Investigation of packaging adhesive properties by molecular dynamics and experiments

Adhesive polymer is a common and important material used for packaging of microelectronics and microsystem by attaching dies onto packaging shell, and its mechanical property plays a vital role in isolating dies from the thermal stress of substrate. Therefore, it is extremely significant to evaluate the polymer property in a specific packaging process. The molecular dynamics (MD) simulation is conducted in this article to investigate the material properties of the cross-linked epoxy resin formed by epoxy resin component diglycidyl ether bisphenol A (DGEBA) and curing agent 1,6-Diaminohexane. The polymer network with conversion up to 87.5% is successfully generated and simulated by constant pressure-constant temperature ensemble (NPT) and canonical ensemble (NVT) at different temperatures of curing process. Glass transition temperature (T_g) and Young's modulus are extracted and the predicted material properties are in great agreement with the experimental data. The conclusion provides a guideline to design the special curing process for different adhesive requirements.     

Self-assembly of telechelic polymers bearing adamantane groups via host-guest inclusion complexes with cyclodextrin polymer

Self-assembly and supramolecular inclusion complexations between telechelic polymers bearing one or double adamantane groups and linear poly(β-cyclodextrin) (P(β-CD)) were investigated in water. An adamantane (Ada) attached to poly (acrylic acid) (PAA) was prepared by reversible addition-fragmentation chain transfer polymerization using s-1-dodecyl-s″ -(α,α′-dimethyl-α″-acetic acid) trithio-carbonate functionalized Ada with tert-butyl acrylate, followed by functional modification. Additionally, two Ada groups capped triblock copolymer F127 were obtained via an esterification reaction. The dynamic light scattering, transmission electron microscope and ¹H 2D NOSEY NMR spectroscopy were conducted to characterize the self-assembly behaviors. With the inclusion complexation of Ada/CD in 1:1 M ratio in water, the spherical micelles were enlarged at 25°C than that of the adamantyl polymer precursors. Due to the PPO segment of Ada-F127-Ada, the micelles aggregation showed temperature dependence from 4 to 37°C for precursor and corresponding inclusion complexation; while in Ada-PAA/P(β-CD) system, the hydrodynamic diameters decreased with pH decreasing.     

Prestructured MXene fillers with uniform channels to enhance CO2 selective permeation in mixed matrix membranes

The packing pattern of two-dimensional (2D) sheet-like fillers in membranes is relatively random, leading to the unfavorable permeability from tortuous diffusion pathway. A new strategy that using prestructured materials with uniform channels as fillers was proposed. In this work, Ti₃AlC₂ is etched to prepare multilayered MXene (m-MXene), the channels aggregate as a whole unit, ensure the impossibility of ineffective packing compared with traditional individual sheets, largely facilitating the selective permeation. Then, the m-MXene/Poly (amide-6-b-ethylene oxide) (Pebax) MMMs are synthesized. SEM images demonstrate the accordion shaped structure of filler, which is the multi-channels laminates. Furthermore, the results of gas permeation test exhibit enhanced performance of m-MXene/Pebax MMMs. MMM with 0.5 wt.% m-MXene behaved best, CO₂ permeability of 86.22 Barrer as well as CO₂/N₂ selectivity of 104.85, transcending the Robeson upper bound (2008). Having distinct enhancement for CO₂ separation, the m-MXene/Pebax MMMs in this work offer prospective practical applications.     

Synthesis and characterization of poly(hexamethylene terephthalate/hexamethylene oxamide) alternating copolyamide (alt-PA6T/62)

As a representative polyoxamide, poly(hexamethylene oxamide) (PA62) has good comprehensive performance. However, the high T_m (330°C) creates an obstacle for processing. To improve the processability of PA62, poly(hexamethylene terephthalate/hexamethylene oxamide) alternating copolyamide (alt-PA6T/62) was synthesized by hexamethylene diamine-terminated 6T6-diamine and dibutyl oxalate via solution/solid state polycondensation. Random copolyamide (ran-PA6T/62) was also synthesized for comparison. The structure and properties of the copolymer were analyzed by Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Wide-angle X-ray diffraction (WAXD) and the saturated water absorption test. The NMR results confirm the alternating structure of alt-PA6T/62. The DSC and TGA results demonstrate that the novel alternating copolyamide alt-PA6T/62 (T_m = 321°C, T₅ = 420°C) exhibited better thermal properties than those of ran-PA6T/62 (T_m = 294°C, T₅ = 412°C). The saturated water absorption of alt-PA6T/62 was found to be 3.2 wt%. These results revealed that the novel alt-PA6T/62 had an alternating sequence distribution, showed a high melting point as well as good processability and thermal stability, and possessed low saturated water absorption and excellent dimensional stability.     

