of organo-montmorillonite/SBS modified bitumen

Organo-montmorillonite(OMMT)/Styrene-butadiene-styrene(SBS) modified bitumen nanocomposites were prepared by melt blending. The microstructures of OMMT/SBS modified bitumen were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and atomic force microscopy (AFM), respectively. The effect of OMMT on ultraviolet (UV) aging properties of SBS modified bitumen was investigated. FTIR and XRD analyses indicate that the OMMT/SBS modified bitumen forms an intercalated structure. It is observed that the phase contrast between the dispersed domains and the matrix is inverted in SBS modified bitumen, which is decreased with the introduction of OMMT according to AFM analysis. As a result of UV aging, both viscosity aging index and softening point increment of OMMT/SBS modified bitumen decrease significantly. There is a single phase trend in the morphology of the bitumen after aging, which is accelerated by the existence of SBS. However, these changes can be effectively prevented under the influence of OMMT, indicating the good UV aging resistance of OMMT/SBS modified bitumen.     

Inclusion of a thermoplastic phase to improve impact and post-impact performances of carbon fibre reinforced thermosetting composites — A review

Infusion processing methods have become a popular manufacturing alternative to the autoclave procedure to meet the increased demand for high-performance composites with shorter production times and lower cost. These processes are primarily limited to low viscosity, thermosetting matrices that are inherently brittle, and hence are susceptible to impact damage. It has been shown that introducing a thermoplastic modifier to create a “three-phase composite” can improve the ability of the laminate to resist damage formation and growth, and enhance a damaged laminate's structural performance. A comprehensive review is presented herein of the state-of-the-art on the incorporation of a thermoplastic phase into a fibre-reinforced thermosetting composite laminate to improve its damage resistance and tolerance properties when subjected to a low-energy impact. Several material properties govern the response of a laminate to an impact event, and for this reason, a discussion on the impact damage process and post-impact performance is also presented. Techniques from two main areas of toughening are considered — namely, bulk resin modification and interlaminar toughening. The improvements in laminate performance brought about by the thermoplastic additive are discussed, and each technique is assessed based on its suitability for inclusion in infusion manufacturing processes.     

Nanomanipulation by Atomic Force Microscopy

The linking of our macroscopic world to the nanoscopic world of single molecules, nanoparticles and functional nanostructures is a technological challenge. Researchers in nanobiotechnology face the questions “How extract and analyze a single nano‐object?”, “How to pick and place nano‐objects?” and “How to prototype a functional nanostructure?”. Here, nanomanipulation by an atomic force microscope (AFM) in combination with optical manipulation by a microbeam laser offers a practicable solution. In such a system, the AFM can be operated as a nanorobot for manipulation purposes allowing for nanometer precision. A contact free manipulation is achieved by the laser microbeam.     

Sources of variability in uncured aerospace grade unidirectional carbon fibre epoxy preimpregnate

Two sources of variability have been investigated in uncured unidirectional carbon epoxy preimpregnate (prepreg). The variability in mass/unit area properties has been measured at various scales and compared to the specification limits as defined by the manufacturer. Both random variability and a structured variation in mass properties across the width of the roll can be detected; and as might be expected the variability rises rapidly as the scale on which the measurements are performed is reduced. The variability in fibre straightness has been studied in two ways, by direct measurements of fibre misalignments in as-delivered prepreg, and by inference from measurements of the tensile load response of uncured prepreg. A significant level of fibre misalignment is detectable in as-delivered prepreg, largely as in-plane wrinkling, although both macroscopic out of plane wrinkling and very localised small scale out of plane wrinkling can also be detected. This misalignment increases with forming, both in and out-of plane wrinkling becoming more severe. The influence of these variabilities on laminate and component response are considered.     

