1. Introduction
Nowadays, the commercial applications of carbon fibre-reinforced thermoplastics (CFRTPs) are increasing owing to the advantageous properties of carbon fibres (CFs), such as high strength-to-weight ratio, damping capability and rigidity [
1]. One way to prepare raw composite materials is to employ the extrusion–pultrusion method, which combines the working principle of extrusion and pultrusion to produce CFRTP filament. It provides a uniform filament shape with constant fibre content. The quality of CFRTPs is indicated by the final product’s mechanical properties, which are mainly influenced by the fibre–matrix interactions. This factor can be thermally and mechanically driven by optimising processing parameters and die design. However, both the CF and thermoplastic contribute to weak interfacial bonding. CF has low adsorption and wetting when interfaced with most types of thermoplastics. The surface of CF is nonpolar; therefore, the interfacial shear strength (IFSS) between the fibre and matrix is poor, and consequently the mechanical performance of the composite is not optimal [
2].
Moreover, impregnation exists between thermoplastic matrices and fibre bundles in a composite system because of the high thermoplastic melt viscosity (500–5000 Pa·s) [
3]. Low impregnation quality may deteriorate the mechanical properties of the composite [
4,
5]. To increase the surface energy and roughness, surface treatment is suggested to increase the surface area and contact points, micropores or surface grooves on the CF surface. In general, three methods can be used for fibre surface treatment: plasma, chemical and electrochemical treatments [
5]. Coupling agent (CA) treatment is the most popular chemical method because it provides ease of use on a laboratory scale and increases bonding properties without degrading fibre properties [
5,
6]. Silane CA forms the alkoxysilane group that reacts with the hydroxyl group after hydrolysis. CFs can be modified by surface oxidation as well. Yuan et al. [
7] oxidised the CF surface by heating CF in 40 wt.% H
2SO
4 and 15wt.% KClO
3 at 85 °C for 30, 60, 90 and 120 min. Thereafter, the oxidised fibres were thoroughly rinsed with deionised water and dried at 50 °C. The results indicated that CF surface treatment by oxidation and (γ-aminopropyl) triethoxysilane (APTS) improved the surface chemical activity and surface roughness and increased the surface area of the fibre. Wen et al. [
8] applied a two-step fibre treatment—electrochemical oxidation followed by a silane CA. After oxidation, CFs were immersed in a silane solution made by mixing 5% KH550 CA with a mixture of 5% distilled water and 90% ethanol; before immersing CFs, the solution was mechanically stirred for 1 h. Furthermore, the fibre drying process was performed in an oven at 100 °C. The application of KH550 CA to the fibre surface yields a remarkable improvement in fibre surface energy and the wetting effect between the CFs and polymer matrices. The tensile strength of the treated fibres also significantly increased. In addition to CAs, some researchers used liquid nitrogen for fibre treatments. The effects of liquid nitrogen treatment on the interfacial bonding of carbon fibre-reinforced polypropylene (CFRP) and mechanical properties of CF were investigated by Kim et al. [
9]. The composite had a tensile strength value of 70 MPa, Interlaminar Shear Strength (ILSS) of 9.5 MPa and impact strength of 7.8 kJ/m
2.
