Thermoplastic Resin Transfer Molding Research Articles

Effective Impregnation of ε-Caprolactam with Polyamide 6 Oligomer in Thermoplastic Resin Transfer Molding

Effective Impregnation of ε-Caprolactam with Polyamide 6 Oligomer in Thermoplastic Resin Transfer Molding

Non-Isothermal Crystallization Kinetics of Polyamide 6/Graphene Nanoplatelets Nanocomposites Obtained via In Situ Polymerization: Effect of Nanofiller Size.

Thermoplastic resin transfer molding (T-RTM) technology was applied to synthesize graphene nanoplatelets-based nanocomposites via anionic ring-opening polymerization (AROP). Polyamide 6 (PA6) was obtained by AROP and was used as the polymeric matrix of the developed nanocomposites. The non-isothermal crystallization behavior of PA6 and nanocomposites was analyzed by differential scanning calorimetry (DSC). Nanocomposites with 0.5 wt.% of graphene nanoplatelets (GNPs) with two different diameter sizes were prepared. Results have shown that the crystallization temperature shifted to higher values in the presence of GNPs. This behavior is more noticeable for the nanocomposite prepared with smaller GNPs (PA6/GN). The crystallization kinetic behavior of all samples was assessed by Avrami and Liu's models. It was observed that GNPs increased the crystallization rate, thus revealing a nucleating ability, and also validated the reduction of half-time crystallization values. Such tendency was also supported by the lower activation energy values determined by Friedman's method.

The degradation during recycling of polyamide 6 produced by anionic ring-opening polymerization of ε-caprolactam

As the plastics industry continues to grow, the amount of plastic waste is also increasing. The European Union is controlling plastic waste through various regulations, focusing primarily on recyclability. A good alternative to traditional thermoset composites is thermoplastic polyamide 6 composites produced by Thermoplastic Resin Transfer Molding (T-RTM). Polyamide 6 has high strength and is produced by in-situ anionic ring-opening polymerization in T-RTM. Products made with this technology can replace traditional thermoset composites in many areas, which greatly increases recyclability. In this paper, the recyclability of the high molecular weight polyamide 6 matrix material of T-RTM composites is investigated. Products were mechanically recycled and then processed by injection molding. Thermal, mechanical and rheological properties of the samples were compared with the properties of the original product, as well as a general injection molding–grade PA6. Results show that the parts prepared with this innovative technology can be mechanically recycled and reprocessed by injection molding without a processing aid. After reprocessing, a significant reduction in properties is observed due to degradation, but the properties of the resulting product are in good agreement with those of a conventional commercially available injection molding grade PA6 material.

Reproducibility Study of the Thermoplastic Resin Transfer Molding Process for Glass Fiber Reinforced Polyamide 6 Composites

Polyamide 6 (PA6) thermoplastic composites have higher recyclability potential when compared to conventional thermoset composites. A disruptive liquid molding manufacturing technology named Thermoplastic Resin Transfer Molding (T-RTM) can be used for processing composites due to the low viscosity of the monomers and additives. In this process, polymerization, crystallization and shrinkage occur almost at the same time. If these phenomena are not controlled, they can compromise the reproducibility and homogeneity of the parts. This work studied the influence of packing pressure, as a process variable, throughout the filling and polymerization stages. To assess the process reproducibility and parts’ homogeneity, physical, thermal and mechanical properties were analyzed in different areas of neat PA6 and composite parts. This study showed that a two-stage packing pressure can be successfully used to increase parts’ homogeneity and process reproducibility. The use of 3.5 bar packing pressure during the polymerization stage resulted in mechanical properties with lower standard deviations, indicating a higher degree of homogeneity of the manufactured parts and higher process reproducibility. These results will be used for establishing the actual state of the technology and will be a base for future process optimization.