Contribution to the understanding of the mechanical behaviour of CFRP-strengthened RC beams subjected to fire: Experimental and numerical assessment

Recent experimental tests and numerical simulations about the fire resistance behaviour of CFRP-strengthened RC beams proved that CFRP strengthening systems are able to attain considerable fire endurance, provided that adequate fire protection systems are used. In a fire event, even though a CFRP laminate may rapidly debond from the central part of the beam in which it is installed, if sufficiently thick insulation is applied in the anchorage zones, the laminate transforms into a “cable” fixed at the extremities, thus maintaining a considerable contribution to the mechanical response of the strengthened beam. This paper presents experimental and numerical investigations on CFRP-strengthened RC beams with the objective of understanding in further depth their fire resistance behaviour, namely the influence of the above mentioned “cable” mechanism on the mechanical response of the beams. The experimental campaign, performed at ambient temperature, comprised 4-point bending tests on RC beams strengthened with CFRP laminates according to either the EBR or the NSM techniques, in both cases fully or partially (only at the anchorages, thus simulating the cable mechanism) bonded to the soffit of the beams. For the test conditions used in this study, for both types of strengthening systems, partially bonding the CFRP laminates did not affect the stiffness of the beams and caused only a slight reduction of their strength (6–15%). The numerical study comprised the simulation of the structural response of all beams tested. Non-linear finite element models were developed in Atena commercial package, in which a smeared cracked model was adopted to simulate concrete and appropriate bond-slip constitutive relations were defined for the CFRP-concrete interfaces. A very good agreement was obtained between experimental data and numerical results, providing further validation to the “cable” mechanism and the possibility of taking it into account when designing fire protection systems for CFRP-strengthened RC beams.     

A Stacked-Shell Finite Element Approach for Modelling a Dynamically Loaded Composite Bolted Joint Under in-Plane Bearing Loads

This paper presents the results of a study into a novel application of the “stacked-shell” laminate modelling approach to dynamically loaded bolted composite joints using the explicit finite element code PAM-CRASH. The stacked-shell approach provides medium-high fidelity resolution of the key joint failure modes, but is computationally much more efficient than full 3D modelling. For this work, a countersunk bolt in a composite laminate under in-plane bearing loading was considered. The models were able to predict the onset of damage, failure modes and the ultimate load of the joint. It was determined that improved debris models are required in order to accurately capture the progressive bearing damage after the onset of joint failure.     

AFM Characterization of Elastically Micropatterned Surfaces Fabricated by Fill‐Molding In Capillaries (FIMIC) and Investigation of the Topographical Influence on Cell Adhesion to the Patterns

We have employed our recently developed method Fill‐Molding In Capillaries (FIMIC) to fabricate elastically micropatterned substrates, using two poly(ethylene glycol) (PEG)‐based polymers with different elastic properties and swelling behavior. We have evaluated the FIMIC process and the quality of the eventual substrates (the “FIMICs”) by atomic force microscopy (AFM); imaging the surface topography and quantifying the local surface elasticity. Topographical imaging reveals that the surface of the FIMICs is never perfectly smooth; a slight topographic difference of 30 nm up to several hundreds of nm is observed, with the filler material always being depressed with respect to the mold. Moreover, when the FIMICs are immersed in water (or cell culture medium), the topographical landscape changes due to differential swelling of the two constituents of the FIMICs. We have used this differential swelling to our advantage in order to diminish the topography differences present on the sample surface by employing a filler that swells more than the mold. Finally, cell culture experiments with fibroblasts underlines the topographical influence on cell adhesion on the more or less anti‐adhesive PEG‐based materials.     

Citation curves of “all-elements-sleeping-beauties”: “flash in the pan” first and then “delayed recognition”

“Delayed recognition” refers to the phenomenon where papers did not achieve recognition in terms of citations until some years after their original publication. A paper with delayed recognition was termed a “sleeping beauty”: a princess sleeps (goes unnoticed) for a long time and then, almost suddenly, is awakened (receives a lot of citations) by a prince (another article). There are a sleeping period and an awakening period in the definition of a “sleeping beauty”. Apart from and prior to the two periods, an awaking period was found in citation curves of some publications, “sleeping beauties” was hence expanded to “all-elements-sleeping-beauties”. The opposite effect of “delayed recognition” was described as “flash in the pan”: documents that were noticed immediately after publication but did not seem to have a lasting impact. In this work, we briefly discussed the citation curves of two remarkable “all-elements-sleeping-beauties”. We found they appeared “flash in the pan” first and then “delayed recognition”. We also found happy endings of sleeping beauties and princes, and hence suggest the citation curve of an “all-elements-sleeping-beauty” include an awaking period, a sleeping period, an awakening period and a happy ending.     

