Simulation of polymer melt processing

Polymer melt processing requires an integration of fluid mechanics and heat transfer, with unique issues regarding boundary conditions, phase change, stability and sensitivity, and melt rheology. Simulation has been useful in industrial melt processing applications. This brief overview is a personal perspective on some of the issues that arise and how they have been addressed. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Analytical study on the interface of polymer blends from advanced COPNA-resin and nylon 6

In the previous work, we introduced new polymer blends from the advanced COPNA-resin and nylon 6.¹ The morphology of the polymer blends were quite different between the B-staged state and the fully cured state. In order to investigate a phenomenon occurred in the curing process, ¹³C Fourier transform-nuclear magnetic resonance (FT-NMR) spectral analysis, ¹⁵N FT-NMR spectral analysis, and Fourier transform infrared absorptional spectral analysis were carried out on the blends in a solid state. From the spectral analyses, it was revealed that a graft reaction occurred at the interface between the advanced COPNA-resin and the nylon 6. The difference of the morphology on the fully cured polymer blends was due to the following reason. In the curing process, generated benzyl-type cations of the B-staged Advanced COPNA-Resin initially attacked and combined with nitrogen in the amino groups of the nylon 6. In the late stage of the curing process, the cations mainly attacked and combined with π electrons of the condensed aromatics. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 549–557, 1997     

Mechanical and structural properties of melt spun polypropylene/nylon 6 alloy filaments

Investigated in the present study are the physical properties, morphology, and structure of PP/N6 alloy filaments (10, 20 wt % N6) made with or without PP‐g‐MAH as compatibilizer. The alloy filaments produced at the take‐up speeds of 300 and 800 m/min were drawn with draw ratio of 3.5 and 2, respectively. Stress–strain curves of PP and alloy filaments show ductile and brittle behavior, respectively. It is suggested that the brittle behavior of alloy filaments is due to the presence of microvoids or micropores at the interface of PP and N6; these lead to stress concentration and thus to a decrease in tenacity, modulus, and elongation at break. Effects of the blending of N6 with PP on birefringence and crystalline and amorphous orientation factors of the composite filaments are studied. The amorphous orientation factor, f_am, of PP was found to increase with an increase in the amount of N6. The alloy filaments behaved like isostrain materials and most of the force in spinning and drawing was born by the PP phase. The presence of N6 fibrils helped to orient PP chain molecules in amorphous regions. However, the crystalline factor, f_c, of PP decreased with the increase in nylon fraction. This means the presence of the crystals of N6 caused a decrease in the orientation of the PP crystals. LSCM micrographs of the filament showed the presence of matrix–fibril morphology with the N6 fibrils oriented along the axis. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 532–544, 2005     

Conducting polymer composites of zinc‐filled nylon 6

The present work is concerned with the effect of processing variables and filler concentration on the electrical conductivity, hardness, and density of composite materials prepared by compression molding of a mixture of zinc powder and nylon 6 powder. The electrical conductivity of the composites is <10^?12 S/cm, unless the metal content reaches the percolation threshold at a volume fraction of about 0.18, beyond which the conductivity increases markedly by as much as 10 orders of magnitude. The density of the composites was measured and compared with values calculated by assuming different void levels within the samples. Furthermore, it is shown that the hardness increases with the increase of metal concentration, but for values of filler volume fraction higher than about 0.30 the hardness of samples remains almost constant. Two parameters of molding process, temperature and time, were shown to have a notable effect on the conductivity of composites, whereas pressure has no influence on this property in the pressure range considered. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1449–1454, 2001     

硅灰石粉体对增强尼龙6的影响研究

试验以典型的江西新余硅灰石为原料,进行了硅灰石超细粉碎与表面改性深加工粉体制备,研究了硅灰石粉体复配玻璃纤维对增强尼龙6的影响。     

Changes in orientation caused by UV irradiation of nylon 6 fibers

The effect of UV radiation on the structural parameters that relate to the optical properties of nylon 6 fibers are investigated using interferometry. When the optical parameters are known, we can use them to calculate various orientation functions given by Hermans and de Vries. The properties of concern are the surface reflectivity, transparency, stress optical coefficient, stress due to UV irradiation, optical configuration parameter, segment anisotropy, dielectric constant, and susceptibility. The number of molecules per unit volume, isotropic refractive index, polarizability of a monomer unit, specific refractivity of the dielectric (along and across the fiber axis) and the form birefringence were obtained. The results are established by relationships designed to relate the calculated structural parameters to the time of exposure. The study demonstrates how the structural parameters change during exposure to UV radiation. Illustrations are given using graphs and microinterferograms. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3202–3211, 2003     

Phase behavior and reaction of nylon 6/6 in water at high temperatures and pressures

