Instrumented thermoforming of advanced thermoplastic composites. II: Dynamics of double curvature part formation and structure development from PEEK/carbon fiber prepreg tapes

Poly(ether ether ketone) (PEEK) carbon fiber prepreg tapes (APC-2) have been thermoformed into a hemispherical double curvature part under a variety of processing conditions. Conventional matched die molding using aluminum molds (at 200°C) were not successful in thermoforming acceptable parts. Parts with severe wrinkling and folding were obtained. A novel three-piece (steel) mold with built-in sheet clamping arrangement was, therefore, designed and fabricated. This mold was used at 400°C temperature to thermoform parts from preheated preconsolidated laminates. More interestingly, using the above conditions, 8- and 16-ply unconsolidated laminates could be directly thermoformed into parts that were microstructurally sound and exhibited good shape conformity. Results suggest a cycle time of 15 min, with scope for further reduction, if mold cooling is employed. Notwithstanding the simplicity of the thermoforming process, such a short cycle time compares quite favorably with cycle times of several hours for conventional thermosetting resin based composites.     

Thermoforming of advanced thermoplastic composites. I: Single curvature parts

Thermoforming has been studied for a single curvature part made from various advanced thermoplastic matrix composite prepregs. For parts with acceptable shape conformity, preheating of the composite laminates to a processing temperature of 350 to 400°C is necessary prior to forming with molds maintained at 200°C. However, only PEEK/carbon fiber prepreg tapes yielded parts with acceptable microstructural integrity and a matrix crystallinity level of about 30 percent. Amorphous matrix based PXM 8505/T500 fabric prepregs also result in lamination and void free parts, but fiber matrix distribution in this case was rather poor. Parts thermoformed from other prepreg laminates contained voids and/or were delaminated, thereby indicating the need for higher mold temperature and forming pressure than that afforded by the present study, in which a standard lab-scale thermoforming machine was used.     

Mechanical performance and moisture absorption of various natural fiber reinforced thermoplastic composites

Natural fibers are seeing increased use in composite applications due to their reduced cost, low density, and environmental benefits (more sustainable and lower carbon footprint). Although many natural fiber systems have been examined over the last decade, there have been relatively few studies which have compared a variety of fiber types and processing methods directly in the same experimental set. In this study, natural fiber composites made from low density polyethylene (LDPE) and a variety of Canadian based fiber feedstocks were examined including hemp bast, flax bast, chemically pulped wood, wood chips, wheat straw, and mechanically pulped triticale. The effect of fiber type, fiber fraction and maleic anhydride polyethylene (MAPE) coupling agent on the mechanical properties and long‐term moisture absorption behavior was quantified. In general, addition of natural fiber to LDPE results in an increase in modulus (stiffness) with a corresponding loss of material elongation and impact toughness. Of the fiber types tested, composites made from chemically pulped wood had the best mechanical properties and the least moisture absorption. However, the use of MAPE coupling agent was found to significantly increase the mechanical performance and reduce moisture absorption for all other natural fiber types. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 969‐980, 2013     

Issues in diaphragm forming of continuous fiber reinforced thermoplastic composites

A literature survey is presented on sheet-forming methods and mechanisms for continuous fiber reinforced thermoplastics. The diaphragm forming process is shown to be one of the more promising fabrication routes for complex-curvature structures. The primary deformation mechanisms involved in the sheet-forming processes are identified and discussed. Earlier approaches to develop mathematical models either have been kinematically based or have treated only one of the primary deformation mechanisms. A promising constitutive model for the highly anisotropic behavior of the composite at forming temperature is examined. The composite sheet is assumed to behave as a transversely isotropic Newtonian fluid that is both incompressible and inextensible in the fiber direction. The second section of the paper treats the experimental development of the polymeric diaphragm forming process for thermoplastic composites. The viscoelastic properties of the diaphragm material are characterized by dynamic mechanical analysis. The rate sensitivity of the phenomenon of shear-buckling during forming of certain cross-ply and quasi-isotropic composite laminates is investigated, using a shallow female mold. Finally, the interface condition between the diaphragm and the composite during forming is examined.     

