Contactless Raman Spectroscopy-Based Monitoring of Physical States of Silyl-Modified Polymers during Cross-Linking

Cross-linking of silyl-modified polymers occurs at the alkoxysilane groups attached to the ends of polymer chains by hydrolysis and polycondensation mechanisms in the presence of moisture. During these reactions, three different physical states can be identified (viscous, skin effect and cross-linked state). Knowledge of the evolution of these states at each reaction time is essential to determine the open time for the adhe-sive industry and is generally obtained by a manual method. Automation of this moni-toring could avoid operator error and could be used for very long cross linking reac-tions or to screen a large number of catalysts. Thus, a contactless micro process tech-nology was developed to correlate these physical states with an optical technology, Raman spectroscopy, by monitoring the decrease in intensity of the Si-OCH3 groups during chemical reactions. This online characterization method can also be used to compare the efficiencies of several catalysts for the cross-linking of silyl-modified polymers, using a minimum amount of chemical materials.

Analysis of Aging Mechanism of SBS Polymer Modified Asphalt based on Fourier Transform Infrared Spectrum

The aging mechanism of SBS modified asphalt during its aging process was studied.The characterizations of base asphalt,SBS polymer and its modified asphalt were determined in different aging time by Fourier transform infrared spectrum（FTIR）.FTIR shows that oxidative dehydrogenation reaction occurs in asphalt,and unsaturated carbon bond is generated under short-term thermal aging condition.Additionally,SBS polymer was aged significantly under that condition,the speed of which was faster than that of base asphalt.The aging laws of both asphalt and SBS polymer during the aging process of SBS modified asphalt were similar to their aging laws respectively.Due to the protective effect between asphalt and SBS polymer,the aging degrees of asphalt and SBS polymer were lower than those aged independently.

Compound Rejuvenation of Polymer Modified Asphalt Binder

The objective of this research was to show a way to conduct rejuvenation of aged polymer modified asphalt binder（PMB） successfully.To fully evaluate and understand the rejuvenation of aged PMB,the Penetration grade tests including penetration,soften point,ductility and elastic recovery and SuperpaveTM PG grade tests including DSR,BBR and DDT were conducted.The rejuvenation effect of aged PMB by utilizing a fluid recycling agent in common use for binder rejuvenation was evaluated.And then the compound rejuvenation effect of aged PMB by utilizing the recycling agent with a new modifying additive for binder modification was evaluated.The experimental results indicated that the recycling agent in common use currently does not apply to polymer modified asphalt binder rejuvenation.But the recycling agent together with the modifying additive can restore the characteristics of aged polymer modified binder very well.Therefore,compound rejuvenation of polymer modified asphalt binder is recommended.

Rheological Evaluation of Polymer Modified Asphalt Binders

The microstructure and dynamic rheological characteristics of asphalt containing different polymer modifiers （crumb rubber, styrene-butadiene-styrene and crumb rubber mix with styrene- butadiene-styrene） at mid and high service temperature levels were investigated by using scanning electron microscopy（SEM）, dynamic shear rheometer（DSR） and repeat creep test. The main objective of the investigation was to rank the modifiers based on their effect on performance characteristics of asphalt under service conditions. To evaluate the effect of different modifiers on the viscoelastic response of asphalt, the temperature and frequency dependences of the dynamic viscoelastic properties were compared. The mid-temperature fatigue resistance and high-temperature rutting resistance of three polymer modified asphalts were evaluated to predict their field performance in roads. Based on the current results, an improved rutting factor was proposed to determine the rutting resistance of asphalt pavements. In addition, the viscous stiffness （Gv）, defined as the reciprocal of viscous compliance, was used to evaluate the high-temperature deformation resistance of asphalt mixtures. The experimental results indicate that the asphalt containing crumb rubber only shows superior performance at mid and high service temperatures in all three modified asphalt binders due to the action of the crumb rubber.

Rheological and Morphological Characterization of Modified Bitumen with Cup Lump Rubber

Pure bitumen is not suitable for heavy traffic loads;hence modifiers are used to improve the bitumen performance.Recently,cup lump rubber(CLR)has become a preferred modifier due to its outstanding performance and less cost.However,little is known about the interactions between CLR and bitumen.Thus,this study investigates the behavior of bitumen with CLR.Four percentages of CLR(2.5%,5.0%,7.5%,and 10.0%by weight of bitumen)were used to modify conventional 60/70 penetration grade bitumen.The modified bitumen was evaluated through different laboratory testing such as dynamic shear rheometer,rotational viscosity,softening point,bending beam rheometer,ductility,and elastic recovery.The testing results show that the addition of CLR increased the bitumen’s rutting resistance by 3 PG grades at high temperatures.At low pavement temperatures,the cup lump rubber modified bitumen(CMB)can withstand up to−34℃.Fourier Transform Infrared(FTIR)analysis shows that the Aromaticity index at 1600 cm^(−1) rose as the CLR percentage increased,indicating the formation of a binder with a compact structure.This is expected to improve the elasticity of bitumen throughπ-πinteractions.Atomic Force Microscopy(AFM)results showed the Catana phase increased in size and quantity at 5.0%and 7.5%CLR content.While contact angle measurement revealed that the binders are hydrophobic and tend to repel the dropped water on the bitumen surface.

