Studies on disulfide-crosslinked nylon. I. Elastic disulfide-crosslinked polycaprolactam fiber

Elastic disulfide-crosslinked polycaprolactams of different sulfur contents (0.4-3.3%) were prepared by the reaction of N-methoxymethyl polycaprolactam (D.S., 0.30) with different amounts of thiourea, the hydrolysis with excess potassium hydroxide, and the spinning into aqueous hydrogen peroxide. The fibers obtained exhibited high elongation at break (500-300%), low initial modulus (13-1 kg/mm²), and high elastic recovery. The initial modulus decreased with increased crosslinking. Heat-treatment of the fibers at 140°C lowered the initial modulus remarkably. The effect of the crosslinking and the residual methoxymethyl substitution on the structure and the physical properties of the untreated and heat-treated fibers is discussed. The residual methoxymethyl groups were removed completely from the fibers by hydrolysis with formic acid. The removal led to marked reduction in the elongation and much increase in the initial modulus.     

Studies in the properties of nylon 6–glass fiber composites

Caprolactam has been anionically polymerized within the planar-random continuous glass mat reinforcement using a technique similar to reaction injection molding and up to 55% (w/w) [i.e., 33% (v/v)] glass fiber loading was achieved. The fiber volume fraction distribution across the diameter of the composite was observed to be reasonably uniform. The tensile stress–strain properties were determined. Composite modulus and strength appeared to be linearly dependent on the fiber volume fraction and increase with fiber volume content. The type of composite material studied has been used for compression molding of articles. Therefore, some tensile data were redetermined after compression molding and possible changes in degree of crystallinity resulting from the change in the thermal history monitored by differential scanning calorimetry. A 50% drop in the percent degree of crystallinity (monoclinic modification) of the as-polymerized composite and a deterioration in the tensile properties of the composite were observed after compression molding. On compression molding the mold surface needs to be completely covered with the composite sheet material; otherwise, matrix polymer flows out of the composite, and areas deficient in reinforcement result.     

Investigations on nylon 4 membranes. Synthesis and transport properties. I. Synthesis of nylon 4 polymer

The synthesis of nylon 4 (polypyrrolidone) by the anionic polymerization of 2-pyrrolidone through the use of the CO₂/potassium pyrrolidonate catalyst system for use in preparing polymer membranes for separation purposes was investigated in detail. The effects of the quantity of CO₂, the potassium pyrrolidonate catalyst, and the reaction temperature on the yield and molecular weights of the nylon 4 were studied. At reaction temperatures of 50°C and a reaction time of 120 hr, a yield of 50.9% with intrinsic viscosity of 4.42 (corresponding to M_n of 108,200 and M_w of 135,850) was obtained. The molecular weight distributions of the nylon 4 were determined by gel permeation chromatography (GPC) using m-cresol as the eluting solvent and were found to have a relatively narrow distribution.     

Studies on melt spinning of nylon 6. I. Cooling and deformation behavior and orientation of nylon 6 threadline

The melt spinning of nylon 6 filament yarns was studied by measuring the filament tensions at the takeup roll, the filament temperatures θ(x), filament diameters d(x), and birefringence Δn(x) as functions of distance x from the spinneret, and by observing how the molecular orientation was affected by these differences in cooling and thinning. Results were as follows: The thinning of the filament line, d(x), is affected little by the spinning temperature or by the degree of polymerization of the yarns taken up; it however depends heavily on the takeup speed V_Tu and the rate Q of production. Trouton viscosity β(T) as a temperature function derived from these experiments on nylon 6 is expressed consistently by the equation β ? 0.34 exp (3250/T), where T is absolute temperature. Nylon 6 filaments exhibit higher Trouton viscosity values than polyester or polypropylene filaments under the same spinning temperature. Filament temperature θ(x) versus distance x agreed well with theoretical values. The speed of molecular orientation was highest in the temperature range from 120°C to 40°C (the latter being the glass transition temperature of nylon 6). Furthermore, the larger the time rate of polymer deformation and the longer the residence time of polymer in the above temperature range, the higher was the orientation of the filament yarns taken up.     