Some issues on impregnation in manufacturing of thermoplastic composites by using a double belt press

The manufacturing of thermoplastic composite intermediates by a continuously running double belt press (System of Held Comp., Germany) has become one of the most effective techniques for high quantity production. The process of combining thermoplastic materials and reinforcing fabrics during the manufacturing results in impregnation phenomena of the reinforcing layers distinct from one in resin transfer molding (RTM). Here, the work is focused on the clarification of the impregnation process that occurred in such a continuous manufacturing process. A composite intermediate of 50 wt% fibers consisting of E-glass fabrics and nylon 66 films (Zytel, DuPont) was produced at different processing conditions to exhibit the influence of the degree of impregnation on mechanical properties and damage patterns of thermoplastic composites. It can be proved that because of strong inhomogeneity in the fabric concerning the permeability of the yarns and the weaving structure, respectively, the time required to impregnate the fabrics is governed by transversal micro-flow into the fiber bundles rather than macro-infiltration of the polymer into the fabric structure. Imperfect impregnation resulted in specific damage pattern in the center of the compressed yarns after flexural loading. The results are to be applied to guide the optimization of the manufacturing process with respect to material selection and preselection of processing conditions.     

Use of wood fibers in thermoplastic composites II: Polyethylene

Wood fibers of aspen in the form of chemithermomechanical pulp (CTMP) has been used as reinforcement in polyethylene (PE). The secant modulus, tensile strength, energy, and elongation at yield were measured. It was found that the mechanical properties of the composite were higher than those of PE by a factor of 2.6 for modulus, 2.3 for stress, and 2.1 for energy at yield. Compared to glass fiber composites, the CTMP composites showed higher elongation, about 100 percent higher energy, 106 percent higher stress, and 75 percent higher modulus. Note that the cost of treated wood fibers is several times lower than that of treated glass fibers.     

Use of grafted aspen fibers in thermoplastic composites: IV. Effect of extreme conditions on mechanical properties of polyethylene composites

Hardwood fibers of aspen in the form of chemithermo-mechanical pulp (CTMP) have been used as reinforcement in linear low density polyethylene (LLDPE). The effect of composite treatment (immersion in boiling water, heat exposure at 105°C for seven days or at a temperature of −40°C) on resulting mechanical properties were evaluated. The grafted aspen CTMP composites showed by far the best results with regard to secant modulus, tensile strength, energy, and strain when compared to those of wood flour, mica or glass–fiber filled LLDPE, as well as to virgin LLDPE. Finally, the dimensional stability of CTMP aspen-filled LLDPE composites immersed for four hours in boiling water was better than that of mica or glass–fiber filled LLDPE.     

Random glass mat reinforced thermoplastic composites. Part I: Phenomenology of tensile modulus variations

The mechanical properties of random continuous glass mat reinforced composites, as determined by standard tensile tests, are known to have a very large scatter. To understand this scatter, new test procedures were developed to map the local tensile elastic moduli in a large plaque at 12.7-mm (½-in) intervals. Surprisingly, the tensile modulus in these materials can vary by a factor of two over the 12.7-mm distance. The elastic modulus is shown to vary by a factor of three in a 150 × 305-mm (6 × 12 in) plaque. Expressions have been obtained for the average moduli measured by tensile and bend tests. These expressions have been used to compare measured flexural moduli with values predicted by using measured tensile moduli.     

