A new bismaleimide system for resin transfer molding

A new bismaleimide (BMI) resin system, designated 4503A, suitable for resin transfer molding (RTM) has been developed. It is prepared by employing allyl methyl phenol and diallyl bisphenol A as reactive diluents for BMI. The processing properties of 4503A were investigated by time-temperature-viscosity curves, gel characteristics, and differential scanning calorimetry (DSC). Data show that the injection temperature of 4503A prepolymer can be as low as 75°C, while its viscosity is only 0.34Pa · s. In addition, after being maintained at 75°C for 12h, the viscosity is <0.95Pa · s. The cured 4503A resin has a glass transition temperature (T_g) and a heat deflection temperature (HDT) of 266 and 232°C, respectively; properties include tensile strength of 81MPa, flexural strength of 108MPa, and G_1C of 213J/m². Other properties of a composite based on 4503A system and woven glass cloth are also discussed. Regarding short beam shear (SBS) strength, for tests at 150 and 180°C, 80 and 61% of the original room temperature (RT) strength is retained. A similar strength retention (86 and 68%) is noted for flexural properties.     

Bubble transport through constricted capillary tubes with application to resin transfer molding

This paper describes and expounds a theoretical and experimental study of bubble motion through constricted capillary tubes. In the experiment, two liquidfilled capillaries are used. They have unequal radii and are glued together. Gas bubbles are injected into the larger capillary. Then the pressure required to force the bubbles through the constriction is measured for various liquids, bubble lengths, capillary radii and constriction geometry. It appears that the pressure directly follows Young's-Laplace law for capillary pressure. The results of the study are used to understand the bubble transport through fiber reinforcements, which generally takes place during the manufacturing of composites. The bubbles are carried if: (i) the pressure gradient is high enough, (ii) the surface tension of the liquid is low enough, (iii) the cross-sectional area of the channels in the reinforcement is sufficiently uniform. The theory reveals that the bubbles are more likely to be trapped on a small scale, i.e. within fiber bundles rather than on a large scale, i.e. between the bundles. It is also concluded that, if the bubbles are trapped at the resin flow front, a converging flow is better for the transport of the voids than a diverging flow.     

A new approach for kinetic modeling and optimization of rubber molding

Although extensive research has been carried out on the understanding of the complex vulcanization process, the influence of reversion through exposure time and temperature on the vulcanization degree remains unclear. Therefore, the main aim of this study was a novel optimization approach that can help the industrial practitioners to select the optimal operating parameters, exposure time, and molding temperature, to achieve desired vulcanization degree of selected product. Spheres of four different diameters (2.5, 5, 10, and 20 cm) were selected as test geometry for simulation and optimization of rubber molding. Obtained vulcanization rheometer data for commercially available rubber blend (NR/SBR) were fitted by a new modeling approach, dividing vulcanization curve into two fitting sets: curing and reversion. The heat transfer equations for chosen geometry were coupled with proposed kinetic model. A new temperature-dependent kinetic parameter x, as the maximal reversion degree, was introduced, enabling determination of the lowest operating molding temperature (T_min = 132.36 °C), preventing high reversion and overheating of the rubber product. The final optimization goal was assessment of the optimal temperature and vulcanization time dependence on the rubber products dimensions. Proposed models have precise prediction with R² values greater than 0.8328 and MAPE less than 2.3099%.     

Reactive processing of thermoset/thermoplastic blends: A potential for injection molding

Poly(2,6-dimethyl-1,4-phenylene ether) (PPE) is an engineering plastic with high heat distortion temperature. Melt processing of neat PPE is usually accompanied with thermal degradation. The degradation problem is solved by blending with polystyrene to reduce the processing temperature. We propose an alternative using triallylisocyanurate (TAIC). TAIC is a low viscosity liquid that can be cured by peroxide, e.g. α,α′-bis(t-butylperoxy-m-isopropyl)benzene (PBP), to provide a thermoset. The PPE/TAIC mixture was shown to have the upper critical solution temperature (UCST) type phase behavior. At the single-phase regime above UCST and below the cure temperature (∼180°C for PBP), the mixture had a low viscosity, less viscous than a conventional thermoplastic such as PC and PP. That is, a nice window for injection molding was available, e.g., at 100°C to 160°C for a 50/50 blend. After injecting into a hot mold set at cure temperature, the blend cured in a short time (∼80% conversion in 5 min). Then the molded and partly cured material kept its shape and dimensions during post-cure in a hot chamber at higher temperature (e.g. 250°C). Using transmission electron microscopy and dynamic mechanical analyses, it was shown that the cured blend had a bicontinuous two-phase structure with periodic spacings of ∼30 nm, suggesting a structure formation via a spinodal decomposition driven by the increase in molecular weight of TAIC during cure. The cured material showed excellent flexural strength and high chemical resistance.     

