Currently, the mechanical performance reduction caused by excessive phosphorus content in the halogen-free flame-retardant EP has been an obstacle to its extensive application. This study presents the effective synthesis of a novel flame-retardant BDD with great efficiency, achieving an optimum phosphorus level of merely 0.25 wt %. The structure of BDD was verified by FTIR, 1H NMR, 31P NMR and XPS spectra. To investigate the flame-retardant properties of BDD, several EPs with various phosphorus levels were synthesized. The addition of phosphorus to the EP significantly increases its LOI value from 25.8% to 33.4% at a phosphorus level of 0.25 wt%. Additionally, the resin achieves a V-0 grade in the UL 94 test. The P-HRR and THR of the modified resin measured by the cone calorimeter are also significantly reduced. At the same time, the addition of a modest quantity of BDD has a minimal impact on the mechanical properties of epoxy resin. This study shows that the removal of hydroxyl groups significantly enhances the fire resistance of phosphate-based flame retardants, thereby providing a novel approach to synthesizing efficient flame retardants.
Properties of reinforcement fabrics, such as permeability, are typically characterized in a volume-averaging sense, whereas the fabric microstructure may vary spatially. This makes designing an effective resin infusion strategy for defect-free composite fabrication challenging. Our work presents a concurrent method for simultaneously measuring the local and global in-plane permeability and offers a handy technique for evaluating spatial variability. This experimental setup was similar to that of unidirectional in-plane permeability tests. The fabric, however, should be cut and tested along the angle bisector of warp and weft directions. The evolution of resin flow fronts was analyzed in real-time using in-house code through live video monitoring. The local and global in-plane permeability components were then obtained by applying Darcy's law regionally and globally. The results are in good agreement with those obtained by radial permeability experiments. Statistical analysis of local permeability reveals that the microstructure variability follows a normal distribution. A complete description of fabric microstructure provided by X-ray microcomputed tomography suggests that local permeability and microstructure variation are closely related, confirming the efficacy of the newly proposed method. This work enables the estimation of fabric structure variability and local and global in-plane permeability in a single test without resorting to expensive volume imaging techniques.
In this work, a novel phosphorous-nitrogen based charring agent named poly(1,3-diaminopropane-1,3,5-triazine-o-bicyclic pentaerythritol phosphate) (PDTBP) was synthesized and used to improve the flame retardancy of high-density polyethylene (HDPE) together with ammonium polyphosphate (APP). The results of Fourier transform infrared spectroscopy (FTIR) and 13C solid-state nuclear magnetic resonance (NMR) showed that PDTBP was successfully synthesized. Compared with the traditional intumescent flame retardant (IFR) system contained APP and pentaerythritol (PER), the novel IFR system (APP/PDTBP, weight ratio of 2:1) could significantly promote the flame retardancy, water resistance, and thermal stability of HDPE. The HDPE/APP/PDTBP composites (PE3) could achieve a UL-94 V-0 rating with LOI value of 30.8%, and had a lower migration percentage (2.2%). However, the HDPE/APP/PER composites (PE5) had the highest migration percentage (4.7%), lower LOI value of 23.9%, and could only achieve a UL-94 V-1 rating. Besides, the peak of heat release rate (PHRR), total heat release (THR), and fire hazard value of PE3 were markedly decreased compared to PE5. PE3 had higher tensile strength and flexural strength of 16.27 ± 0.42 MPa and 32.03 ± 0.59 MPa, respectively. Furthermore, the possible flame-retardant mechanism of the APP/PDTBP IFR system indicated that compact and continuous intumescent char layer would be formed during burning, thus inhibiting the degradation of substrate material and improving the thermal stability of HDPE.
Transverse cracking is probably the first and most dominant mode of damage in composite materials. In this paper, transverse cracking of cross-ply [02/90n]s (n = 2,3,4) laminates under uniaxial tension load was studied by means of experimental and numerical methods. In the numerical simulations, a simplified computational strategy only focusing on the damage of the resin was proposed and the mechanical response of the cracking cross-ply laminates was studied by finite element analysis of multi-scale representative volume elements (RVEs). In the RVEs, the longitudinal 0° plies were represented by macro-scale, homogeneous, orthotropic elastic solids while the 90° plies were modeled by the discrete fibers and the surrounding matrix resin in micro-scale. Based on researching the critical longitudinal mechanical strain ε x which initiates the cracks, the in-situ transverse ply strength and the stiffness degradation of the transverse plies, the simplified computational strategy proposed was proven correct. In addition, the crack initiation is sensitive to residual stress. Higher process-induced residual stress levels are dangerous to laminates, leading to early crack initiation.
Predicting and controlling process-induced deformation of composites during cure can play a significant role in ensuring the accuracy of manufacture and assembly of composite structures. In this paper the parametric investigation on the process-induced stress and deformation of variable-stiffness composite cylinders was presented. The Kamal model was used to simulate the cure kinetic for carbon/ epoxy prepreg. A cure hardening instantaneously linear elastic (CHILE) constitutive model was adopted to determine the modulus of matrix resin. Self-consistent micro-mechanical models were employed to represent the mechanical properties and behaviors of the lamina. The three-dimensional model of a variable-stiffness composite cylinder was established using a linear fiber angle variation. The influence of the inner radius, the fiber end angle and the thickness on the stress and deformation of the variable-stiffness cylinder was evaluated using ABAQUS. The results show that the maximum stress increases with increases of the inner radius, the fiber end angle and the thickness. The inner radius of the cylinder have little effect on deformation, the deformation increases as the fiber end angle and the thickness increases. The present model and method can provide a useful tool for prediction of variable-stiffness composite cylinders.
In order to improve the efficiency of intumescent flame retardants (IFRs), a novel macromolecular charring agent named poly(ethanediamine-1,3,5-triazine-p-4-amino-2,2,6,6-tetramethylpiperidine) (PETAT) with gas phase and condense phase synergistic flame-retardant capability was synthesized and subsequently dispersed into polypropylene (PP) in combination with ammonium polyphosphate (APP) via a melt blending method. The chemical structure of PETAT was investigated by Fourier transform infrared spectroscopy (FTIR), and ¹H nuclear magnetic resonance (NMR) spectroscopy. Thermal properties of the PETAT and IFR systems were tested by thermogravimetric-derivative thermogravimetric analysis (TGA-DTG) and thermogravimetry-Fourier transform infrared spectroscopy (TG-FTIR). The mechanical properties, thermal stability, flame-retardant properties, water resistance, and structures of char residue in flame-retardant composites were characterized using tensile and flexural strength property tests, TGA, limiting oxygen index (LOI) values before and after soaking, underwritten laboratory-94 (UL-94) vertical burning test, cone calorimetric test (CCT), scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDXS), and FTIR. The results indicated that PETAT was successfully synthesized, and when the ratio of APP to PETAT was 2:1 with 25 wt % loading, the novel IFR system could reduce the deterioration of tensile strength and enhance the flexural strength of composites. Meanwhile, the flame-retardant composite was able to pass the UL-94 V-0 rating with an LOI value of 30.3%, and the peak of heat release rate (PHRR), total heat release (THR), and material fire hazard values were considerably decreased compared with others. In addition, composites also exhibited excellent water resistance properties compared with traditional IFR composites. SEM-EDXS and FTIR analyses of the char residues, as well as TG-FTIR analyses of IFR were used to investigate the flame-retardant mechanism of the APP/PETAT IFR system. The results indicated that the efficient flame retardancy of PP/IFR composites could be attributed to the synergism of the free radical-quenching and char layer-protecting mechanisms in the gas phase and condense phase, respectively.
