The Effect of Particle Matrix Adhesion on the Mechanical Properties of Silica Filled Cyanate Ester Composites

Summary: The effect of silica and its surface treatment on the mechanical properties of composites was studied as part of the evaluation of cyanate ester matrices as potential electronic encapsulants. Three filler surface treatments were used, as a qualitative interfacial adhesion scale, in an attempt to gauge the magnitude of interfacial adhesion between untreated filler and the cyanate ester matrix. There was strong interfacial adhesion between matrix and untreated filler. The level of silica content most affected composite modulus and fracture toughness. Filler surface treatment most affected composite strength and fracture toughness/energy. Composite fracture was found to occur via crack pinning and/or crack blunting depending on the strength of adhesion. The composites evaluated were found to possess suitable mechanical properties for potential use as electronic encapsulants.

     

Transcrystallinity in Surface Modified Aramid Fiber Reinforced Nylon 66 Composites

Aramid (kevlar‐49) fibers were surface treated by two different methods to induce roughness and then used to produce unidirectional nylon 66 based composites. The transcrystallinity generated around the treated fibers was characterized by SEM and polarized light microscopy and compared with the regular transcrystalline layers produced by pristine aramid under the same processing conditions. The treated fibers generated a double transcrystalline layer, the inner layer being thinner and more compact than the regular nylon 66 transcrystallinity. In addition, mechanical testing of the composites showed the longitudinal Young's modulus of the treated fiber composites to be significantly higher than the control in a wide range of fiber volume fractions.

Polarized light microscopy picture of double transcrystallinity in Br/NH₃ treated aramid fiber reinforced nylon 66.     

Thermoplastic Polyurethane Nanocomposites Produced via Impregnation of Long Carbon Nanotube Forests

TPU was infiltrated into vertically aligned, 3.5 mm‐long MWNT forests to produce continuously reinforced anisotropic nanocomposites, and thermomechanical and electrical testing has revealed multifunctionality which shows promise for numerous applications. A 1000% increase in the storage modulus at 70 °C was observed as compared to the neat TPU, and these continuously aligned composites showed electrical conductivity two orders‐of‐magnitude greater (≈1.5 S · cm^?1) than randomly aligned composites prepared using CNTs from these forests. The heightened improvement for the continuously reinforced composite appears to be owed to the extremely high aspect ratio of these CNTs and the interconnected network which remains after infiltration.

     

Study of the Fire Performance of Magnesium Hydroxide Sulfate Hydrate Whisker Flame Retardant Polyethylene

Summary: Halogen‐free, flame retardant low density polyethylene (LDPE) composites, using magnesium hydroxide sulfate hydrate (MHSH) whiskers as a flame retardant, combined with microencapsulated red phosphorous (MRP) as a synergist, have been prepared using a two‐roll mill. Their fire properties were determined by using the limiting oxygen index (LOI), the UL‐94 test and cone calorimetry. The results showed that MRP was a good synergist in improving the flame retardance of the LDPE/MHSH whisker system. Poly[ethylene‐co‐(vinyl acetate)] (EVA), used as a compatibilizer, increased the fire performance of LDPE/MHSH whisker composites.

HRR curves for LDPE/MHSH whisker composites.     

High Temperature Thermosets With a Low Coefficient of Thermal Expansion

Summary: Polymeric thermosetting composites can be used as metal substitutes for certain applications if they possess high temperature stability in air, low coefficient of thermal expansion (CTE), and sufficient flexural strength, in combination with competitive costs. Commercial bismaleimide, bisnadimide, and cyanate ester thermosetting materials were selected due to their excellent thermal stability. Low CTEs were achieved by adding high loading levels of fused silica or silicon nitride fillers. Several optimized composites were fabricated by varying the materials, composition, and cure conditions. Characteristic composite properties, such as CTE, thermal stability, glass transition temperature (T_g), flexural strength, and filler distribution were investigated. The best system developed consists of Matrimide 5292, a commercial two‐component bismaleimide resin, filled with 75% Silbond FW100EST, and additionally reinforced with 0.5% Twaron short fibers. This composite is distinguished by a CTE around 15 ppm · K⁻¹, a T_g around 340 °C, flexural strength above 100 MPa, and attractive material costs.