Processing and properties of carbon fiber/Triple-A polyimide composites fabricated from imide oligomer dry prepreg

Triple-A polyimide (TriA-PI) concept, “amorphous, asymmetric, and addition type”, was originally proposed by Yokota in 1999 for high temperature polymer matrix composites. The first version polyimide “TriA-PI-1” was developed from a-BPDA (2,3,3′,4′-biphenyltetracarboxylic dianhydride), 4,4′-oxydianiline (4,4′-ODA), and phenylethynyl phthalic anhydride (PEPA). The cured polyimide exhibits excellent mechanical properties with high glass transition temperature.In this study, a new prepreg system, namely imide-oligomer dry prepreg was developed by impregnating imide-oligomer into unidirectional carbon fiber bundles directly. Carbon fiber/TriA-PI-1 composites were fabricated from the imide-oligomer dry prepreg, and mechanical properties were evaluated. It was demonstrated that the TriA-PI-1 composite exhibits excellent compressive and tensile strengths at 300 °C as well as room temperature. It was easy to make a high quality composite laminate without complicated process using imide-oligomer dry prepreg.     

Investigations into the early stages of “in vitro” calcification on chitosan films

This work investigated the mechanisms involved in the “in vitro” calcification of chitosan films. The calcification process on chitosan films is a phenomenon that has not been sufficiently studied, despite its importance in the understanding of many natural processes, such as bone and shell formation. Three different techniques were used in the present investigation: X-ray fluorescence (XRF), atomic force microscopy (AFM) and X-ray diffraction (XRD). Natural and acetylated chitosan films were used as substrates for calcification. The experiments were carried out by immersing chitosan membranes in simulated body fluid (SBF) or in a modified version of SBF, prepared without phosphate ions, during 30 min, 3 or 12 h. Calcium maps obtained by XRF showed that the initial calcium distribution on the chitosan surface was influenced by the acetylation treatment of chitosan films. AFM indicated the distribution pattern of calcium compound deposits at different times, obtained by film surface morphological analysis. The results suggest that the calcification mechanism is nucleation on membranes followed by the crystal growth of calcium compounds. AFM showed that the deposit formation is a function of immersion time: the deposits became more homogeneous and covered the surface more evenly with longer immersion times. XRD showed that the acetylated membranes produced more organized calcium deposits.     

In-situ observation of transition between surface relief and wrinkling in thin film shape memory alloys

Significant surface morphology evolution between relief and wrinkling was observed on a 3.5 microm thick TiNiCu film sputter-deposited on a silicon substrate. At room temperature, variation in surface relief morphology (from separated martensite crystals embedded in amorphous matrix to fully interweaved martensite plates) was observed with slight change in film composition. The phenomenon was attributed to variations in crystallization temperatures of as-deposited amorphous films during annealing because of the compositional difference. During thermal cycling between room temperature and 100 degrees C, reversible surface morphology changes can be observed between surface relief and wrinkling patterns. The formation of the surface wrinkling is attributed to the large compressive stress in the film during high temperature post-annealing and crystallization, whereas surface relief is caused by the martensitic transformation to relieve the large tensile stress in the film. Compositional effect on this surface morphology evolution is discussed. Results also indicate that there is a critical dimension for the wrinkling to occur, and a small circular island can only relax by in-plane expansion.     