Toughness of Polymer Modified Steel Fiber Reinforced Concrete

An experimental investigation is carried out to study the toughness of polymer modified steel fiber reinforced concrete. Volume fraction of steel fibers is varied from 0% to 7% at the interval of 1% by weight of cement. 15% SBR latex polymer was used by weight of cement. Cubes of size 150 × 150 × 150 mm for compressive strength, prism specimens of size 150 mm × 150 mm × 700 mm for flexure strength and, specimen of size 150 × 150 × 150 mm with 16 mm diameter tor steel bar of length 650 mm embedded in concrete cube at the center for bond test were prepared. Various specimens were tested after 28 days of curing. Area under curve (toughness) is measured and mentioned in this work.

Performance improvement in polymeric thin film transistors using chemically modified both silver bottom contacts and dielectric surfaces

An efficient interface modification is introduced to improve the performance of polymeric thin film transistors. This efficient interface modification is first achieved by 4-fluorothiophenol（4-FTP） self-assembled monolayers（SAM） to chemically treat the silver source–drain（S/D） contacts while the silicon oxide（SiO2） dielectric interface is further primed by either hexamethyldisilazane（HMDS） or octyltrichlorosilane（OTS-C8）. Results show that contact resistance is the dominant factor that limits the field effect mobility of the PTDPPTFT4 transistors. With proper surface modification applied to both the dielectric surface and the bottom contacts, the field effect mobilities of the bottom-gate bottom-contact PTDPPTFT4 transistors were significantly improved from 0.15 cm^2·V^-1·s^-1 to 0.91 cm^2·V^-1·s^-1.

Acrylate Copolymers as Impact Modifi er for Epoxy Resin

P（BA-GMA）（PBG）, having various molecular weights, was synthesized by in situ polymerization of butyl acrylate（BA） and glycidyl methacrylate（GMA）, and further used as a modifier to improve the comprehensive properties of the epoxy curing system. The copolymers were characterized by gel permeation chromatography（GPC）. The effects of various molecular weights of copolymers on the mechanical properties, thermal performance, and phase behavior of the curing system were carefully evaluated. The experimental results of differential scanning calorimetry（DSC） and dynamic mechanical analysis（DMA） showed that glass transition temperature decreased and the tan δ peak shifted to a lower temperature with decreasing molecular weight of copolymer. Mechanical properties analysis of curing films showed that the impact strength and fracture toughness increased significantly upon the addition of PBG, indicating good toughness of the modified epoxy resins. From scanning electron microscopy（SEM） studies of the fracture surfaces of ER/PBG systems, the fracture behavior of epoxy matrix was changed from brittleness to toughness.

Physical and Thermo-Oxidative Characterization of Asphalt Modified with High Density Polyethylene and Recycled Engine Oil

Modification of asphalt using polymers, oils and other additives has been an option to improve asphalt pavement performance and extend its lifespan. The present work aims to evaluate the influence of the addition of engine oil on the consistency and thermal properties of HDPE-modified asphalt. For this study, compositions containing asphalt, engine oil and high-density polyethylene (HDPE) were prepared, varying the concentration of engine oil by 2.5 wt%, 5 wt%, 7.5 wt% and 10 wt% and keeping the concentration of HDPE at 5 wt%. The samples were characterized by conventional tests of penetration, softening point and viscosity, aging in a Rotational Thin Film Oven (RTFO), Thermogravimetric Analysis (TGA). According to the results, the addition of HDPE to virgin asphalt causes an increase in the consistency of the virgin asphalt, which then decreases linearly as the engine oil is added into the matrix. Conventional tests showed improvements in the applicability of the asphalt in terms of resistance to cracks and permanent deformation. TGA showed a slight increase in stability for the modified asphalt samples at elevated temperatures. The RTFO showed mass gain and loss for samples with and without engine oil, respectively.

