Some studies on glass fiber-reinforced polypropylene. Part I: Reduction in fiber length during processing

The reduction in fiber length during extrusion and injection molding of two commercial glass fiber-reinforced polypropylene products containing 30 percent by weight of glass fibers was studied. The first product had very small fibers of average length around 0.5 mm and also contained a coupling agent. The second product contained relatively longer glass fibers of 9 mm length and no coupling agent. In both cases, fiber attrition occurs predominantly at the solid-melt interface in the meiting zone of the extruder. However, in the short fiber granules, the maximum of the length distribution, which for the initial sample is around 0.5 mm, moved to shorter fiber lengths along the screw channels further from the hopper. In the long fiber granules, a bimodal length distribution was obtained in the intermediate channels; the first maximum was around the original length of 9 mm and the second centered around 0.5 mm. Thus, the forces at the solid-melt interface result in fiber breakage to lengths which are predominantly around 0.5 mm. The fiber attrition was observed to be more severe in injection molding apparently because of higher shear rates and also because the fibers had to pass through narrow channels. The measured distributions of fiber length along the screw channels for the two products are presented, and the possible mechanisms of fiber breakage are discussed. The mechanical properties of samples containing different fiber length distributions and the effects of fiber length and interfacial adhesion on properties are presented and discussed in Part II.     

Fatigue resistance of continuous glass fiber/polypropylene composites: Temperature dependence

The effect of testing temperature on the fatigue resistance of continuous glass fiber/polypropylene (CGF/PP) composites was studied. Fatigue resistance curves (or S-N curves) were obtained at −40°C, 23°C and 50°C. Both on an absolute stress basis and on a normalized stress basis (with respect to the yield stress at the temperature considered), the S-N curves showed that CGF/PP composites had excellent fatigue performance at 23°C and that their performance was actually improved at −40°C (below T_g of the PP matrix). The S-N curves at 50°C showed that, although the composite flexural strength was reduced because of PP matrix softening, their fatigue performance remained relatively high, as it is controlled by the CGF reinforcement. Comparison with a CGF/thermoset isophthalic polyester composite of identical fiber architecture and similar flexural strength at 23°C indicated that the properties of the thermoplastic PP matrix provided improved fatigue resistance, both on an absolute and a normalized basis, especially below the glass transition temperature. It was concluded that the fact that the fatigue performance of the CGF/polyester composite is only weakly temperature-dependent, while that of the CGF/PP composite is strongly temperature-dependent, does not necessarily mean that it shows superior performance. Polym. Compos. 25:622–629, 2004. © 2004 Society of Plastics Engineers.     

New thermosetting resins for high performance composites

Investigations leading to the development of a new family of heat-stable thermosets, the Xylok

1 Registered trademark.

resins, are outlined. These polymers are the condensation products of aralkyl ethers or halides with phenols, and in some instances other classes of aromatic, heterocyclic and organometallic compounds, in the presence of a Friedel-Crafts catalyst. They are fast curing and Xylok composites have been prepared with glass, asbestos and carbon fibre reinforcement, which give excellent high-temperature mechanical strength and strength retention on prolonged exposure up to 250°. A comparative evaluation of the mechanical and electrical properties of a series of glasscloth laminates prepared with various classes of thermosetting resins has shown the Xylok resins to give outstanding overall performance. In addition, the chemical and radiation resistance, and ablative, wear and frictional properties of the Xylok composites suggest that they will find use in chemical plant, aircraft aerospace and bearing applications. Asbestos flour-filled Xylok moulding compounds have been shown to give similar flow and curing characteristics to phenolic based products, but the mouldings are significantly more heat stable.     

Chromatographic studies of some thermosetting resins

The molecular weight distributions of resins produced by reaction of formaldehyde with phenols, melamine, or urea have been studied by gel permeation chromatography.     