玻璃纤维增强尼龙66复合材料的结构与性能

使用双螺杆挤出机,采用共混改性方法制备玻璃纤维(GF)增强尼龙66(PA 66)复合材料(GF-PA 66),并对其结构、热性能和力学性能进行了表征。结果表明:制备的GF质量分数分别为20%,25%,30%的GF-PA 66复合材料的密度均低于1.4 g/cm³,GF在GF-PA 66复合材料体系中呈现纤维交错复杂的网络结构;GF-PA 66复合材料的起始热降解温度均在320℃以上,具有较好的耐热性;随着GF含量的增加,GF-PA 66复合材料的拉伸强度、弯曲强度、弯曲模量升高,当GF质量分数达到30%时,复合材料的拉伸强度为147.4 MPa,比纯PA 66提高了75%,弯曲强度达到202 MPa,比纯PA 66提高了112%,弯曲模量达到7 783.3 MPa,比纯PA 66提高了175%;随着GF含量的增加,GF-PA 66复合材料的悬臂梁冲击强度先降低后升高,当GF质量分数为30%时,复合材料的悬臂梁冲击强度高于纯PA 66。     

Mechanical and some other properties of acrylic-monomer-grafted nylon 6 fiber

Nylon 6 fiber, grafted with various vinyl monomers, viz., methyl methacrylate (MMA), ethyl methacrylate (EMA), and n-butyl methacrylate (n-BMA) were evaluated for their tensile, dye uptake, moisture regain, and solubility characteristics and compared to those of the parent nylon 6 fiber. The tensile properties (tenacity and initial modules) of the grafted samples show a decreasing trend and the percentage breaking elongation an increasing trend with the increase in the graft level in the case of all the three monomers compared to parent nylon 6 fiber. Disperse dye uptake also shows a decrease with the increase in the graft level in all the three monomers grafted only onto nylon 6 fiber. With the introduction of hydrophobic groups in the polymer backbone the moisture regain values decrease. This is true for all the samples and follows the order MMA-g-nylon > EMA-g-nylon > n-BMA-g-nylon. Solubility of the polymer in the solvent orthochlorophenol (OCP) and metacresol (MC) also decreases with the increase in the graft level for all the three monomers used in the following manner: OCP: EMA-g-nylon > n-BMA-g-nylon > MMA-g-nylon; MC: n-BMA-g-nylon > EMA-g-nylon > MMA-g-nylon.     

Impact properties of short carbon fiber reinforced nylon 6.6

The impact properties of injection-molded nylon 6.6 composites containing different loadings of short carbon fibers have been studied using an instrumented falling weight impact tester (IFWIT). Analysis of the impact data using linear elastic fracture mechanics (LEFM) has enabled the evaluation of the critical strain energy release rate, G_c. Instrumentation of the impact machine has facilitated the determination of another fracture mechanic parameter, the fracture toughness, K_c. Both parameters are observed to increase with increasing volume fraction of fibers. Examination of fracture surfaces using scanning electron microscopy (SEM) has revealed that the main energy dissipative processes responsible for toughening the composites is the fiber pull-out mechanism.     

Studies on mechanical properties of polyethylene–organic fiber composites. I. Nut shell flour

Composites were made from polyethylene and an organic fiber (pecan shell and peanut hull flour) using a compression-molding technique. Studies of variations in molding temperature (145–180°C), fiber concentration (0–40% by weight), and fiber mesh size (100, 200, and 325) were correlated to the mechanical properties of the composites (tensile strength, elongation, fracture energy, modulus, and impact strength). In untreated nut shell composites, tensile strength decreased steadily as the fiber concentration increased. This was due to poor bonding between the untreated fiber and polymer. Polyisocyanate was used as a coupling agent and its effect on mechanical properties of the composites was studied. Significant improvement in tensile strength was achieved with an isocyanate coupling agent, but it had no effect on modulus of the composites. Both untreated and isocyanate-treated composites had lower impact strength values; further composite matrix modifications would be necessary to maintain or improve impact strength.     

Studies of the development of fibrillar structure in nylon 6

Very thin films of poly(vinyl alcohol) could be prepared by utilizing the adsorption of polymer molecules at air/water interface from the aqueous solutions of the poly(vinyl alcohol) derived from vinyl trifluoroacetate. The films prepared by the bubble method were thinner than those obtained by the frame method. The minimum thickness of the former films was 260 Å and that of the latter was 1800 Å. These very thin films resisted water at temperatures below 55°C. The maximum Young's modulus of the drawn/annealed films prepared from these samples was 30 GPa. The permeability of water, J_w/δP, was 2–6 × 10^?3 cm · s^?1 atm^?1 (0–55°C) for the untreated film (thickness: 1800 Å) prepared by the frame method and 0.8–2.2 × 10^?2cm · s^?1 · atm^?1 (5–55°C) for the untreated film (360 Å) prepared by the bubble method, and depended on the thickness of film.     