Highly filled thermoplastic composites. II: Effects of particle size distribution on some properties

The effect of irregularly shaped glass particle size and size distribution on the packing density and flexural mechanical properties of highly-filled composites with a rubbery thermoplastic matrix was studied. Increasing the particle's median size and size distribution width significantly increases the packing density of the composites. Compression molding causes the glass particles to fracture at a decreasing level with an increasing distribution width. Particle median size, rather than size distribution, affects the mechanical properties; The flexural modulus and strength increase and the ultimate deflection in flexure decreases with a decreasing median size. A “glass network” is formed in the compression molded composites because of the mechanical interlocking of particles. The nature of this continuous glass phase predominates the composites mechanical behavior. The particle's size and shape determine the nature of the glass network and, thus, have a dominating effect on the mechanical properties. The latter are significantly affected by the particle's surface properties. A specific silane treatment of the glass particles acts to reduce the particle/particle friction, resulting in a higher packing density. The treatment also acts as a cohesive liquid to increase the strength of the glass network, and to increase the particle/polymer adhesion, increasing the composites' strength and ductility.     

Use of wood fibers in thermoplastic composites: VI. Isocyanate as a bonding agent for polyethylene–wood fiber composites

Linear low density (LLDPE) and high density (HDPE) polyethylenes were reinforced with wood fibers of aspen chemithermomechanical (CTMP) pulp. The different isocyantes: (i) polymethylene (polyphenyl isocyanate), (ii) tolene –2–4-diisocyanate, (iii) 1–6 hexamethylene-diisocyanate, and (iv) ethyl isocyanate used as bonding agents improved the tensile properties of the composites. HDPE performed better in comparison with LLDPE composites. Also, shorter fibers (mesh size 60) produced higher tensile strength and modulus in HDPE. The comparison of HDPE reinforced with aspen, mica, and glass fibers showed the effectiveness of wood fibers in terms of their cost and performance.     

Modeling of heat transfer and crystallization kinetics in thermoplastic composites manufacturing: Pultrusion

Whereas pultrusion with thermoset resins has been widely analyzed, there is a scarcity of knowledge about pultrusion with thermoplastic resins. The aims of this work were to strive towards deeper knowledge of temperature distribution and degree of crystallinity in the composite during processing, to develop a tool for process simulations with a variety of processing parameters, and to provide input data to models for pressure and matrix flow. The heat transfer model presented herein describes the temperature distribution within the composite throughout the thermoplastic pultrusion process. The transient heat transfer situation is modeled one-dimensionally through a transverse cross section far from the edges of a high aspect ratio composite. Temperature-dependent thermal properties, partly non-infinite contact conductance, and heat contribution from crystallization were taken into consideration. The degree of crystallinity within the composite was determined as well. The analysis also includes an experimental verification of the heat transfer model. Results show good agreement with experimental data.     

Anti-adhesion performance of various nitride and DLC films against high strength steel in metal forming operation

High strength steel (HSS) is widely used for automobile reinforcement parts and the quantity required is rapidly grown. However, the strength and hardness of the steel are relatively high, its formability is very low and adhesion to tool material can be easily found under forming operation. This paper aimed to evaluate the anti-adhesion performance of commercial nitride and DLC films coated on cold work tool steel against HSS in forming operation. The friction coefficient and wear rate of the non-coated ball (SKD11; hardness 60 ± 2 HRC), balls coated with TiN-PVD, TiCN-PVD, AlTiN-PVD, Nitride + CrN and DLC have been evaluated in sliding contact against SPFH 590 (JIS) disk. The scratch and nano-indentation tests were done on each type of coated tools to characterize the adhesive strength between the film and the substrate, and the hardness and the elastic modulus, respectively. The anti-adhesion performance of various films coated tool in metal stamping process was also investigated by performing U-bending experiment. The cold roll carbon steel; SPCC (JIS) was also used to compare a material transfer problem to the case of using HSS (JIS: SPFH590). As the results, for HSS sheet, the adhesion of workpiece material on a non-coated die surface was detected after 49 strokes whereas adhesion could not be found in case of stamping SPCC sheet up to 500 strokes. The TiCN, AlTiN, and Nitride + CrN films showed good anti-adhesion performance when forming HSS, while the TiN and DLC films did not provide the satisfied results.     