热固性树脂补强NBR的性能研究

研究环氧树脂(EP)、酚醛树脂(PF)和不饱和树脂(UP)对NBR胶料性能的影响.结果表明,在无炭黑NBR胶料中,EP的补强效果最佳,UP最差;在白炭黑补强NBR胶料中,PF和UP用量在12～20份之问补强效果较好,胶料的抗撕裂性能提高最明显.SEM显示,复合材料内部形成了局部互穿网络结构,树脂相直径约为200 nm.     

Techniques for compounding glass fiber-reinforced thermoplastics

The processing characteristics of various glass fiberreinforced thermoplastics (FRTP) and the basic approaches for their production are discussed. Experimental work on twostage production-scale continuous kneaders was conducted to define the most important process variables in compounding FRTP materials. Results demonstrate how processing conditions and screw design influence the temperature profile in the kneader and the glass-fiber length in finished products. Feed steek appearance (i.e., pellet shape and size), melt viscosity, and volume percentage of fibers are basic material variables. High quality products can be achieved through a careful, layout of the continuous kneader in order to minimize thermal degradation of the base polymer and to effect adequate dispersion of the glass fibers in the matrix.     

Mechanisms of fracture in filled thermosetting resins

Fracture properties of a wide range of filled unsaturated polyester resin composites have been investigated with respect to filler size, shape, loading and adhesion to the matrix resin. Mechanisms are proposed for the fracture behaviors found, based on geometrical considerations of interacting filler particles and stress concentrations which result from them.     

Amine/epoxy stoichiometric ratio dependence of crosslinked structure and ductility in amine-cured epoxy thermosetting resins

Epoxy-amine thermosetting resins undergo different reactions depending on the amine/epoxy stoichiometric ratio (r). Although many desirable properties can be achieved by varying the stoichiometric ratio, the effects of the variation on the crosslinked structure and mechanical properties and the contribution of these factors to the ductility of materials have not been fully elucidated. This study investigates the brittle-ductile behavior of epoxies with various stoichiometric ratios and performs curing simulations using molecular dynamics (MD) to evaluate the crosslinked structures. The molecular structure is predominantly branched in low-stoichiometric ratio samples, whereas the chain extension type structure dominates the high-stoichiometric ratio samples. As a result, the higher-stoichiometric ratio samples enhances the ductility of materials and the elongation at break increases form 1.4% (r = 0.6) to 11.4% (r = 1.4). Additionally, the tensile strength (105.4 MPa) and strain energy (7.96 J/cm³) are maximum at r = 0.8 and 1.2, respectively. On the other hand, the Young's modulus is negatively impacted and it decreased from 4.2 to 2.7 GPa with increasing stoichiometric ratio.     

Effects of fiber length on the tensile strength of epoxy/glass fiber and polyester/glass fiber composites

In discontinuous fiber-reinforced composites, the shear strength at the fiber–matrix interface plays an important role in determining the reinforcing effect. In this paper, a method was devised to accurately determine this shear strength, taking the strength distribution of glass fiber into consideration. Calculated strength values based on the shear strenght obtained by the method were in better agreement with the experimental observations than those calculated by employing the shear strength obtained on the assumption that the fiber strength was uniform. The tensile strength of composites increases with increasing aspect ratio of the reinforcing fibers. This trend is almost the same regardless of the kind of matrix, the nature of interfacial treatment, and the environmental temperature. When composites are reinforced with random-planar orientation of short glass fibers of 1.5 times the mean critical fiber length, the tensile strength of composite reaches about 90% of the theoretical strength of composites reinforced with continuous glass fiber. Reinforcing with glass fibers 5 times the critical length, the tensile strength reaches about 97% of theoretical. However, from a practical point of view, it is adequate to reinforce with short fibers of 1.5–2.0 times the mean critical fiber lenght.     