Development and Analysis of an In-Mold Coating Procedure for Thermoplastic Resin Transfer Molding to Produce PA6 Composites with a Multifunctional Surface

We have developed a complex Thermoplastic Resin Transfer Molding procedure to create polyamide 6 composites and their multifunctional coatings in a single production cycle with low cycle time. The advantage of the new process is that it has low emission of volatile organic compounds due to the closed mold and the products can be recycled easily, decreasing the negative impact on the environment. In addition to developing the process steps and parameters, we produced samples with different curing time and fabric content of the base layer, waiting time before coating injection, surface thickness and titanium dioxide content of the surface layer. Then we analyzed the adhesion between the surface and base layers and the warpage of the complex part. SEM analysis proved that the reinforcement fabrics could be properly impregnated with the reactive thermoplastic system during the production of the base layer. Furthermore, we showed that the strength of the interlayer bonding can be improved when the base layer is properly polymerized in the first step. Using our method developed to assess warpage, we demonstrated that the warpage of the base layer can be reduced by applying the appropriate manufacturing parameters to the surface layer.

Novel tooling for direct melt impregnation of textile with variotherm injection moulding: Methodology and proof of concept

Thermoplastic compression resin transfer moulding coupled with injection moulding is an appealing process for the production of thermoplastic composites. However, its implementation at an industrial scale remains challenging as variotherm injection moulding could prevent solid skin formation in the parting line, making cavity sealing difficult. In this study, a tool for thermoplastic compression resin transfer moulding and the related methods and process parameters for an implementation at an industrial scale are presented. The validity of the concept is proved by producing and characterizing composite plates with elevated fibre volume fractions and advantageous mechanical properties at a range of production temperatures within a cycle time not exceeding 20 min. The best mechanical properties were obtained at a production temperature of 270°C with a bending strength of 477 MPa, a flexural modulus measured at 25.7 GPa and a fibre volume content of 67%.

Effect of Catalyst and Activator on Properties of Polyamide 6 Prepared by Thermoplastic Resin Transfer Molding Technology

Effect of Catalyst and Activator on Properties of Polyamide 6 Prepared by Thermoplastic Resin Transfer Molding Technology

Effect of glass fibre sizing on the interfacial properties of composites produced using in-situ polymerised Polyamide-6 transfer moulding

The fibre-matrix interfacial properties of glass-fibre/polyamide-6 (GF/PA-6) composites produced by thermoplastic resin transfer moulding (TP-RTM) were investigated. Two different fibre sizings were compared, a specially-developed novel reactive fibre sizing and a standard silane glass fibre sizing. Scanning electron microscopy, atomic force microscopy and a number of mass-loss techniques were employed to study the form, distribution, quantity and degradation temperature of the fibre sizings. Activated PA-6 monomer precursor materials with viscosities of ∼10 mPa s were injected into the glass-fibre fabrics, contained between heated press platens, and polymerisation occurred in-situ within several minutes. Glass-fabric laminates with fibre volume fractions of ∼53% and low void content were produced at a pressure of ∼4 bar, with the low viscosity of the monomer negating the need for expensive high-pressure injection. Similar quality between the laminates was demonstrated by measuring density, thickness, fibre volume fraction, void content and fibre bundle distribution. Transverse mechanical properties of the composites reinforced with the novel reactive sizing were 20–28% higher than those with the standard fibre sizings, demonstrating improved fibre-matrix interfacial properties. Average mode I fracture toughness was also measured to be 10–30% higher than with the standard fibre sizing. Scanning electron microscopy and 3D depth composition were used to investigate fracture surfaces and determine the surface roughness. The novel reactive fibre sizing resulted in improved fibre-matrix adhesion and improved fracture toughness.

Thermoplastic matrix‐based composites produced by resin transfer molding: A review

AbstractThe recycling of thermoset‐based composites is challenging. The replacement of thermosetting resins with thermoplastics is an initial step to address this issue, together with the use of green reinforcements. Owing to the recent development of low‐viscosity thermoplastic resins, it is possible to produce thermoplastic matrix composites using the resin transfer molding (RTM) technique, which was originally conceived for the production of thermosetting matrix composites. These resins are based on cyclic esters, methyl methacrylate, and cyclic (butylene terephthalate) oligomers. This review presents the state‐of‐the‐art works reported on the production of thermoplastic matrix composites via a thermoplastic RTM (TP‐RTM) process, from the in situ polymerization of the resins through the optimization of the TP‐RTM parameters for the evaluation of the composite properties.