1,4-Bis(2,3-dicarboxyl-phenoxy)benzene dianhydride-based phenylethynyl terminated thermoset oligoimides for resin transfer molding applications

A series of thermoset oligoimides have been prepared by the thermal polycondensation of 1,4-bis(2,3-dicarboxyl-phenoxy)benzene dianhydride with three different aromatic diamines in the presence of 4-phenylethynylphthalic anhydride as an end capping reagent. The aromatic diamines included 4,4′-oxydianiline, 2,2′-bis(trifluoromethyl)benzidine (TFDB) and 2-phenyl-4,4′-diaminodiphenyl ether (p-ODA). Effects of the chemical structures and molecular weights of the oligoimides on their aggregated structures, melt processability as well as the thermal and mechanical properties of the cured films were then systematically investigated. X-ray diffraction results indicated that ODA series oligoimides and TFDB series oligoimides showed crystallinity; however, the asymmetrical p-ODA enables the p-ODA series oligoimides to exhibit amorphous forms. So the p-ODA based oligoimides with molecular weight of 750 g mol⁻¹ showed much lower melt viscosity at a low temperature and the melt viscosity could maintain below 1 Pa s⁻¹ after isothermal aging for 2 h at any temperature in the range of 220–280 °C by rheological measurements. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47967.     

Evaluation of compatibility of methacrylic copolymers by capillary viscometry

The estimation of the compatibility of different pairs of polymers can be based on capillary viscometry data for ternary polymer‐polymer‐solvent systems using mathematical models based on the slope of the Huggins equation (Δb) and Huggins constant (Δk′). In this study, the compatibility of binary mixtures of six types of methacrylic copolymers with similar molecular weights but different functional groups [one characterized by amine groups (EuE), two by ammonium groups (EuRL EuRS), two by carboxylic groups (EuL EuS), and one without charge (EuNE)] was evaluated using these methods. On the basis of Huggins and Kraemer constants, acetone and tetrahydrofurane were selected as good solvents for the programmed blends. Cationic copolymers mixed with anionic copolymers showed the formation of visible aggregates. The study performed on the other blends showed that EuRL and EuRS could be considered compatible with EuE; EuNE was incompatible with both EuL and EuE, EuL and EuS were incompatible between them. EuRL and EuRS could be considered compatible even if the weight ratio seems to influence the behavior of the two copolymers. The Δk′ approach seems to be more robust than the Δb model. The compatibility of different pairs of methacrylic copolymers with similar molecular weights could be evaluated using capillary viscometry. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1662–1668, 2000     

Improving the crack resistance of bulk molding compounds and sheet molding compounds

Fiber-reinforced plastics exhibit two types of mechanical failure: gross fracture and microcracking. Gross fracture involves both matrix and fiber failures. Principal resistance to crack propagation derives from partial decoupling of fibers and then stressing, remove finite volumes of them to fracture. Classical concepts of fracture mechanics can be applied to such composites, though modifications of methodology to treat anisotropy and other special effects are required. Microcracking occurs principally in the matrix phase and usually accompanies cyclic fatigue, drop impact, bending, or rapid cooling from molding temperatures. It lowers composite stiffness, environmental resistance and may reduce strength. Matrix resins require high fracture toughness to minimize or eliminate microcracking. This paper discusses cracking in bulk molding compounds and sheet molding compounds, complex materials containing high percentages of glass fibers and calcium carbonate filler. Microcracking can be greatly reduced by tire addition of small amounts of a rubber to the polyester matrix. Various tests such as impact, bending, acoustic emission and crack propagation demonstrate the improved toughness properties which result. No sacrifice of original strength characteristics occurs, and markedly improved resistance to damage has been noted with rubber modified epoxy and polyester matrix resins.     