双邻苯二甲腈改性环氧及其玻纤复合材料制备

采用双邻苯二甲腈树脂(BAPh)对环氧树脂E-44(EP)进行改性,同时制备了BAPh/EP/玻纤复合材料。采用示差扫描量热仪,热重分析,力学性能测试及氧指数仪研究了改性树脂的热性能、力学性能及阻燃性能,并对BAPh/EP/玻纤复合材料的力学性能进行了表征。结果表明,当BAPh质量分数达到50%时,改性树脂固化物在空气中的起始分解温度达到377.6℃,比纯环氧提高74.3℃,氧指数达到34.5%,复合材料的弯曲性能指标达到最大,添加双邻苯二甲腈后环氧树脂的耐热性、力学性能和阻燃性能得到了明显改善。     

玻璃纤维长度对硅灰-玻璃纤维隔热材料性能的影响

以d50≈200 nm的硅灰为主要原料,掺加20％(w)经过热处理和酸处理的不同长度(分别为3、6、9、12mm)的玻璃纤维,经混练、压制成型、350℃保温2h热处理后,检测烧后硅灰-玻璃纤维试样的体积密度、耐压强度、重烧线变化率、热导率,并分析试样的显微结构.性能检测发现:随着纤维长度的增加,烧后试样的耐压强度和热导率略有增大,体积密度和重烧线变化率几乎保持不变;掺加长度为12 mm的玻璃纤维的试样烧后的体积密度为0.438 g· cm-3,常温耐压强度达到1.74 MPa,在300、500、900℃的热导率分别为0.050、0.061、0.092 W·m-1·K-1.显微结构分析发现:长度为3 mm的玻璃纤维在试样中呈弥散分布;而长度为6、9、12 mm的玻璃纤维在试样中均出现不同程度的团聚,且长度为12 mm的纤维的团聚体内部存在较大的孔隙.     

Biobased thermosetting resins composed of terpene and bismaleimide

Prepolymers prepared by reactions of 1,1′‐(methylenedi‐4,1‐phenylene)bismaleimide (BMI) with myrcene (Myr) and limonene (Lim) in 1,3‐dimethyl‐2‐imidazolidinone (DMI) at 150°C were compressed at 250°C to produce crosslinked Myr/BMI [molar ratio = 2:2–2:5 (MB22–MB25)] and Lim/BMI [molar ratio = 1:1 (LB11)] resins. The ¹H‐NMR analysis of the model reaction products of Lim and Myr with N‐phenyl maleimide (PMI) in DMI at 150°C revealed that a Diels–Alder reaction for Myr/PMI and a vinyl copolymerization for Lim/PMI preferentially proceeded in addition to the occurrence of the ene reaction to some extent. The Fourier transform infrared data of the cured resins were consistent with the results of the model reactions. All of the cured resins, except for MB22, showed tan δ peak values and 10% weight loss temperatures that were higher than 330 and 440°C, respectively. The flexural strength and modulus values of the MBs were higher than those of LB11. Field emission scanning electron microscopy analysis revealed that MB22–MB24 were homogeneous, whereas some combined particles appeared in LB11. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Modeling the chemorheology of thermosetting resins during processing

The curing conditions determine the rheological changes in the resin during the lamination of prepregs into multilayered circuit boards. In order to specify the optimum curing conditions during lamination, it is necessary to understand the rheology of the resin as it cures. In this study, the chemorheological behavior of two commercial epoxy resins and one cyanate-based resin was characterized using an engineering model for the resin viscosity. A linear regression technique was used to evaluate the model parameters from the conditions at the minimum viscosity obtained during resin cures at constant heating rates. The technique was extended to predict the minimum viscosities reached by the resins when subjected to temperature conditions commonly encountered during lamination. The utility of the technique for specifying the curing conditions necessary to have a desired resin flow during lamination and for selecting resin systems for lamination based upon chemorheology has been demonstrated.     