The phase behavior and reaction of nylon 6/6 in water were studied with a diamond anvil cell (DAC) technique and visual microscopy. Nylon 6/6 concentrations in water and cell temperatures were varied from 11 to 46% and from 264 to 425°C, respectively. The pressures studied ranged from 30 to 900 MPa. When an aqueous solution of 27% nylon 6/6 was rapidly heated (2.6°C/s) to 372°C at 30 MPa, the solution became homogeneous at 331°C. Upon cooling, the final pressure was 30 MPa and both particles and gas were observed. Analysis of the particles by Raman indicated decomposed nylon 6/6 solid. When an aqueous solution of 31% nylon 6/6 was rapidly heated (2.9°C/s) to 425°C at 58 MPa, the solution became homogeneous at 323°C. Upon cooling, the final pressure was 143 MPa, and, remarkably, only a second liquid precipitated and no gas or solids were observed. From the experiments, we concluded that the reaction pathways are completely different between the subcritical and supercritical water conditions. For the case of subcritical conditions, the final products were solid particles having a nylon character along with a considerable amount of gas. At supercritical water conditions, the final products were liquids having little nylon character and no gas. Experiments were performed at a constant temperature of 272°C at initial pressures ranging from 87 to 400 MPa. As the reaction proceeded, the pressure was measured at 30‐s intervals. At average pressures less than 300 MPa, the nylon 6/6 samples melted and appeared to become homogeneous. At average pressures higher than 520 MPa, the nylon 6/6 samples remained heterogeneous. From these results, the rate of hydrolysis was concluded to increase with pressure. The reaction volume was found to be −21.1 cm³/mol, which can be explained by the overall formation of water‐soluble products. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1062–1073, 2000     

尼龙6固相缩聚——实验数据与模型数据的比较

研究了不同起始相对分子质量、不同含水量的圆球状尼龙6切片在不同温度和反应时间下的连续固相缩聚行为.结果说明了起始相对分子质量和温度对尼龙6的固相增黏效果影响很大,和模型得出的结论一致;而不同含水量和反应时间同样也会影响尼龙6切片的固相增黏效果.此外,结果还发现在实际生产中,切片的起始氧化温度远远低于模型推断出的起始氧化温度.实验结果为今后的模型设计和改进提供了极有参考意义的数据,同时也为固相缩聚提出了新的研究方向.     

Amine-terminated nylon 6/66/1010 (AM-6/66/1010) used for hot melt adhesives: synthesis and properties

A new amine-terminated nylon 6/66/1010 (AM-6/66/1010) copolyamide hot melt adhesive with the molecular weight of 21,000–96,000 Da was synthesized and blocked with 1-hexadecylamine. The AM-6/66/1010 samples were characterized by ¹H-NMR spectroscopy, differential scanning calorimetry (DSC), thermal gravimetric analysis, and gel permeation chromatography. The ¹H-NMR spectroscopy demonstrated that 1-hexadecylamine functions as blocking agent in this polymerization. The DSC thermograms showed that the extra peak (peak (II)) and the melting peak (peak (I)) of AM-6/66/1010 are moving left and the glass transition temperature of AM-6/66/1010 decreases as the mole ratio α_H/C (1-hexadecylamine/total carboxyl) increases. The thermal gravimetric analysis indicated that AM-6/66/1010 hot melt adhesive has a high thermal stability. The peel strength of the test specimen obtained by hot melt glutinous lining of AM-6/66/1010 or AC-6/66/1010 and fabric 6535 (65% PET, 35% cotton) was studied using T-peel tests, and the results showed that the washable and dry-cleaning resistant of AM-6/66/1010 copolyamide hot melt adhesive is better than that of carboxyl-terminated nylon 6/66/1010 (AC-6/66/1010) copolyamide hot melt adhesive.     

Silver sulfide as a staining agent for scanning electron microscopy of nylon 6/MXD6 blends

BACKGROUND: In transmission and scanning electron microscopy imaging, the ability to obtain sufficient contrast between the components of a blend when they are both of a similar chemical structure still remains problematic. This paper investigates the domain morphology of a polymer blend containing two polyamides, nylon 6 and the semi‐aromatic polyamide poly(m‐xylene adipamide) (MXD6), using scanning electron microscopy in backscattered electron imaging mode. The efficiency of three staining agents, ruthenium tetroxide, phosphotungstic acid and silver sulfide, in obtaining optimum phase contrast between the two polymers is discussed. RESULTS: The use of silver sulfide as a staining agent was found to be a fast and reliable approach which required basic sample preparation and provided excellent compositional contrast between the phases present in the nylon 6/MXD6 blends compared to the other staining agents. CONCLUSIONS: The technique described in this paper is believed to be a novel and versatile method that has the potential to further improve the ability to study complex polymer blends where one polymer contains an aromatic ring. Copyright © 2009 Society of Chemical Industry     