Mesostructure development during molding of sheet molding compounds

Experiments have been carried out with sheet molding compounds in which the amount of shear developed during molding was varied by changing the charge size. The effects of pressure and temperature were also investigated. The moldings were characterized by their mesostructures and the influence of the mesostructures on the Izod toughness and flexural strength was examined. It was found that high degrees of shear resulted in fiber orientation and the spreading of the fiber bundles. However, this did not improve properties, and it was concluded that for optimum properties, small amounts of shear were desirable.     

Processing-property relationships in compression molding of sheet molding compounds

An experimental investigation was conducted into establishing relationships between the processing variables and the mechanical properties of compression-molded parts of sheet molding compounds (SMC). Emphasis was placed on investigating the effects on the tensile properties, impact strength, and dynamic mechanical properties of composite specimens, of low-profile additives, and of treating glass fibers (for reinforcement) with sizing chemicals. The processing variables investigated were cure time, mold temperature, and mold pressure. It was found that: (1) An optimum cure time and mold temperature exist for achieving molded SMC composites of the greatest tensile and impact strengths; (2) Of the four different types of low-profile thermoplastic additives employed, the poly(vinyl acetate) modified with acrylic acid gives rise to molded SMC composites having the greatest tensile and impact strengths; (3) An optimum cure time and mold temperature exist for achieving the highest glass-transition (T_g) of the low-profile additive; (4) The values of cure time and mold temperature that have yielded the greatest tensile and impact strengths also yield molded specimens having the highest T_g of the low-profile additive.     

A nonlinear control method for resin transfer molding

In performing permeability measurements on the fiber reinforced preforms typically used in the resin transfer molding (RTM) process, two types of fluid injection are commonly utilized: constant fluid pressure and constant fluid flow rate. The constant pressure condition is often enforced by placing the test fluid within a pressure pot and supplying a constant gas pressure, thereby forcing the fluid into the mold under a constant pressure. In the case of constant fluid flow rate, the fluid is often supplied by forcing a piston through a fluid-filled cylinder at a constant rate of displacement through the use of a press or Instron machine. This paper presents a nonlinear control method for providing constant flow rate RTM processes with a pressure pot solely through the use of a regulator. Computer simulations of the control examined the effect of various parameters on the ability to maintain constant flow rate. Rectilinear flow experiments were carried out to evaluate the theoretical development. Experimental results are in good agreement with the computer simulations. Both computer simulations and experiments show significant promise for the proposed control methodology.     

Thermoset injection molding dynamics and the distribution of cure in thermoset molded parts

A detailed characterization of a commercial-filled unsaturated polyester molding compound has been carried out to determine the kinetics of cure and the rheological behavior of the material at various temperatures and shear rates. Molding experiments were conducted in a 2 1/3 oz, 68 ton reciprocating screw injection molding machine, in conjunction with a simple rectangular cavity. The cavity and nozzle were equipped with pressure transducers to determine, the variation of pressure with position throughout the injection molding cycle. The injection speed was determined with the help of a position transducer. Finally, the moldings were analyzed to determine the distribution of cure states and tensile properties in the molding at various cure times. Significant differences have been observed. It is expected that studies of this type should be helpful in obtaining a better understanding of the thermoset injection molding process and the development of mathematical models to simulate this process.     

Resin transfer molding process optimization using numerical simulation and design of experiments approach

The art of resin transfer molding (RTM) process optimization requires a clear understanding of how the process performance is affected by variations in some important process parameters. In this paper, maximum pressure and mold filling time of the RTM process are considered as characteristics of the process performance to evaluate the process design. The five process parameters taken into consideration are flow rate, fiber volume fraction, number of gates, gate location, and number of vents. An integrated methodology was proposed to investigate the effects of process prameters on maximum pressure and mold filling time and to find the optimum processing conditions. The method combines numerical simulation and design of experiments (DOE) approach and is applied to process design for a cylindrical composite part. Using RTM simulation, a series of numerical experiments were conducted to predict maximum pressure and mold filling time of the RTM process. A half‐fractional factorial design was conducted to identify the significant factors in the RTM process. Furthermore, the empirical models and sensitivity coefficients for maximum pressure and mold filling time were developed. Comparatively close agreements were found among the empirical approximations, numerical simulations, and actual experiments. These results were further utilized to find the optimal processing conditions for the example part.     