Carbon fiber structure and stability studies

A study has been made of the thermal-oxidative stability of several commercially available carbon fibers. Significant differences in the weight loss behavior were observed in air aging studies run on the bare fibers at 600°F (589 K). The stability of high temperature laminates, such as those based on NR-150 polyimide precursor solutions, was found to be directly affected by the stability of the reinforcing carbon fibers. In studies carried out to determine the reasons for carbon fiber instability, residual sodium sulfate was found to be the principle destabilizing factor. A mechanism whereby the sodium sulfate promotes the oxidation of carbon in the presence of air is proposed.     

Effect of organoclay structure on nylon 6 nanocomposite morphology and properties

A carefully selected series of organic amine salts were ion exchanged with sodium montmorillonite to form organoclays varying in amine structure or exchange level relative to the clay. Each organoclay was melt-mixed with a high molecular grade of nylon 6 (HMW) using a twin screw extruder; some organoclays were also mixed with a low molecular grade of nylon 6 (LMW). Wide angle X-ray scattering, transmission electron microscopy, and stress-strain behavior were used to evaluate the effect of amine structure on nanocomposite morphology and physical properties. Three surfactant structural issues were found to significantly affect nanocomposite morphology and properties in the case of the HMW nylon 6: decreasing the number of long alkyl tails from two to one tallows, use of methyl rather than hydroxy-ethyl groups, and use of an equivalent amount of surfactant with the montmorillonite, as opposed to adding excess, lead to greater extents of silicate platelet exfoliation, increased moduli, higher yield strengths, and lower elongation at break. LMW nanocomposites exhibited similar surfactant structure-nanocomposite behavior. Overall, nanocomposites based on HMW nylon 6 exhibited higher extents of platelet exfoliation and better mechanical properties than nanocomposites formed from the LMW polyamide, regardless of the organoclay used. This trend is attributed to the higher melt viscosity and consequently the higher shear stresses generated during melt processing.     

Effect of glass fiber surface chemistry on the mechanical properties of glass fiber reinforced, rubber-toughened nylon 6

The mechanical properties of nylon 6 and its blends with maleated ethylene-propylene rubber (EPR-g-MA) plus glass fibers were examined as a function of the chemical functionality of the silane surface treatment applied to the glass fibers. Three reactive silane coupling agents, with anhydride, epoxy, or amine functionality, were used and found to have little effect on the mechanical properties when no EPR-g-MA is present. When 20 wt% EPR-g-MA is used as a rubber toughener, however, the yield strength and Izod impact strength were lowest for the amine functional silane and highest for the anhydride silane, while the epoxy silane fell in-between. These results were attributed to the differences in reactivity of the three reactive silanes. An unreactive silane (octyl groups) was used as a release agent on the glass fibers and compared with the anhydride functional silane. The octyl silane did not improve the ductility of the composite, as may have been speculated, and had poor yield strength and impact resistance when compared to the anhydride silane. Both octyl and anhydride treated glass fibers improve the heat distortion temperature such that most of the high temperature stiffness that is lost on addition of EPR-g-MA is regained by adding glass fibers.     

高强锦纶6长丝的制备及其结构与性能研究

采用相对黏度2.485的半消光聚酰胺6切片为原料,通过熔融纺丝-多级拉伸工艺制备了高强锦纶6长丝,研究了多级拉伸工艺中拉伸温度及拉伸倍数对纤维结构和性能的影响。结果表明:受二级拉伸温度的影响,纤维中存在γ晶型向α晶型的转变,在一定范围内适当地提高纤维的各级拉伸温度,有利于纤维晶体结构更加稳定,而拉伸倍数的变化并未引起纤维晶型的转变;各级拉伸倍数较高时高强锦纶6长丝的取向度显著增加,二级拉伸温度较高时纤维取向度增加明显;拉伸倍数相对于拉伸温度对高强锦纶6长丝力学性能的影响更明显,当一级拉伸倍数为1.145、二级拉伸倍数为3.12、一级拉伸温度为55℃、二级拉伸温度为178℃时,纤维断裂强度最大,达7.23 cN/dtex。     

Dimensional stability and tensile properties of drawn polystyrene composites

Recovery experiments above T_g and tensile tests have been performed on glass bead and short glass fiber–polystyrene composite sheets obtained from extrusion and subsequent hot drawing. A shift procedure has been applied to the recoil data using a WLF equation. The data reported show that both dimensional stability and mechanical properties are enhanced by adding rigid fillers to the drawn thermoplastic matrix. The presence of short fibers reduces strongly the recoverable strain of the oriented material. A simple model able to predict the equilibrium values of the length reversion ratio of glass bead composites is developed and compares well with the experimental data.     