Hierarchically porous N-doped carbon nanofibers derived from ZIF-8/PAN composites for benzene adsorption

Coupling with electrospinning technique, metal–organic-frameworks (MOFs)-derived porous carbon fibers exhibit a great potential application in the adsorption of volatile organic compounds (VOCs) because of their huge surface area, high porosity, as well as sufficient heteroatom-doped active sites. In this work, the hierarchically porous N-doped carbon nanofibers are obtained after the pyrolysis of zeolite imidazole framework-8 and polyacrylonitrile (ZIF-8/PAN) composite fibers synthesized by electrospinning method. The N-doped carbon nanofibers fabricated in N₂ atmosphere (N-CF-N₂) present an enhanced adsorption capacity of 694 mg/g for benzene because of the synergistic effect of the hierarchically porous structure and the abundant N-species-containing active sites. It is also interesting that the N-doped hierarchical carbon nanofibers fabricated in Ar atmosphere (N-CF-Ar) exhibit a low benzene adsorption as compared with the N-CF-N₂, which can be attributed to the porous structure damage caused by the bombardment of heavy Ar atoms on the pore shells during the pyrolysis. These results not only show a promising application of the as-fabricated N-CF-N₂ in adsorption of VOCs for air purification due to its merit of cost-efficient, large-scale production, and excellent adsorption capacity, but also expand the potential of electrospinning technology and composite fibers in volatile organic gas adsorption.     

Preparation and properties of styrene ethylene butylene styrene / polypropylene thermoplastic elastomer powder for selective laser sintering 3D printing

As one of the most important thermoplastic elastomer materials, the application of styrene ethylene butylene styrene (SEBS) in selective laser sintering (SLS) has not been reported. In this study, SEBS and polypropylene (PP) are blended and then pulverized at low temperatures. We find that SEBS with high molecular weight and styrene segment content is difficult to melt and flow under laser irradiation, which is not suitable for SLS 3D printing. SEBS with low molecular weight can be printed, and its tensile properties can reach 2.1Mpa and 134% elongation at break. We test the enhanced absorption effect of two different infrared absorbers and find that graphene (GE) can enhance absorption mainly rely on its special structure to increase the optical path of the laser. The absorption enhancement effect of each enhancer rises first and then decreases. 0.4‰ addition of GE can bring 22.5% enhancement. With the enhancement of GE, we get a product of 2.8 MPa tensile strength and 176% elongation at break.     

Sustainability-guided life-cycle design and assessment for bio-based composite foams: Integrate flame retardancy/lightweight in usage and energy utilization after service

Sustainable development strategy has aroused a great interest in biomass resources as alternative raw materials. A kind of biomass-derived poly(butylene succinate) (PBS), has been developed as porous foams to reduce resource exhaustion and meet lightweight demands. For fire-safety in-service, graphene oxide (GO) was functionalized by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) to combine flame-retardant elements and heat-barrier function. Hence, a very low loading level of P-containing GO as only 5 wt% could reduce peak heat release rate (pHRR) and total heat release (THR) of PBS-based foams by 58.5% and 22.3%, respectively. Meanwhile, N-/P-doped mesoporous char with a specific surface area of 136 m²/g, which derived from combustion of flame-retardant foaming PBS, contributes to a potential of energy storage applications in the capacitor or the anode of Li-ion battery with long-term stability. Overall, the sustainability of bio-based polyester could integrate lightweight of foaming, and be extended to utilization after use via facile combustion inspired by flame-retardancy design.     