The Role of Liquid Ink Transport in the Direct Placement of Quantum Dot Emitters onto Sub‐Micrometer Antennas by Dip‐Pen Nanolithography

Dip‐pen nanolithography (DPN) is used to precisely position core/thick‐shell (“giant”) quantum dots (gQDs; ≥10 nm in diameter) exclusively on top of silicon nanodisk antennas (≈500 nm diameter pillars with a height of ≈200 nm), resulting in periodic arrays of hybrid nanostructures and demonstrating a facile integration strategy toward next‐generation quantum light sources. A three‐step reading‐inking‐writing approach is employed, where atomic force microscopy (AFM) images of the pre‐patterned substrate topography are used as maps to direct accurate placement of nanocrystals. The DPN “ink” comprises gQDs suspended in a non‐aqueous carrier solvent, o‐dichlorobenzene. Systematic analyses of factors influencing deposition rate for this non‐conventional DPN ink are described for flat substrates and used to establish the conditions required to achieve small (sub‐500 nm) feature sizes, namely: dwell time, ink‐substrate contact angle and ink volume. Finally, it is shown that the rate of solvent transport controls the feature size in which gQDs are found on the substrate, but also that the number and consistency of nanocrystals deposited depends on the stability of the gQD suspension. Overall, the results lay the groundwork for expanded use of nanocrystal liquid inks and DPN for fabrication of multi‐component nanostructures that are challenging to create using traditional lithographic techniques.     

Thermo-oxidative aging of bitumen

Thermo-oxidative bitumen ageing has been commonly recognised as the main cause of asphalt cracking. The effect of thermo-oxidative ageing level on bitumen has been studied in this work by means of a simple and effective mechanical stirring process. Physical characteristics of the material as Softening Point, Penetration and Viscosity were measured to samples with different ageing conditions. Chemical changes in the material were evaluated by means of SARA fractioning to measure the effect of ageing on the fundamental components of bitumen, and Infrared Spectroscopy in order to study the changes found on the oxidation-related compounds of the material. Microstructural changes on the material were evaluated using atomic force microscopy (AFM) finding that the ageing process on bitumen increases the number and size of the phases related to asphaltenes and resins, and decreases the amount of phases related to aromatics. The changes in chemical and physical characteristics of bitumen were found to be strongly dependent on the carbonyl formation. An extension to a previously proposed oxidation kinetics model was used to predict the fast rate (transient) and constant rate (steady-state) oxidation behaviour of bitumen and its relation to physical properties. The thermo-oxidative changes suffered by bitumen are associated with increasing hardening of the material, making it susceptible to cracking when in contact with aggregate as thin films in flexible pavements.     

缝纫泡沫夹芯复合材料失效强度的理论预测与试验验证

基于经典层板理论和细观力学桥联模型, 提出了缝纫泡沫夹芯复合材料失效强度的理论预测方法, 并进行了失效强度的相关试验验证。其中, 将缝纫复合材料面板看作单层组成的准层状结构, 采用经典层板理论进行逐层失效分析, 并同时考虑了局部皱曲的面板失效模式; 而对缝纫泡沫夹芯, 引入桥联模型计算其各组分材料中的应力, 并通过对各组分材料选取适当失效准则来建立失效判据; 对于缝纫泡沫夹芯复合材料采取逐级加载方式, 当面板或者夹芯失效时, 则认为其发生整体失效, 由此可以确定其在不同载荷形式下的失效强度。此外, 通过试验得到了缝纫泡沫夹芯复合材料板试件在平压、 侧压、 横向剪切及三点弯曲载荷形式下的失效模式及其失效强度, 并利用本文方法对缝纫泡沫夹芯复合材料的失效强度进行了理论预测, 所得结果与试验吻合, 证明了本文方法的有效性。      

Effect of different yield criteria on prediction of wrinkling initiation of interstitial-free galvanized steel sheet

Thin interstitial-free (IF) galvanized steel sheets have great usage in auto industry due to their high formability and corrosion resistance. However presence of wrinkle waves in deep drawn parts of thin IF steel sheets is a common challenging issue. Achieving a reliable method to predict the wrinkling onset enables the manufacturers to avoid wrinkling by modification of forming parameters. In the present study, sidewall wrinkling of an IF-galvanized steel sheet was both analytically and experimentally examined during a conical cup wrinkling test. Using an energy method approach together with a newly developed deflection function, Hosford and Hill-1948 yield criteria were employed to predict the critical values of stress and cup height at the onset of wrinkling. According to the obtained results, applying Hill-1948 yield criterion resulted in prediction of wrinkling onset closer to the experimental value than Hosford yield criterion. It was also found that the newly presented deflection function has a great suitability for prediction of the real status of wrinkling phenomenon.