Thermoplastic RTM: Impact Properties of Anionically Polymerised Polyamide 6 Composites for Structural Automotive Parts

This study investigates the impact behaviour and post-impact performance of polyamide-6 glass fibre reinforced composites, manufactured by thermoplastic resin transfer moulding. Impact test samples were extracted from quasi-isotropic laminates using two different glass fibre sizings, both with a fibre volume fraction of approximately 52%. A previous study showed that one of these sizings enhanced the interfacial strength and Mode I fracture toughness; however, the effects of the sizing on out-of-plane impact is of greater significance in terms of automotive applications. A drop-weight impact tester was used to determine out-of-plane impact performance for both sizings in terms of impact load-induced and energy returned from the striker. High-speed video of the impact response was simultaneously captured. Testing was carried out at three impact energy levels: two sub-penetration and one full penetration. The impact damage area was observed, and the post-damage compression properties of samples were measured to determine the reduction in their strength and stiffness. Results showed that the use of different sizing technologies had little effect on the post-impact compressive properties and that penetration led to only a 29% drop in compression strength. Overall, the outcomes of this work demonstrate the potential of these materials in automotive applications.

Interfacial enhancements between a three-dimensionally printed Honeycomb-Truss core and woven carbon fiber/polyamide-6 facesheets in sandwich-structured composites

A novel sandwich-structured composite comprising a three-dimensionally (3D) printed core and a woven carbon fiber/polyamide-6 facesheet was fabricated and characterized. By using selective laser sintering, which is a 3D printing technology, a structurally reinforced honeycomb-truss hybrid core was produced, which had superior compressive stiffness in various directions compared with conventional honeycomb cores. The interface between the core and the facesheet was enhanced by laser power control during the sintering as well as plasma surface treatment. The sandwich composite was produced by the reactive thermoplastic resin transfer molding (T-RTM) technique using anionic polymerization of ε-caprolactam, which has an ultra-low viscosity in the molten state. This in-situ polymerization not only enabled manufacturing process simplification by combining fabrication and bonding processes of the facesheet, but also provided excellent resin impregnation into the fiber fabrics and core surface. Therefore, the 3D printing technology, interfacial strengthening techniques, and T-RTM process induced synergistic effects on mechanical properties of the sandwich composite by forming structural reinforcement and strong mechanical and chemical interactions. The edgewise compressive properties of the hybrid core were significantly better than those of a normal honeycomb core. In addition, the interlaminar fracture toughness, impact energy absorption, and penetration limit of the sandwich composite consisting of the structurally and interfacially strengthened hybrid core increased by 76, 77, and 125%, respectively, compared to those of a nonreinforced sandwich composite.

Moisture Adsorption and Desorption Behavior of Raw Materials for the T-RTM Process

The use of fiber reinforced plastics (FRPs) has significant potential to reduce the weight of components. As regards the sustainability of these components, thermoplastic matrices offer more potential for recycling than thermoset ones. A possible manufacturing process for the production of thermoplastic FRPs is thermoplastic resin transfer molding (T-RTM). In this very moisture-sensitive process, ε-caprolactam in addition to an activator and catalyst polymerizes anionically to polyamide 6 (aPA6). The anionic polymerization of aPA6 is slowed down or even completely blocked by the presence of water. This study analyses the sorption behavior of the matrix, fiber, binder and core materials for the production of anionic polyamide 6 composites, which are processed in the thermoplastic RTM process. Water vapor sorption measurements are used to determine the adsorption and desorption behavior of the materials. The maximum moisture loading of the materials provides information about the water adsorption capacity of the material. This knowledge is crucial for correct handling of the materials to achieve a fast process and good properties of the final product.