Matrimid 5292 (75%)/Silbond FW100AST (24.5%), and Twaron 2 mm short fibers (0.5%). Three fibers are visible, embedded and well dispersed in the matrix.     

Injection Moulding: Evaluation of Appropriate Melt Injection Points for the Gas Injection Technique

In gas assisted injection moulding the melt front advancement has a considerable effect on the gas penetration. The evaluation of an appropriate melt filling is an important step to avoid instabilities in the process sequence. Taking a sample moulded part a procedure is presented that enables the part designer to evaluate required melt and gas injection points according to the gas injection technique. Using finite element simulations, different calculations for the melt front advancement lead to the correct gate location.

Presentation of different degrees of filling for the optimised article geometry.     

Intercalated Polycarbonate/Clay Nanocomposites: Nanostructure Control and Foam Processing

Intercalated polycarbonate (PC)/clay nanocomposites (PCCN)s have been prepared successfully through the melt intercalation method in the presence of a compatibilizer. The internal structure and morphology of the PCCNs has been established by using wide‐angle X‐ray diffraction (WAXD) analyses and transmission electron microscopic (TEM) observations. The morphology of these nanocomposites and degradation of the PC matrix after nanocomposites preparation can be controlled by varying surfactants used for the modification of clay and compatibilizer. The intercalated PCCNs exhibited remarkable improvements of mechanical properties when compared with PC without clay. We also discuss foam processing of one representative PCCN using supercritical CO₂ as a foaming agent.

TEM bright field image of intercalated polycarbonate/synthetic fluorohectorite nanocomposite.     

Preparation and Characterization of Organic/Inorganic Polymer Composites Based on Mg‐Silicates

Summary: An organic‐inorganic hybrid material consisting of a 3‐(methacryloxy)propyl functionalized SiO₂/MgO framework was synthesized. This hybrid was successfully reacted with styrene, butyl acrylate and butyl methacrylate via a free radical emulsion polymerization to form polymer composites. The polymer composites were investigated by means of FT‐IR spectroscopy, TGA, DSC and rheometry. It is shown that the polymer is linked covalently to the organic/inorganic hybrid. Although the polymer content is rather low, the composites exhibit a polymer‐like character and enhanced mechanical properties compared to the corresponding homopolymers.

     

The Anisotropy of Fibrillar Silicate/Rubber Nanocomposites

Summary: Fibrillar silicate (FS)/rubber nanocomposites were successfully prepared by directly mixing modified FS with rubber matrix. It is found that FS could be separated into nano‐fibrils with diameters less than 100 nm by the shear forces during mixing. The stress‐strain characteristics of these composites are similar to those for short micro‐fiber/rubber composites (SFRC). Nevertheless, these FS/rubber composites have some outstanding advantages over the conventional SFRC, even though the reinforcing effect of FS is restricted due to its small shape aspect ratio. More importantly, the differences in mechanical properties of the composites in the two different directions show that SBR/FS and NBR/FS composites both exhibit obvious anisotropy, which strongly depends on the preparation process, FS concentration, and rubber matrix. These factors were thoroughly investigated in this paper, and it can be concluded that the anisotropy of the composites was due to the orientation of nano‐fibrils.

     

Ternary Gels of a Polymer Blend and a Recycled Oil: Their Use as Bitumen Modifiers

A blend of random ethylene‐vinyl acetate copolymer (EVA) and triblock styrene‐butadiene‐styrene copolymer (SBS) was dissolved in a recycled engine oil to obtain ternary thermoreversible gels. As the temperature was increased, first a network associated with EVA disappeared, and a second one associated with SBS dominated, maintaining the elastic response of the system. The principal advantage of these ternary systems is that their mechanical properties and thermal stability are better than that of binary gels. These gels, made from waste, can be used as bitumen modifiers to obtain binders of improved properties and good stability, which are useful for road surfacing.

Temperature sweeps of elastic modulus performed at a frequency of 1 Hz.     