Review on laboratory preparation processes of polymer modified asphalt binder

Several previous studies have documented the progress in polymer modified asphalt binder with respect to materials'types and properties.However,limited or no effort was made to document findings on the laboratory preparation practices of polymer modified asphalt binder.Full and clear disclosure of asphalt blend preparation method is necessary for research continuity,reproducibility,and accurate adaptation by future studies for analogy and reliable conclusions.The laboratory preparation processes of various modified asphalt binders have been reviewed in this study.Factors affecting the optimal mixing of asphalt-polymer blends were summarized.The optimal mixing conditions associated with different asphalt modifiers were documented.Gap in the literature on the current practice for the preparation and reporting of various modified asphalt binder was discussed.Modifiers include styrene butadiene styrene(SBS),polyethylene(PE),waste tire rubber or crumb rubber(CR),ethylene vinyl acetate(EVA),sulfur,polyphosphoric acid(PPA),epoxy,polyurethane,nano-materials,etc.Currently,there is lack of modern innovative approached in the preparation of modified asphalt towards better performance.There is no clear standardized definition of term associated with asphalt binder preparation process.Given the limited and common types of polymers utilized for the modification of asphalt binder,it is possible to standardize the mixing procedure for several polymers.Doing so could ease research continuity and facilitates accurate comparison of new studies with earlier ones.

Molecular dynamics simulation and microscopic observation of compatibility and interphase of composited polymer modified asphalt with carbon nanotubes

Interfacing and compatibility are the most challenging issues that affect the performance of polymer modified asphalt.Mechanisms of interfacial enhancement among four base asphalt components(asphaltenes,resins,aromatics,and saturate),styrene-butadiene-styrene(SBS),and carbon nanotubes(CNTs)were investigated by molecular dynamics simulation,with the aim of understanding the key parameters that control the compatibility of CNTs and interphase behavior on the molecular scale.The compatibility of SBS-modified asphalt(SBSMA)was simulated based on self-assembly theory using indexes of binding energy,mean square displacement,diffusion coefficient,and relative concentration distribution.The interphase behavior and microstructure were observed by fluorescence microscopy and scanning electron microscopy.In addition,a rutting experiment was used to verify the molecular dynamics simulation based on macroscopic performance.The results showed that after adding CNTs,the binding energy of the SBS and aromatics increased from 301.8343 to 327.1102 kcal/mol.The diffusion coefficient of the SBS and asphaltenes decreased more than 3.2×10-11 m2/s,and the correlation coefficients between the diffusion coefficient and the molecular weight,surface area and volume were all lower than 0.3.Relative concentration distribution curves indicated that CNTs promote the ability of SBS to swell.Microscopic observations demonstrated that the swelling ability of SBS was increased by CNTs.Overall,the interphase of SBSMA was improved by the additional reinforcement,swelling,and diffusion provided by CNTs.Finally,the rutting experiment found that no matter what the temperature,the rutting factor of CNT/SBSMA is higher than that of SBSMA,which corroborates the findings from the molecular dynamics simulations.

Effects of Surface Modifi cation on the Properties of Microcapsules for Self-healing

Poly（urea-formaldehyde）（UF） microcapsules with epoxy resin E-51 as core material used as self-healing materials were prepared by interfacial polymerization method. The surface of UF microcapsules was modifi ed by γ-（2,3-epoxypropoxy） propytrimethoxysilane（KH-560）. The interfacial interactions between UF microcapsules and KH-560 were studied by Fourier transform infrared spectroscopy（FTIR） and X-ray photoelectron spectrometric analysis（XPS） of microcapsules. The surface topography of microcapsules was characterized by scanning electron microscopy（SEM）. The thermal stability and mechanical properties were evaluated. FTIR and XPS results showed that there were physical and chemical combinations between the silicon coupling agent and the microcapsules surface. The thermal stability and mechanical property analysis showed that the addition of KH-560 could greatly improve the thermal stability, tensile property and elastic property. SEM results indicated that the addition of KH-560 could improve the bonding between the surface of microcapsules and resin matrix and improve the ability of self-healing.

Regulated CO adsorption by the electrode with OH^(-) repulsive property for enhancing C–C coupling

Electrochemical CO_(2) reduction driven by renewable electricity is one of the promising strategies to store sus-tainable energy as fuels.However,the selectivity of value-added multi-carbon products remains poor for further application of this process.Here,we regulate CO adsorption by forming a Nafion layer on the copper(Cu)electrode that is repulsive to OH^(-),contributing to enhanced selectivity of CO_(2) reduction to C_(2) products with the suppression of C 1 products.The operando Raman spectroscopy indicates that the local OH^(-)would adsorb on part of active sites and decrease the adsorption of CO.Therefore,the electrode with repulsive to OH^(-)can adjust the concentration of OH^(-),leading to the increased adsorption of CO and enhanced C–C coupling.This work shows that electrode design could be an effective strategy for improving the selectivity of CO_(2) reduction to multi-carbon products.