Recent Advances in the Synthesis and Analysis of Polyamide 6 and Products Therefrom: From Polymerization Chemistry of ε-Caprolactam to Thermoplastic Resin Transfer Molding (T-RTM)

Significant research and developments are taking place in the field of synthetic polyamides (Nylons). One of the most investigated members of this family of polymers is poly (ε-caprolactam) (PCL, Polyamide 6, PA6, Nylon 6). Herein, a brief overview will be presented on the major recent advancements in the anionic ringopening polymerization (AROP) of ε-caprolactam (CL) by the initiating combinations of metal lactamates and carbamoylcaprolactams and by some other initiating systems, e.g. protected N-heterocyclic carbenes , NaHMDI and σ-borane-barium complexes. The in situ polymerization of CL in the presence of additives, such as flame retardants, reinforcing agents and fillers, is also discussed. Examples are presented on the determination of the molecular weight distributions (MWD) and average molecular weights of Polyamide 6 by GPC (SEC) measurements with 1,1,1-trifluoroethanol as eluent used routinely in our laboratories. Finally, a glimpse will be provided into the ongoing intensive research related to thermoplastic resin transfer molding (T-RTM) processes aiming at producing Polyamide 6 products, such as reinforced PA6 and composites, by rapid in situ polymerization of CL.

Development and Validation of a Test Mold for Thermoplastic Resin Transfer Molding of Reactive PA-6.

Thermoplastic resin transfer molding (T-RTM) is a cutting-edge manufacturing technique for high-volume production of composites with a recyclable thermoplastic matrix. Although a number of reactive thermoplastic matrices as well as industrial manufacturing equipment for T-RTM are commercially available today, the design of a T-RTM mold is still based on the skills and personal experience of the designer. This study summarizes the best knowledge and expertise in mold design and manufacturing and introduces an innovative mold for T-RTM. A concept and basic principles for designing a T-RTM mold are formulated in this study. The mold developed is manufactured and validated.

Manufacturing of unidirectional stitched glass fabric reinforced polyamide 6 by thermoplastic resin transfer moulding

This study aims to address barriers which remain to adoption of reactive thermoplastic resin transfer moulding in terms of knowledge and equipment. Glass fibre reinforced polyamide 6 composites with ~52% fibre volume fraction and ~1% voids were produced within 5 min using thermoplastic resin transfer moulding by injection of low viscosity monomer precursors and in-situ polymerisation. Unidirectional laminates were produced using injection pressures of around 10% of those required to achieve the same fibre volume fraction and degree of wet-out using a typical thermoset RTM resin, negating the need for expensive equipment. The equipment and process employed are described in detail and the quality and properties of the polymer matrix and composite laminates were characterised extensively in terms of chemical, thermo-morphological and mechanical properties. The paper demonstrates the high quality parts that can be achieved by accurately controlling some of the most important parameters.

Material Modeling in Forming Simulation of Three-Dimensional Fiber-Metal-Laminates – A Parametric Study

Forming of fiber-metal-laminates (FML) into complex geometries is challenging, due to the low fracture toughness of the fibers. Several researchers have addressed this topic in recent years. A new manufacturing process has been introduced in our previous work that successfully combines deep drawing with thermoplastic resin transfer molding (T-RTM) in a single process step. During molding, the fabric is infiltrated with a reactive monomeric matrix, which polymerizes to a thermoplastic after the forming process is completed. In our previous work, a numerical modeling approach was presented for this fully integrated process, investigating a hybrid laminate with 1 mm thick metal sheets of DC04 as top layers and three inner glass fiber layers. Although initial results were promising, there were still some pending issues regarding the modeling of material behavior. The current study aims to address several of these open issues and to provide a general modelling framework for future enhancements. For this purpose, the existing modelling approach is extended and used for parameter analysis. Regarding the influence of different material characteristics on the forming result, shear, bending and compression properties of the fabric are modified systematically. It is shown, that the compression behavior and particularly the tension-compression anisotropy of the fabric is of high importance for modelling the combined forming of fabric and metal. The bending and shear properties of the fabric are negligible small compared to the metal stiffness which dominates the draping process. Finally, it is demonstrated that modelling the fabric layers using continuum shells provides a promising approach for future research, as it enables a suitable way to account for transversal compaction during molding.