High‐flow nylon 6 by in situ polymerization: Synthesis and characterization

A new synthetic strategy for high‐flow nylon 6 was developed in this article. Generation 1, 2, 3 (G1, G2, G3) polyamidoamine (PAMAM) dendrimers reacted with p‐phthalic acid by equimolar terminal groups in water solution, respectively, and mother salt solution was then prepared. The high‐flow nylon 6 was prepared with suitable quantity of mother salt solution, end‐capping agent, and ?‐caprolactam by in situ polymerization. Blue shifts are found for the peaks of NH (γN? H and 2δN? H) of the high‐flow nylon 6 compared with pure nylon 6 in the IR spectra. Comparing with the pure nylon 6, the high‐flow nylon 6 containing low content of PAMAM units, has high‐flow property and almost the same mechanical property. The high‐flow nylon 6 with low content of PAMAM units has greater melt‐flow index (MFI) (the value of MFI increased by 70–90%). Hardly any decrease in the tensile strength is observed with the elongation at break decreasing by 20–35%. But the izod impact strength of the high‐flow nylon 6 increases. The SEM images show that the high‐flow nylon 6 presents brittle fracture with conglomeration‐like structure, while pure nylon 6 exhibits plastic fracture with island‐like structure. DSC thermograms of nonisothermal crystallization exhibit that the peak of high‐flow nylon 6 broadens compared with pure nylon 6, and the broader peak means the wider processing temperature. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

尼龙6改性研究

采用经化学改性的芳纶纤维增强尼龙6,并通过红外光谱和电镜分析其界面层,结果表明芳纶纤维经异氰酸酯化及封端稳定处理后,其表面所接技的不稳定基团-NCO转化成稳定的-NHCO-,封端结果较为明显;改性后纤维表面附有接枝物,从而使表面粗糙程度大大增加。用挤出和注塑的方法加工了PA6／Kevlar纤维（KF）复合材料,研究了它的拉伸、弯曲和冲击性能破坏形态。力学性能测试表明了改性尼龙6复合材料的拉伸和弯曲强度得到了改善,但冲击性能略为下降。     

The influence of silane treatment on nylon 6/nano‐SiO2 in situ polymerization

Silane treatment has been applied to the preparation of nylon 6/nano‐SiO₂ composites through in situ polymerization. The influence of such treatment on the reactivity of silica, polymerization of nylon 6, and the mechanical properties of the achieved composites has been studied. Fourier transform infrared (FTIR) spectroscopy and thermal gravimetric analysis (TGA) of silicas isolated from the composites have shown that the conversion of surface silanol groups to amino and epoxy groups did not cause a significant change in the reactivity of silica and that the percentage of silica surface grafting was around 15% for all treated and untreated silicas. End group analysis has shown that the presence of silica (pretreated or not) in the composite system resulted in the decrease of the average molecular weight of the polymer matrix. However, dynamic mechanical analysis and mechanical tests revealed that treating silica with silane improved the strength and toughness of the composite materials, while untreated silica improved their strength at the expense of toughness. This can be attributed to the existence of the flexible interlayer introduced by silane treatment. © 2002 John Wiley & Sons, Inc. J Appl Polym Sci 84: 827–834, 2002; DOI 10.1002/app.10349     

Effect of composite preparation techniques on electrical and mechanical properties and morphology of nylon 6 based conductive polymer composites

Nylon 6/carbon black conductive composites were prepared using two different methods, masterbatch dilution and melt mixing. Their effect on the size and distribution of carbon black agglomerates in the matrix was studied in terms of electrical and mechanical properties and morphology. The electrical resistivity of composites prepared by both methods decreased with increasing filler composition. The electrical resistivity of the diluted masterbatch composites and the melt mixed composites was reduced from the resistivity of pure nylon 6, 10¹⁵ “ohm, cm”, to 10⁷ “ohm, cm” at 1 and 6 wt % of carbon black, respectively. As the filler content increased, elongation at break and impact strength decreased, but tensile modulus increased. Masterbatch dilution method provided smaller carbon black clusters in composites compared to melt mixing method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2520–2526, 2006     

Study of blends of nylon 6 with EVOH and carboxyl-modified EVOH and a preliminary approach to films for packaging applications

Blends of nylon 6 (Ny6) with ethylene-co-vinyl alcohol (EVOH) and EVOH modified with the introduction of carboxyl groups (EVOH–COOH) have been studied by Fourier transform infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry, and dynamic-mechanical thermal analysis. The thermal and thermomechanical analyses of the blends show that the melting, crystallization, and relaxational behavior are affected by the blend composition and the presence of carboxyl groups on the EVOH chains. Nevertheless, microscopic and thermal investigations demonstrate the biphasic nature of the two-blend systems. Selective solvent extraction of the EVOH or EVOH–COOH phase in their blends and Fourier transform infrared analysis of the residual products indicates the occurrence of ionic linkages between the amino groups of the polyamide and the carboxyl groups of the modified EVOH, whereas specific interactions are evidenced for Ny6/EVOH blends. Tests performed on extruded Ny6/EVOH films show that the addition of EVOH effectively reduces the gas permeability of Nylon, whereas the addition of small amounts of EVOH–COOH helps to control and stabilize melt rheology. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 637–648, 1998     