Random glass mat reinforced thermoplastic composites. Part V: Statistical characterization of the tensile modulus

Random glass mat thermoplastic composites (GMT), which can be thermostamped to form complex deep-drawn parts with ribs and boxes, are complex material systems in which the local elastic modulus and local strength vary widely and randomly across the material (the tensile modulus can vary by a factor of two over a 12.7-mm length scale). And the values of these local properties depend on the length scale of measurement. The random, large-scale point-to-point variations in their properties cannot be described by a single number. The broad distribution of elastic moduli in GMT has been modeled by a four-parameter probability density function. Moments of this distribution function provide numerical measures that can be used for comparing data sets representing properties of different material samples. This statistical characterization is used to establish the consistency and the random nature of previously obtained elastic moduli data sets. The framework is also used to predict the effect of the gage length used to measure the local elastic modulus on the shape of the modulus probability density function.     

Interfacial properties in commingled yarn thermoplastic composites. Part I: Characterization of the fiber/matrix adhesion

The paper aims to assess the fiber/matrix interface and adhesion quality in commingled GF/PP composites by means of complementary experimental methods. For this purpose, different interfacial qualities were obtained by a modification of the sizing of the fiber reinforcement (polypropylene specific sizing, non-specific sizing and no sizing), and of the matrix (with or without coupling agent). Transverse tensile stress-strain curves have been recorded while monitoring acoustic emissions. An analysis of acoustic emission data associated with fracture surface examinations has helped explain the differences observed in mechanical properties and damage mechanisms, emphasizing the importance of the interphase in the performance of these new composites. Thus it has been shown that the association of three experimental investigation methods (transverse tension, acoustic emission, and fracture surface analysis) makes it possible to characterize both the glass/silane bond (so-called fiber/matrix interface) and the global fiber/matrix adhesion (addition of several different zones and interfaces). Polym. Compos. 25:577–588, 2004. © 2004 Society of Plastics Engineers.     

Layered particle-based polymer composites for coatings: Part I. Evaluation of layered double hydroxides

Layered double hydroxides (LDH) suitable as fillers for the formulation of waterborne polyurethane (WPU) nanocomposites in coating applications are designed and characterized. Their elaboration follows a simple and reproducible process leading to samples without impurity. The attention is paid to the impact of the LDH nature (M_xAl/CO₃^2?, M = Mg and/or Zn, and x = 2, 3 and 4) on the structure characteristics, i.e. cell parameters and coherent domain dimensions. Focusing on two end-member phases M₂Al/CO₃^2?, M = Mg or Zn, the microstructural characterization performed from X-ray diffraction peak profile analyses permits to point out larger coherent domain sizes for Zn₂Al species than for Mg₂Al ones, and then to correlate with the “macroscopic” crystallinity of the samples. The evolution of LDH slurries over time is tentatively considered in a prediction interest. The stability of a chosen organic–inorganic hybrid, taken Mg₂Al as inorganic host structure with anions of the 4-aminobenzene sulfonic acid (4-ABSA), is studied as function of its carbonate contamination in time. Finally, the dispersion of LDH fillers in WPU is scrutinized in terms of WPU/LDH structure revealed by indirect and direct observations, XRD and TEM, respectively.     

Compaction of textile reinforcements for composites manufacturing. III: Reorganization of the fiber network

The objectives of this series of papers are to describe the mechanical behavior of textile reinforcements under normal load and to quantify the effects of diverse processing parameters on that behavior. In the first and second papers of the series, experimental compaction and relaxation results were reported; general trends were identified and the effects of changes in the processing parameters were analyzed. In this paper, the results of sequences of successive compaction cycles applied to dry textiles and to textiles saturated in distilled H₂O and silicone oil are presented. The reinforcements investigated are produced by assembling tows or rovings following different patterns; it is shown that the resulting heterogeneity, or regular variation of the local fiber volume fraction, can be associated to some particular elements of the mechanical behavior of the reinforcements. The reorganization of the fiber network and the effect of friction at the fiber contacts are demonstrated. Different stages in the reorganization process are identified; each stage is controlled by different parameters and corresponds to a precise behavior. Successive compaction cycles applied to a preform can reduce the void content of the final part.     