Synthesis and characterization of thermosetting polyacetylene-terminated silicone resins

A novel polyacetylene-terminated silicone (PTS) resins possessing low curing temperature and high heat resistance has been prepared by Grignard reaction using m-diacetylenylbenzene (DEB), 1,3,5-triacetylenylbenzene(TEB), and dichlorosilane as original materials. The reaction of the functional groups was characterized by in situ Fourier transform infrared spectrometer. The experimental results indicated that Si─H and C≡CH bonds are almost exclusively involved in the crosslinking reaction, while ─C≡C─ bonds only partially react. Further, Si─H and C≡CH bonds can participate in the curing reaction at relatively low temperatures, but ─C≡C─ bonds require higher temperature, indicating the higher activity of Si─H and C≡CH bonds than ─C≡C─ bonds. As determined by differential scanning calorimetry, PTS resins have low peak exothermic temperature at 184.5 °C, which is lower than MSP resin (~ 210 °C); in addition, rheological test showed that PTS resins have a very wide processing window from 40 to 163.3 °C, indicating that the PTS resins have excellent processability with a low curing temperature and wide processing window. What is more, TGA results of thermal-cured PTS resins revealed that T_d5 (5% weight loss temperature) of PTS-H10 reached the highest of 684.4 °C. Compared with PTS-H0 resin, there is an increase of 124.2 °C and the remarkably increased heat resistance correlated with a higher m-DEB input ratio. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48783.     

Weibull parameters obtained from dependence of fiber strength on fiber length and area

Weibull strength parameters of ceramic fibers can be inferred from variations in strength with fiber diameter or gauge length. The goal of this article is to provide a critical assessment of the efficacy of these methods. The issues are addressed using theorems in regression analysis and uncertainty propagation as well as Monte Carlo simulations. The results show that, when Weibull moduli are obtained from strength variations with fiber area, inordinately large sample sizes (>1000) are required to achieve reliable results. In contrast, Weibull moduli can be accurately estimated from the dependence of average fiber strength on gauge length for a modest sample size at each of two gauge lengths, provided the gauge length range is sufficiently large. The dependence of strengths of bundles containing many (ca. 500) fibers on gauge length yields yet more reliable results. The results are used to assess the fidelity of Weibull moduli obtained from these methods and provide guidance for preferred test methods.     

Temperature dependence of the zero-shear melt viscosity of oligomeric epoxy resins

The melt viscosities of a homologous series of five epoxy resins based on bisphenol A and epichlorohydrin have been measured over a wide range of temperatures. It is shown that the temperature dependence of the zero-shear viscosity can be well described by the three-parameter Vogel equation. The Vogel parameters B and T_o were found to increase with increasing glass transition temperature, T_g, of the resin, while the ratios $\text{B}\text{T}{}_{\mathrm{<mtext>g</mtext>}}$ and $\text{T}{}_{\mathrm{<mtext>o</mtext>}}\text{T}{}_{\mathrm{<mtext>g</mtext>}}$ remained approximately constant. This constancy of the reduced Vogel parameters implies that T_g can be used as a corresponding states parameter to superimpose the viscosity-temperature data of all five resins onto a single master curve. The existence of such a master curve is of practical use, as it enables melt viscosities of epoxy resins to be predicted over a fairly extensive temperature range from only two quantities, viz. the value of T_g and one single viscosity value at a given temperature.     

Characterization of random glass fiber-reinforced polypropylene for processing

DSC thermal analysis and multi-channel recording have been used to investigate the processing conditions for fiber-reinforced thermoplastic composites. The process combined the film stacking and intermingled fiber techniques using needle-punching to improve the fiber-matrix distribution. The preheating temperature and mold temperature for fiber-reinforced polypropylene composites were in the ranges of 180 200 °C and 60 100 °C, respectively. DSC analysis and X-ray methods showed the presence of an a crystalline form for PP and PP/GF with the cooling rate at 10 °C/min. Increasing the cooling rate to 20 °C/min, they revealed the presence of a mixture of the monoclinic a crystalline form and the hexagonal crystalline form. A multi channel recorder was used to determine the completion of impregnation on multi-layer glass fiber reinforced polypropylene, which could significantly reduce the manufacturing cycle time. The main steps in the processing cycle on the surface of composite or inside the composite were determined. The concept of a processing window with respect to solidification rate and molding pressure is introduced and briefly discussed. The mechanical properties of fiber-reinforced polypropylene composite inside the processing window were better than those outside the processing window and were comparable to GE AZDEL®.