Transcrystalline morphology of nylon 6 on the surface of aramid fibers

In this paper, the isothermal crystallization of nylon 6 in the presence of Kevlar 129 fiber was investigated by polarized optical microscopy (POM). The formation of a transcrystalline domain was found to be mainly controlled by crystallization conditions, such as the temperature of the isothermal crystallization, residual time at melting temperature and the cooling rate of the melt. The nucleation rate of nylon 6 on the fibers was mainly affected by the crystallization temperature. The interfacial transcrystallinity of nylon 6 occurred on the surface of Kevlar 129 fiber in the temperature range 130–190 °C. The reason for the formation of interfacial transcrystalline morphology is discussed from the molecular level, based on the understanding of the packing mode of nylon 6 chains around fibers and the interaction between matrix and fibers. It was found that the lattice matching and hydrogen‐bonding between nylon 6 and poly(p‐phenylene terephthalamide) (PPTA) crystals play an important role in the epitaxial crystallization. Copyright © 2004 Society of Chemical Industry     

Effect of the type of nylon chain‐end on the compatibilization of PP/PP‐GMA/nylon 6 blends

Polyamide and polypropylene (PP) are two important classes of commercial polymers; however, their direct mixing leads to incompatible blends with poor properties. Polypropylene functionalized with glycidyl methacrylate (PP‐GMA) was used as a compatibilizer in blends of PP and nylon 6, because of the possible reaction of ? NH₂ and ? COOH groups with the epoxide group of GMA. Two types of nylon 6 with different ratios between ? NH₂ and ? COOH groups were used. The one with higher concentration of ? COOH groups was less compatible with PP in a binary blend. When PP‐GMA was used as a compatibilizer, a better dispersion of nylon in the PP matrix was obtained together with better mechanical properties for both nylons used in this work. © 2001 Society of Chemical Industry     

P(N-phenylmaleimide-alt-styrene) as a heat-resistant agent in the application of nylon 6

P(N-phenylmaleimide-alt-styrene) (PNS) was synthesized, and nylon 6 (PA6)/PNS blends were prepared by melt blending. The heat resistant and crystallographic properties of PA6/PNS blends with different contents were investigated and analyzed. The results showed that the heat deflection temperature (HDT), relative crystallinity (X_n), and dynamic viscosity (η) increased with increasing PNS. The results of differential scanning calorimetry proved that PNS had played a positive role in nucleating PA6. Scanning electron microscosopy showed that the PNS domains were between 0.2 and 4 μm in diameter. The experimental results indicated that the addition of PNS improved the rigidity of PA6/PNS blends, thereby improving the heat-resistant properties of these blends. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47689.     

Preparation of high-modulus nylon 6 fibers by vibrating hot drawing and zone annealing

To prepare high-modulus fibers, the vibrating hot-drawing and zone-annealing methods have been applied to nylon 6. The vibrating hot drawing was repeated two times, increasing the applied tension; further, the zone annealing was superposed on the vibrating hot-drawn fibers. The superstructure and mechanical properties of each step fiber were investigated. The vibration under a cooperation of heating and tension was very useful for increasing the draw ratio, birefringence, and orientation factor of the amorphous chains. Consequently, the obtained fiber indicated high moduli, namely, Young's modulus of 23 GPa and the dynamic storage modulus at room temperature of 25.3 GPa. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1993–2000, 1998     

Combined effect of β‐nucleating agent and processing melt temperature on the toughness of impact polypropylene copolymer

The phase morphology and toughening behavior of impact polypropylene copolymer (IPC) with and without nucleating agent (NA), prepared at different processing melt temperatures (T_p), were investigated. Interestingly, three different structures can be formed in the IPC samples by adding NA or tuning T_p. A well‐defined core–shell structure is obtained in samples with α‐NA or without NA prepared at all T_p. A developing multilayered structure is mainly formed at high T_p with added β‐NA, while an incomplete phase separation structure with interpenetrating chains is the dominant structure for IPC samples prepared at low T_p with added β‐NA. In this case, because of the synergistic effect between phase morphology and relatively high β‐form crystal content, the chain interaction among the components and chain mobility of the amorphous portion of IPC are distinctly improved, resulting in a largely improved toughness under 0 °C. This improvement in toughness is very important for applications. © 2012 Society of Chemical Industry