Effect of thermoplastic resin transfer molding process and flame surface treatment on mechanical properties of carbon fiber reinforced polyamide 6 composite

AbstractThe thermoplastic resin transfer molding (T‐RTM) process for carbon fiber reinforced thermoplastic polymer composites (CFRTP) were experimentally investigated and optimized using high‐pressure resin transfer molding system for mass production. The CFRTP was manufactured by Anionic ring opening polymerization of the T‐RTM process and the curing process was analyzed by in situ cure monitoring using dielectrometry. Mechanical properties, productivity, and crystal structures of the PA 6 matrix and CFRTP were evaluated by differential scanning calorimetry, X‐ray diffraction analysis, tensile, and interlaminar shear strength tests. The crystallinity, impregnation quality and process speed were determined by the curing temperature. In addition, a time‐ and cost‐effective flame surface treatment was developed to remove moisture from the carbon fiber and increase the interfacial bonding strength of the CFRTP. As a result, optimal T‐RTM processing conditions were suggested for realizing maximum productivity and mechanical properties for the CFRTP.

The Effect of the Parameters of T-RTM on the Properties of Polyamide 6 Prepared by in Situ Polymerization.

With the rapid development of the automotive industry, there is also a significant need to improve the raw materials used. Therefore, the demand is increasing for polymer composites with a focus on mass reduction and recyclability. Thermoplastic polymers are preferred because of their recyclability. As the automotive industry requires mass production, they require a thermoplastic raw material that can impregnate the reinforcement in a short cycle time. The most suitable monomer for this purpose is caprolactam. It can be most efficiently processed with T-RTM (thermoplastic resin transfer molding) technology, during which polyamide 6 is produced from the low-viscosity monomer by anionic ring-opening (in situ) polymerization in a tempered mold with a sufficiently short cycle time. Manufacturing parameters, such as polymerization time and mold temperature, highly influence the morphological and mechanical properties of the product. In this paper, the properties of polyamide 6 produced by T-RTM are analyzed as a function of the production parameters. We determine the crystallinity and the residual monomer content of the samples and their effect on mechanical properties.

Nucleation and Crystallization of PA6 Composites Prepared by T-RTM: Effects of Carbon and Glass Fiber Loading.

Thermoplastic resin transfer molding (T-RTM) is attracting much attention due to the need for recyclable alternatives to thermoset materials. In this work, we have prepared polyamide-6 (PA6) and PA6/fiber composites by T-RTM of caprolactam. Glass and carbon fibers were employed in a fixed amount of 60 and 47 wt.%, respectively. Neat PA6 and PA6 matrices (of PA6-GF and PA6-CF) of approximately 200 kg/mol were obtained with conversion ratios exceeding 95%. Both carbon fibers (CF) and glass fibers (GF) were able to nucleate PA6, with efficiencies of 44% and 26%, respectively. The α crystal polymorph of PA6 was present in all samples. The lamellar spacing, lamellar thickness and crystallinity degree did not show significant variations in the samples with or without fibers as result of the slow cooling process applied during T-RTM. The overall isothermal crystallization rate decreased in the order: PA6-CF > PA6-GF > neat PA6, as a consequence of the different nucleation efficiencies. The overall crystallization kinetics data were successfully described by the Avrami equation. The lamellar stack morphology observed by atomic force microscopy (AFM) is consistent with 2D superstructural aggregates (n = 2) for all samples. Finally, the reinforcement effect of fibers was larger than one order of magnitude in the values of elastic modulus and tensile strength.

A Review of Thermoplastic Resin Transfer Molding: Process Modeling and Simulation.

The production and consumption of polymer composites has grown continuously through recent decades and has topped 10 Mt/year. Until very recently, polymer composites almost exclusively had non-recyclable thermoset matrices. The growing amount of plastic, however, inevitably raises the issue of recycling and reuse. Therefore, recyclability has become of paramount importance in the composites industry. As a result, thermoplastics are coming to the forefront. Despite all their advantages, thermoplastics are difficult to use as the matrix of high-performance composites because their high viscosity complicates the impregnation process. A solution could be reactive thermoplastics, such as PA-6, which is synthesized from the ε-caprolactam (ε-CL) monomer via anionic ring opening polymerization (AROP). One of the fastest techniques to process PA-6 into advanced composites is thermoplastic resin transfer molding (T-RTM). Although nowadays T-RTM is close to commercial application, its optimization and control need further research and development, mainly assisted by modeling. This review summarizes recent progress in the modeling of the different aspects of the AROP of ε-CL. It covers the mathematical modeling of reaction kinetics, pressure-volume-temperature behavior, as well as simulation tools and approaches. Based on the research results so far, this review presents the current trends and could even plot the course for future research.