Preparation and characterization of high strength and high modulus PVA fiber via dry-wet spinning with cross-linking of boric acid

To improve the mechanical properties of polyvinyl alcohol (PVA) fibers, a series of PVA fibers were prepared via dry-wet spinning with cross-linking of boric acid (BA) (PVA/BA fibers), and using the mixed solvent of dimethyl sulfoxide and water. Moreover, the final PVA/BA fibers were characterized by Fourier transform infrared spectra (FTIR), scanning electron microscopy (SEM), differential scanning calorimetery (DSC), thermogravimetric analyzer (TGA), powder X-ray diffraction (XRD) and yarn strength tester. Furthermore, with the increasing of BA content, FTIR analysis showed that the degree of crosslinking of BA with PVA increased. SEM images of final PVA/BA fibers presented smooth surfaces, and the diameters decreased firstly and then increased. DSC, TGA, and XRD analysis indicated that the melting temperatures, thermal properties and crystallinities first increased and then decreased with the increasing of BA content. In addition, mechanical properties measurements illustrated that the cross-linking existed at an optimal BA content of 0.3 wt%, and PVA/BA-0.3 fiber had the highest tensile strength and Young's modulus of 13.1 ± 0.4 and 360.2 ± 10.4 cN/dtex, respectively.     

Viscoelastic properties and flow instabilities of aqueous suspensions of cellulosic fibers: Effects of a gelation agent on dispersion,rheology, and flow stability

Processing of concentrated lignocellulosic biomass suspensions typically involves the conversion of the cellulose into sugars and sugars into ethanol. Biomass is usually pretreated via methods like comminution or steam explosion to form fine cellulosic fibers to be dispersed into an aqueous phase for further treatment. The resulting cellulose suspensions need to be pressurized and pumped into and out of various processing vessels without allowing the development of flow instabilities that are typically associated with “demixing”, that is, the segregation of the cellulosic biomass from the aqueous phase via the formation of mats of cellulosic fibers and the filtration of the aqueous phase. Such demixing can prevent continuous processing at high rates. Here, the development of flow instabilities via the demixing effect for cellulose suspensions is demonstrated using capillary and compressive squeeze flows. It is shown that the use of a gelation agent, hydroxypropyl guar gum, at the critical concentration of 0.5 wt% or higher significantly affects the viscoelastic material functions of cellulosic suspensions, improves the dispersive mixing of the fibers within the aqueous phase, and results in the elimination of the flow instabilities and associated demixing effects that are ubiquitously observed during the pressurization and processing of cellulosic suspensions.     

Ionic liquid modified graphene oxide for enhanced flame retardancy and mechanical properties of epoxy resin

In this work, to improve its dispersion and flame retardancy, graphene oxide (GO) was functionalized by silane coupling agent KH550 and 1-butyl-3-methylimidazole hexafluorophosphate (PF₆-ILs), and characteristics of the PF₆-ILs@GO was obtained by transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). Then, the synergistic flame retardant of GO or PF₆-ILs@GO and melamine pyrophosphate (MPP) were applied for epoxy resin (EP) materials. Specifically, the limiting oxygen index (LOI) value of EP with 0.1 wt% PF₆-ILs@GO was increased to 29.2% from 27.5% of EP/MPP composites, and the UL-94 test reached the V-0 rating. The CCT results showed that the total heat release (THR) and total smoke release (TSP) of EP/MPP/PF₆-ILs@GO composites were significantly 24.4% and 53.4% lower than that of EP/MPP composites. Besides, the thermal behavior investigated by TGA indicated that the char-forming effect of GO and PF₆-ILs@GO was great, the residual char of EP/MPP/PF₆-ILs@GO composites was as high as 19.5% at 700°C, and its thermal stability was higher than that of EP/MPP composites. On the other hand, the tensile strength of EP/MPP/GO and EP/MPP/PF₆-ILs@GO composites were increased by 15.6% and 28.3% compared with EP/MPP composites. According to SEM analysis, the EP/MPP/GO composites formed a good protective char layer, which can effectively improve flame retardancy of EP. This research represents a new method of flame retardant modified GO to improve the flame retardancy and mechanical properties of polymers.