Tensile Fracture and Failure Behavior of Thermoplastic Starch with Unidirectional and Cross‐Ply Flax Fiber Reinforcements

Thermoplastic starch (MaterBi®) based composites containing flax fibers in unidirectional and crossed‐ply arrangements were produced by hot pressing using the film stacking method. The flax content was varied in three steps, viz. 20, 40 and 60 wt.‐%. Static tensile mechanical properties (stiffness and strength) of the composites were determined on dumbbell specimens. During their loading the acoustic emission (AE) was recorded. Burst type AE signal characteristics (amplitude, width) were traced to the failure mechanisms and supported by fractographic inspection. The mechanical response and failure mode of the composites strongly depended on the flax content and the flax fiber lay‐up. It was established that the tensile strength increases until 40 wt.‐% flax fiber content but stays almost constant above this value. In the case of 40 wt.‐% unidirectional fiber reinforcement, the tensile strength of the composite was 3 times greater than that of the pure starch matrix. The flax fiber reinforcement increased the tensile modulus of the pure starch by several orders of amplitude.

SEM picture of the fracture surface of a composite with UD flax reinforcement.     

Design of a Microfluidic System to Investigate the Mechanical Properties of Layer‐by‐Layer Fabricated Capsules

A microfluidic system was designed, fabricated and implemented to study the behavior of polyelectrolyte capsules flowing in microscale channels. The device contains microchannels that lead into constrictions intended to capture polyelectrolyte microcapsules which were fabricated with the well‐known layer‐by‐layer (LbL) assembly technique. The behavior of hollow capsules at the constrictions was visualized and the properties of the capsules were investigated before and after introduction into the device.

Time series of video frames showing capsules being compressed into a constriction.     

Preparation and Characterization of Conducting Systems based on EPDM/PE/PS‐co‐DVB/HSb

Summary: Blends of different compositions were prepared from: a thermoplastic elastomer (EPDM), a low density polyethylene (PE), a polystyrene crosslinked with a small amount of divinylbenzene (PS‐co‐DVB) and an inorganic proton conductor: antimonic acid (HSb). The blends obtained were sulfonated heterogeneously with chlorosulfonic acid and were then structurally and electrically characterized by means of the following techniques: differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), crystallization kinetics under non‐isothermal conditions and complex impedance spectroscopy.

Dynamic mechanical analysis for EPDM and EP‐3 blends series.     

An Application of Silica‐Based Monolithic Membrane Emulsification Technique for Easy and Efficient Preparation of Uniformly Sized Polymer Particles

Summary: Uniformly sized polymer particles were prepared by an emulsification and polymerization technique utilizing a silica monolithic membrane, namely the “silica monolithic membrane emulsification technique”. In this paper, we utilized silica monolithic membrane as a device for the preparation of uniformly sized polymer particles. A mixture of monomers, diluents and oil‐soluble initiator was emulsified into a continuous medium through the silica monolithic membrane and polymerized. The particles obtained had a higher size uniformity than that of particles prepared by previously reported membrane emulsification techniques, such as the Shirasu Porous Glass (SPG) emulsification technique. Through the silica monolithic membrane emulsification technique, we could prepare particles having availability as a possible packing material for solid‐phase extraction (SPE) and high performance liquid chromatography (HPLC).

SEM photograph of silica particles prepared through capillary plate membrane.     

Hydroxyapatite Reinforced Chitosan and Polyester Blends for Biomedical Applications

Summary: Hydroxyapatite, chitosan, and aliphatic polyester were compounded using a twin‐screw extruder. The polyesters include poly(ε‐caprolactone) (PCL), poly(lactic acid) , poly(butylene succinate) (PBS), and poly(butylene terephthalate adipate). The mass fraction of chitosan ranged from 17.5 to 45%, while that of HA ranged from 10 to 30%. These blends were injection molded and evaluated for thermal, morphological, and mechanical properties. The addition of hydroxyapatite decreased the crystallinity in chitosan/PBS blends, while in blends containing chitosan/PCL, the crystallinity increased. Addition of hydroxyapatite significantly decreased the tensile strength and elongation of polyester/hydroxyapatite composites as well as chitosan/polyester/hydroxyapatite composites with elongations undergoing decreases over an order of magnitude. The tensile strength of the composite was dictated by the adhesion of HA to the chitosan/polyester matrix. The tensile strength of composites containing hydroxyapatite could be predicted using the Nicolai and Narkis equation for weak filler adhesion (K ≈ 1.21). Tensile‐fractured and cryogenically‐fractured surface indicates extensive debonding of hydroxyapatite crystals from the matrix, indicating weak adhesion. The adhesion of hydroxyapatite was higher for pure polyester than those containing chitosan and polyester. The modulus of the composites registered modest increase. The two main diffraction peaks observed using WAXS are unaffected by the amount of chitosan or hydroxyapatite.