The effect of heat setting on the structure and mechanical properties of poly(ethylene terephthalate) fiber. I. Structural changes

We report structural changes in commercial multifilament poly(ethylene terephthalate) (PET) yarn when it is heat set in silicone oil over a range of temperatures between 100 and 220°C for times ranging from 1 min to 1 hr, while the yarn was (1) free to relax, and (2) held taut at constant length. In one case, viz., a sample heat treated for 1 hr, the cooling time was also varied to study the effect of rate of cooling. The free-annealed and taut-annealed samples showed considerable differences. The predominant role of the temperature of heat setting on structure is discussed in detail. There are considerable changes in the amount and orientation of the amorphous phase, and these will be shown to have important influence on mechanical properties in subsequent reports.     

Developing critical extrusion parameters for nylon 6, nylon 66, and nylon 46 polyamide from the rheology data

This paper describes a new approach to the rheological characterization of engineering plastics such as nylon 6, 66, and 46 polyamides using a capillary rheometer. The melt viscosity data as a function of temperature, shear rate, and residence time were measured and evaluated to demonstrate how to accurately predict critical extrusion parameters, such as barrel temperature profile, stock temperature window, and the screw design requirements, for extruding strip, tubing, and profiles. The results of this work provide a practical and simple quality control tool to select a polyamide resin for optimum processing, and to develop critical processing parameters for extrusion.     

Investigations on nylon 4 membranes: Synthesis and transport properties. II. Transport properties of nylon 4 polymer membranes

The reverse osmosis, ultrafiltration, and dialysis properties of nylon 4 membranes to separations of sodium chloride, urea, a series of ethylene glycols and other compounds in the aqueous phase were investigated. The nylon 4 membranes were prepared from a formic acid solution with and without organic or inorganic additives. The effects of polymer concentration, amount of additives, casting time, and temperature on the membrane performance in terms of salt separation and product rate were investigated. The tensile properties of the nylon 4 membranes in both the dry and wet states were determined. It was found that the highest salt separation of a 0.1% sodium chloride solution did not exceed 53.3%. However, these membranes showed some intersting dialysis properties which were comparable to those of commercial cellophane and cellulose acetate membranes.     

Polyether-segmented nylon hemodialysis membranes. III. Preparation and properties of new polyether-segmented nylon

In order to apply a blood-compatible polymer to hemodialysis membrane, a new polyether-segmented nylon which dissolved in common organic solvents was designed. The basic polyether-segmented nylon was synthesized by melt polycondensation from sebacic acid, m-xylenediamine, and α,ω-bisaminopropyl-poly(ethylene oxide). To improve the solubility, azelaic acid and hexamethylenediamine were copolycondensed with the basic copolymer. The solubility was correlated with the heat of fusion (ΔH_m) of the copolymer. When ΔH_m is < 30 mJ/mg, the polymer is soluble in dimethylsulfoxide and makes a stable solution. The nonthrombogenicity was investigated in the viewpoint of adhesion of platelet onto the copolymer surface. It is made clear that the surface of the block copolymer, having > 10 wt % of poly(ethylene oxide), suppresses the adhesion of platelet, and the composition of the nylon block has no effect on the adhesion of platelet. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1723–1729, 1997     

Optothermal properties of fiber morphology on nylon 66 fibers due to annealing and drawing processes

The changes produced by the effects of annealed and drawn fibers on the microstructure and macrostructure of nylon 66 fibers are considered. The optical properties and strain produced in nylon 66 fibers under different conditions are measured interferometrically at room temperature. Structural parameters are calculated such as the average work per chain, the work per unit volume, the reduction in entropy due to elongation, and the work stored in the body as strain energy. The evaluation of the density aided the calculation of the crystallinity, the mean square density fluctuation, the isotropic refractive index, the harmonic mean polarizability of the dielectric, and the harmonic mean specific refractivity. In addition, the resulting data are utilized to calculate the optical stress coefficient and the optical configuration and to apply the Mooney–Rivlin equation to determine its constants. Also, the number of crystals per unit volume and the average orientation angle for uniaxial stretching are calculated by the extension ratio. The relations between the optical, mechanical, and thermal changes with different parameters are given for the studied fibers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 916–928, 2002; DOI 10.1002/app.10107