High performance thermoplastic composites: Study on the mechanical,thermal, and electrical resistivity properties of carbon fiber‐reinforced polyetheretherketone and polyethersulphone

High temperature processing thermoplastic polymers, polyetheretherketone (PEEK) and polyethersulphone (PES), were melt blended with carbon fibers (CFs) to make composites. These composites were investigated for their mechanical, thermal, and electrical properties. Mechanical properties that are expressed in terms of storage modulus, loss, and damping were enhanced with the addition of CFs. Thermal properties were determined by DSC and TGA. These methods help to understand the effects of fiber content and fiber–matrix adhesion in the composites. Composites were also tested for their electrical and thermal conductivity because CFs leave the composites thermally and electrically conductive. CFs enhanced the crystallinity of the PEEK appreciably that in turn influenced thermal conductivity, electrical resistivity, and the stiffness of PEEK/CF (composites of PEEK with CFs). PES/CF (composites of PES with CF) shows a different behavior due to the amorphous nature of PES. The work involves one filler and two different matrices, and so it provides an interesting comparison of how matrix morphology can influence the properties of composites. POLYM. COMPOS. 28:785–796, 2007. © 2007 Society of Plastics Engineers.     

Polypropylene composites. III: Chemical modification of the interphase and its influence on the properties of PP/mica composites

A surface treatment technology was developed for PP/mica composites that produces a diffuse interlayer with excellent adhesion between the components. The interlayer is created by the silane treatment of the filler and the chemical modification of the polymer components, and its polarity gradually decreases from the surface of the filler to the matrix. Properties of the composites depend on the characteristics of the interphase. With changing chemical composition, the characteristics of the interphase change from a thin, rigid layer to a more diffuse, elastic one. Properties of the composites change accordingly, optimum properties are achieved with a thick interlayer ensuring good stress transfer, strength, hardness, acceptable impact properties, and low mold shrinkage.     

Study on superabsorbent composites. IX: Synthesis,characterization and swelling behaviors of polyacrylamide/clay composites based on various clays

A series of clay-based superabsorbent composite from acrylamide (AM) and various clays, such as attapulgite, kaolinite, mica, vermiculate and Na⁺-montmorillonite, was prepared by free-radical aqueous polymerization, using N,N′-methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator, and then saponified with sodium hydroxide solution. In this paper, the reaction mechanism and thermal stability of the superabsorbent composites incorporated with various clays were characterized by FTIR, XRD and TGA, respectively. The effects of clay kind and clay content on equilibrium water absorbency of these composites were also investigated and compared. In addition, the influences of clay kind on comprehensive swelling behaviors of the PAM/clay superabsorbent composites were studied. The results indicated that the introduced clays could influence physicochemical properties of obtained superabsorbent composites. Mica could improve thermal stability of corresponding superabsorbent composites to the highest degree comparing with the other clays. The PAM/clay superabsorbent composites incorporated with 10 wt% clay of various kinds were all endowed with equilibrium water absorbency of more than 1300 g g⁻¹. The equilibrium water absorbency decreases with increasing clay content and correlates with the kind of clay. Attapulgite-based superabsorbent composite was endowed with higher water absorbency in univalent cationic saline solution, however, the vermiculite- and the kaolinite-based ones acquired the highest water absorbency in CaCl₂ and FeCl₃ aqueous solution, respectively. Moreover, the superabsorbent composites incorporated with Na⁺-montmorillonite have higher swelling rate and that of doped with mica was endowed with higher reswelling capability.