     

Improved Design of Shearing Sections with New Calculation Models Based on 3D Finite‐Element Simulations

New models for the Maddock and spiral shearing sections have been developed, employing three‐dimensional finite element analysis (3D FEA). These models describe the pressure‐throughput and power consumption behavior of the shearing sections for both the extrusion and the injection molding process and have been implemented in the REX 6.0 and PSI 4.0 simulation software. As a consequence it is now possible to describe the process behavior of these shearing sections within just a few seconds with the accuracy of FEA calculations.

Actual Maddock shearing section (left) and actual spiral shearing section (right).     

The Effects of Copper Oxides on the Curing Behaviors of Bismaleimide Triazine Prepreg

The effect of copper oxides on the curing behaviors of the bismaleimide triazine (BT) prepreg is studied with infrared spectroscopy (IR), attenuated total reflection infrared spectroscopy (ATR), and X‐ray photoelectron spectroscopy (XPS). The result of IR analyses indicates that there is a concentration distribution present in the prepreg surface layer and the outer surface layer contains less cyanate, imide, and epoxide but more triazine groups than the inner layer. From ATR, it is concluded that the cuprous oxide attracts more cyanate ester resins but less bismaleimide resins from the prepreg to its surface than the cupric oxide. The copper surface affects the curing extent of the BT resin in contact and the cupric oxide has a more pronounced effect than the cuprous oxide, and this surface effect can extend to at least two microns deep into the BT prepreg from the contacted interface. The XPS results confirm that the BT/CuO interface contains more thermally stable and polar functional groups than the BT/Cu₂O interface, and both two copper oxides attract only a small amount of brominated epoxy resin onto their surfaces. These results are attributed to the difference in preferential adsorptions and catalytic curing effects of two copper oxides on the BT prepreg in contact.

The intensity changes of IR bands obtained from BT prepreg during cure.     

Dynamic Mechanical and Thermal Properties of Phenylethynyl‐Terminated Polyimide Composites Reinforced With Expanded Graphite Nanoplatelets

Summary: This article reports on the dynamic mechanical and thermal properties of thermosetting phenylethynyl‐terminated polyimide (PETI‐5) composites reinforced with expanded graphite (EG) nanoplatelets having various average particle sizes and content. The EG nanoplatelets with varying particle sizes were prepared by different pulverization techniques through intercalation and exfoliation of natural graphite flakes. The effect of the EG particle size and concentration of the thermal behavior of PETI‐5/EG composites was investigated with several thermal analysis methods (DMA, TMA, and DSC). The storage modulus dynamic mechanical properties and glass transition temperature significantly increased with increasing concentration of EG nanoreinforcements regardless of size. The coefficient of thermal expansion significantly decreased, especially in the glass transition region.

     

Micromechanical Processes in PET/PC Multilayered Tapes: High Voltage Electron Microscopy Investigations

Summary: A totally new kind of multilayered tape consisting of two macroscopically ductile polymers (PET and PC) was studied using high voltage electron microscopy (HVEM). Both components were co‐extruded as uniform laminates with thousands of alternating layers. The multilayered PET/PC samples were annealed at high temperature. Investigation of the multilayered PET/PC tapes with various compositions clearly demonstrated a transition of the microdeformation mechanism which was dependent on the thickness of the individual layers. The annealing of the tapes led to a significant change in the deformation behavior. However, no lamellae formation was revealed in the PET phase after annealing, leading to the assumption of constrained crystallization in very thin PET layers.

     

Polyurethane Foams of Improved Thermal Stability

In reactions of polyetherols prepared from hydroxymethyl derivatives of uric acid and typical oxiranes with isocyanates and water one obtains a new group of polyurethane foams containing purine rings in their structure. These polyurethanes withstand prolonged heating at temperatures as high as 200 °C. Preliminary results on the effect of the type of polyetherol and the composition used in preparation of the polyurethane foams on their properties are presented. The results of studies on thermal stability and mechanical properties of the foams before and after thermal treatment are also reported.