As mentioned above, the impregnation quality is one of the main issues in CFRTP production [
10]. By covering all individual filaments of the fibre with a matrix, high-performance composite characteristics can be achieved. In the extrusion–pultrusion system, the wetting of fibre can be improved by pin-assisted die design and fibre movement mechanism in the plastic melt that accommodates sufficient melt impregnation. In a pin-assisted melt impregnation die, the impregnation quality is closely related to the following parameters; melting temperature of the plastic, pressure, pin number, pin dimension, pin layout, fibre tension and fibre pulling speed [
11]. During impregnation, fibre bundles must be stretched out sideways so that each strand moves aligned, does not overlap one another and can be evenly wetted by the matrix. Fibre stretching can be mechanically performed by passing the fibre through several spreader pins attached to the die; the pins that are not aligned make the fibre bundle widely spread as it passes through the pins. The pin cross-curve radius and the height difference between the pins affect the stretching of fibres that pass through it [
12]. In the case of a viscous plastic material, such as polypropylene (PP), the penetration of the resin into the fibre is more difficult. According to Gayman et al. [
13], the impregnation rate was reduced by increasing the pin diameter. Fibre tension on the pins changes with pulling speed, and by increasing the fibre tension, the permeability of the fibre can be decreased. Kabeel et al. [
14] studied the melt impregnation of continuous CFR-PA 66. They developed an impregnation system with a series of parallel pins; the fibre passed along a set of parallel pins, and the impregnation took place in the contact area. The exit die could be used to control the fibre content. Marissen et al. [
15] developed melt impregnation technology by passing the glass fibre bundle on five conical spreading pins in the polypropylene matrix. Nygard and Gustafson [
16] compared the efficiency of different melt impregnation methods—pin-assisted methods, a crosshead impregnation die, use of a slit die and different vibration methods. The radial slot impregnation method afforded the best overall impregnation efficiency; a high degree of impregnation could be held at the haul off maximum speed of 10 m/min. The quality of impregnation depends on the contact time between the fibre bundle and the impregnation bar. A higher speed generates a higher pulling force that can increase values above the maximum fibre bundle strength. In addition, it decreases the contact time, consequently reducing the quality of impregnation. These methods can improve impregnation quality; however, this technology is complex for application in mass production and retains the plastic melt in the container. The proposed method considers only impregnation without observing other quality indicators, such as fibre–matrix interactions.
Moreover, the filament composite manufacturing process involves a combination of many parameters and is not influenced by the factors mentioned earlier. The selection process of a proper combination of parameters is crucial as it highly influences the product quality. Nonetheless, to obtain the optimum process parameters for composite products, one must often rely on time-consuming trial-and-error methods. The optimal process parameters can be determined by response surface methodology (RSM), which is efficient and convenient for experimental design. RSM involves statistical and mathematical methods that are useful for analysing and modelling problems wherein a target response affected by several variables is to be optimised. These designs can fit a second-order prediction equation for the response. Parametric optimisation research using the Taguchi design of experiment was conducted by Xian et al. [
11]; the optimised parameters were melt temperature, roving pretension, pulling speed and the number of impregnation pins, while the target response was the degree of impregnation. The results showed that the pulling speed has the most powerful influence on the degree of impregnation, followed by the melt temperature and the number of pins. Ren et al. [
17] analysed the effect of pulling speed and the number of pins on the fibre fracture in thermoplastic-based composite melt impregnation. They applied RSM to obtain the optimal parameters and compared it with a mathematical model. They found that the number of pins yielded the most significant factor in the fibre fracture. High-quality impregnation can be achieved using low pulling speed as a relatively high melt temperature negatively impacts impregnation quality. Chen et al. [
18] used the RSM, Taguchi method and hybrid genetic algorithms–particle swarm optimization (GA-PSO) to identify the combination of the optimal process variables of the injection moulding machine (melt temperature, packing pressure, injection velocity, cooling time and packing time) to obtain minimum shrinkage and warpage. This study enhances the stability of the injection moulding process by reducing injection costs and the time required for the trial. Fu et al. [
19] performed RSM and analysis of variance (ANOVA) to analyse the effects of melt temperature, screw speed and the recycled component on the melt pressure, mass output, screw torque and temperature increase at the die in a PP blend system. The study presented quantitative data for single-screw extrusion and showed the importance of a design of experiment (DoE) method to predict the variety of potential processing conditions for production operations.
In this study, CFRP composite filaments were manufactured via the extrusion–pultrusion method. This study aims to obtain a composite filament with consistent high impregnation quality. The impregnation quality was quantified using stress-based approaches by measuring IFSS. Processing variables affecting the process, such as melt temperature, pulling speed, number of spreader pins and fibre treatment, were optimised using Box–Behnken RSM. IFSS tests and microscopic analyses were performed to determine the impregnation quality of the filaments.