Compression molding of sheet molding compounds in plate-rib type geometry

The flow of fiber-reinforced composite materials in a plate-rib type mold geometry during compression molding was investigated using a series of sheet molding compounds (SMC). Material anisotropy in relation to the amount and the length of reinforcing fibers was analyzed. The influence of the interfacial friction between SMC charge and the mold surface on the flow and sink mark formation was also examined. The results were explained qualitatively by computer simulation.     

Injection molding of unsaturated polyester compounds

A bulk-molding compound made of unsaturated polyester resin, glass fiber, calcium carbonate fillers, and low profile additives is studied. The viscosity of the compound in the absence of cure reaction is measured by capillary rheometry. The compound exhibits a shear-thinning behavior. Injection molding in a rectangular plaque equipped with pressure transducers shows that the crosslinking reaction can begin during mold filling for low flow rate or high mold temperature. Fiber orientation in the plaque is complex as the reinforcement appears under two aspects, bundles or filaments. Their lengths and orientations are different. A layered structure throughout the thickness is observed at the mold entrance, whereas the orientation becomes progressively unidirectional in the plaque. Two fiber-free layers near the the mold walls are observed. A numerical simulation of mold filling assuming inelastic non-Newtonian kinetic dependent behavior is presented. The results agree well with pressure measurements. A simplified decoupled fiber motion calculation is finally proposed. A qualitative explanation of the basic phenomena which induce fiber orientation is presented.     

Joining strength of sheet molding compounds

Bonding and bolting strengths of a sheet molding compound (SMC-R30) are investigated. Epoxy adhesives are found to give good bonding strength. Surface pretreatment does not affect bond strength. Artificial weathering has practically no effect upon bond strength. Bolting strength depends on the width of the specimen for a certain bolt size. Bolting gives stronger joints than bonding.     

The effect of flow on cavity surface temperatures in thermoset and thermoplastic injection molding

In the Injection molding process, nonuniform heat transfer between the polymer and the mold caused by flow during the cavity filling stage can lead to spatial variations in the cavity surface temperature. This can result in an increase in cycle time or poor part quality. An investigation of the flow-induced, nonuniform, cavity surface temperature is reported here. A flow model for a thin, rectangular, end-gated cavity and a model for the steady-state temperature distribution in a simple mold are developed. These are applied to some thermosetting and thermoplastic systems. For both filled and unfilled thermosets, it is found that a simple plug flow model gives a good approximation for the heat transfer during flow. For thermoplastics, however, the full flow solution must be used. For the cases considered in this study, the steady-state temperature variation along the cavity surface is less for the thermoplastics than for the thermosets.     

Property modification of bulk molding compounds for use in injection molding

Although impact and flexural strength of injectionmolded bulk molding compounds increase initially with glass fiber content, these properties level out at a glass volume fraction between 0.1 and 0.2, limiting the achievable properties. Use of “special purpose” polyester resins gives no significant improvement in impact. The impact strength limitation is not worsened, however, by using the maximum processable level of filler, this being true for all fillers commonly used in polyester compounds. Replacement of a fraction of the glass by poly(ethylene terephthalate) fibers results in a substantial improvement in impact strength.     

Natural fiber hybrid composites—A comparison between compression molding and resin transfer molding

Short randomly oriented intimately mixed banana and sisal hybrid fiber‐reinforced polyester composites having varying volume fraction of fiber were fabricated by compression molding (CM) and resin transfer molding (RTM) techniques by keeping the volume ratio of banana and sisal, 1:1. The static mechanical properties such as tensile, flexural, and impact behavior were studied. The dynamic mechanical properties were also evaluated. Resin transfer molded composites showed enhanced static and dynamic mechanical properties, compared with the compression molded samples. To analyze the fracture surface morphology of the composites, scanning electron microscopy (SEM) was also performed. Water sorption studies revealed that the water uptake of RTM fabricated composites was lower than that of the compression molded composites. The void content of the RTM composites was also found to be lower than that of the other one. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers