Catalytic grafting: A new technique for polymer–fiber composites I. Polyethylene–asbestos composites

In this work we present a new technique to prepare polyolefin-fiber composites. This technique is based on chemical anchoring of a catalyst on reinforcing agents containing OH groups on their surface and then conducting an olefin polymerization on the supported catalyst. This technique offers the possibility to approach the challenging problems encountered in polymer composites, namely, the reinforcement-matrix adhesion, the dispersion, and the wetting of the reinforcement by the resin. As a first part of a systematic research, we report on the procedure of fixation of titanium tetrachloride on the surface of asbestos fibers and the Ziegler-Natta polymerization of ethylene on the surface-modified fibers. The procedure as well as the structure and properties of the composite were investigated by means of FTIR, atomic absorption, SEM, solvent extraction, and tensile testing. The experimental results show that the Ziegler-Natta catalyst can be efficiently anchored on the surface of the fibers to conduct successful polymerization and to “synthesize” a new class of polymer composites.     

Diffusion of dyes in polyester fibers. III. Time delay in establishment of the equilibrium concentration of dye at fiber surface

In the dyeing process of the copolyester fiber Dilana with the disperse dye Synthene Scarlet P3GL, a deviation from the simple model of Fickian sorption occurs. It manifests itself as a time delay in establishment of the equilibrium dye concentration at the fiber surface. As has been stated, the variation of C_s (the surface dye concentration) with time of dyeing fits the equation; C_s = C_∞ (1? e^?βt). Regarding the relation of C_s to t, the diffusion coefficient of the dye in the studied fiber has been calculated by the theoretical equation reported in Crank's monograph. It has been proved that the experimental data on kinetics of dyeing the fiber Dilana with Synthene Scarlet P3GL fit considerably better the tested equation than the classical Hill's equation.     

Carrier‐bound methotrexate. I. Water‐soluble polyaspartamide–methotrexate conjugates with ester links in the polymer–drug spacer

The antifolate‐type anticancer drug methotrexate (MTX) has for many years, in numerous laboratories, been a “workhorse” drug for conjugation with natural and synthetic macromolecular carriers for the purpose of enhancing bioavailability and lowering toxic side effects. In the project here described the polymer–drug conjugation strategy is utilized for the preparation of water‐soluble polyaspartamide–methotrexate conjugates in which the drug is carrier‐anchored through short spacers containing ester groups as biofissionable links. To this end, polyaspartamide carriers 1, poly‐α,β‐D,L ‐N‐(2‐hydroxyethyl)aspartamide, and 2, poly‐α,β‐D,L ‐N‐[2‐(2‐hydroxyethoxy)ethyl]aspartamide, are treated with MTX in DMF solution in the presence of a carbodiimide coupling agent and 4‐(dimethylamino)pyridine catalyst. The molar MTX/OH feed ratios, 0.28 and lower, are chosen in these coupling reactions so as to provide conjugates featuring drug‐loading levels in the approximate range of 3–16 mol % MTX, roughly corresponding to 6–28% by mass. The water‐soluble product polymers are purified by aqueous dialysis, collected in the solid state by freeze‐drying, and structurally characterized by ¹H–NMR spectroscopy. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1844–1849, 2001     

Heterogeneous polymer–polymer composites. II. Preparation and properties of model systems

A two-stage emulsion polymerization procedure has been developed and used to prepare relatively uniform populations of heterogeneous acrylic latex particles (HLP). One class of particles (HLP1) can be described as composite materials comprising a glassy continuous phase and a rubbery discrete phase. Another class (HLP2) can be described (at high rubber content) as composite materials comprising a rubbery continuous phase and a glassy discrete phase. The phase structure of the HLP1 is sufficiently stable to allow fabrication of composites having a uniform spatial distribution of inclusions by direct compression molding. Although the observed particle structure of the HLP2 does not depend markedly on crosslinking, the phase structure and mechanical properties of compression moldings do. Crosslinking of the glassy stage appears to stabilize HLP2 phase structure during molding, while crosslinking of the rubbery stage favors phase inversion. The observed HLP2 particle structures and the morphology of molded HLP1 specimens are consistent with a shell-core model. It is found that the modulus and thermal expansion coefficient of many of these materials can be adequately described in terms of a simple theoretical model for the elastic and thermoelastic properties of particulate composites, provided that an interaction parameter interpreted as a maximum packing fraction is introduced.     

Effects of the moisture and fiber content on the mechanical properties of biodegradable polymer–sisal fiber biocomposites

The matrix of the composites that were used in this work was a commercial blend based on starch and cellulose derivatives. The biodegradable polymer was reinforced by short‐sisal fibers with a range in fiber content of 5–15 wt %. The effects of humidity on the diffusion coefficients, equilibrium moisture content, and mechanical properties were studied. Equations obtained from microscopic mass balances for diffusion in solids were used to predict the absorbed humidity in both components (the sisal fibers and biodegradable polymer) and in the composites as a function of time. Different model predictions of the composite diffusion coefficients as a function of the filler concentration were also examined, and they were found to be in agreement with the experimental results. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4007–4016, 2004     

Electro–optic studies on polymer‐dispersed liquid crystal composite films. I. Composites of PVB–E7

The electro‐optic performance characteristic of polymer‐dispersed liquid crystal (PDLC) composite films out of poly(vinyl butyral) (PVB) and nematic liquid crystal (E7) have been studied for a wide range of PVB–E7 composite compositions (20–70 wt % of E7). Composites were prepared by solvent casting from chloroform at room temperature. A scanning electron microscopy study showed that a E7 phase is continuously embedded in chink‐like structure of PVB matrix. Optical transmittance of the composite films (of 60 and 70 wt % loading of E7) under an alternating current (ac) electric field (0–250, V_p‐p) and frequency (50 Hz to 1 KHz) were measured employing He Ne laser (λ = 632.8 nm). The results indicate that the (PVB–E7) composite exhibits a memory effect. In the memory state, higher transmittance is preserved without applying voltage. The memory state can be erased and changed to the scattering Off‐state by heating the film to the clearing temperature of the liquid crystal. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3485–3491, 1999     

Heterogeneous polymer–polymer composites. I. Theory of viscoelastic properties and equivalent mechanical models

The representation and interpretation of dynamic mechanical properties of heterogeneous polymer–polymer composites are discussed in terms of equivalent mechanical models and the viscoelastic form of the well-known Kerner equation. Model parameters calculated from dispersed phase volume fraction and matrix Poisson's ratio (using the Kerner equation) are in fairly good agreement with experimental values for systems comprising soft inclusions in a hard matrix. The effects of partial phase inversion on dynamic properties are discussed in terms of an extension of the Kerner equation. Model calculations indicate that the in-phase component of the complex modulus depends primarily on dispersed phase volume concentration, while the out-of-phase component depends on both the concentration and the morphology of the dispersed phase. Although substantial information about the microstructure of polymer–polymer composites can in principle be deduced from dynamic measurements, quantitative correlation between dynamic properties and use properties such as impact strength (which may have a quite different dependence on structural parameters) is probably fortuitous.     

阳离子染料可染聚酯纤维生产中管路结焦分析及处理

简要阐述了阳离子染料可染聚酯纺丝生产过程中的结焦现状.测试了结焦物的化学组成,分析了阳离子染料可染聚酯易结焦的原因,在分子层面作出结焦的理论分析,并且对阳离子染料可染聚酯纤维生产中结焦提出解决方案和预防措施.     

Diffusion/adsorption model of cellulose dyeing. II. Ordinary cellulose–direct dye system

The diffusion and adsorption of C.I. Direct Yellow 12 and Blue 15 in water-swollen ordinary cellophane sheets were examined at various ionic strengths. The concentration dependence of apparent diffusion coefficients, D_c, for these dyes was obtained from the diffusion profiles in the substrate, which were measured by the use of the cylindrical film roll method. The decrease of apparent porosity with an increase in the amounts of adsorption was observed. To explain the diffusion/adsorption behaviors of these systems, a variable porosity model was proposed and was applied to analyze the concentration dependence of D_c's. The diffusion/adsorption behaviors of these dyes could be quantitatively described by this model at relatively low ionic strengths. At higher ionic strengths and/or lower values of C, i.e., at the large values of C_im/C_m, where the C's are the concentrations of immobilized (suffix im) and mobile (suffix m) species, it needed to introduce the concept of dynamic equilibria which occurred simultaneously with diffusion but deviated from the true equiliblia measured by the adsorption experiments.     

Water uptake,chemical characterization,and tensile behavior of modified banana–plantain fiber and their polyester composites

Banana–plantain fibers (BPFs) were treated with acetic anhydride (AA), epichlorohydrin (EP), and an acetic anhydride–epichlorohydrin blend (AA_EP). Natural fiber–polyester composites (PCs) were fabricated using untreated and treated BPF by the hand lay‐up technique. Modified BPF Raman and Infrared spectroscopy (ATR‐FTIR) analysis revealed losses of lignin and hemicelluloses and new chemical bonds that confirmed the replacement of part of the raw fiber hydroxyl groups, which gave rise to a degree of hydrophobicity in the treated fibers. This change altered their water sorption isotherms, swelling behavior in water, impedance spectroscopy, and XRD analysis. Assays of water absorption and tensile resistance for untreated BPF (U) and modified BPF polyester composites demonstrated a remarkable reduction in water intake, whereas tensile strength was maintained (P < 0.05) for the modified BPF polyester composites. POLYM. COMPOS., 37:2960–2973, 2016. © 2015 Society of Plastics Engineers     

Diffusion of dyes in polyester fibers. IV. Anomalous sorption of disperse dye synthene scarlet P3GL

The investigations on dyeing of poly(ethylene terephthalate) fibers with disperse dye Synthene Scarlet P3GL have revealed anomalous sorption of the dye in heat-treated samples. In the mathematical solution of the process it has been assumed that anomalous sorption can be treated as superposition in time of two stages of Fickian sorption. The contents of absorbed dye at quasiequilibrium C_I, at the final equilibrium C_II, and the apparent diffusion coefficients D_I, and D_II have been calculated using Hill's equation.     

Preparation of betaine‐modified cationic cellulose and its application in the treatment of reactive dye wastewater

Betaine‐modified cationic cellulose was prepared through the reaction of cellulose with betaine hydrochloride by an efficient one‐step dry method. Dicyandiamide was used as a dehydrating agent to promote the formation of ester bonds between the reactants. Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy were used to characterize the cellulose betainate. Experiments showed that at a molar ratio of the cellulose glucose unit, betaine hydrochloride to dicyandiamide, of 1:1:0.5 at 150°C for 3 h, the degree of substitution of the cationic group reached 0.80. The adsorption of simulated C. I. Reactive Red 24 and C. I. Reactive Red 195 wastewater on the cationic cellulose was carried out, and the effects of the adsorbent dose, initial dye concentration, and salt concentration on the dye removal efficiency were investigated. The equilibrium adsorption isotherm data of the cationic cellulose exhibited a better fit to the Langmuir isotherm model than the Freundlich one. The experimental results suggest that the prepared cationic cellulose materials show potential application for reactive dye wastewater treatment. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40522.     

A morphological investigation of thermosets toughened with novel thermoplastics. I. Bismaleimide modified with hyperbranched polyester

The morphology of a bismaleimide (BMI) toughened with a thermoplastic hyperbranched aliphatic polyester (HBP) was studied by scanning electron microscopy (SEM). The effect of thermoplastic architecture, molecular weight, and end group on the size and arrangement of the dispersed phase was investigated and compared with the thermoset fracture toughness. SEM micrographs showed that higher molecular weight HBP formed roughly spherical dispersed domains of up to ∼ 60 μm, which contained BMI inclusions. Lower molecular weight HBP formed spherical dispersed thermoplastic domains, with diameters up to ∼ 10 μm with no BMI inclusions. A low molecular weight linear polyester with a repeat unit structure, which was similar to that of the HBP, was prepared and used as a control. Within error, BMI toughened with the linear control yielded the same fracture toughness as the best values obtained with HBP‐modified BMI, but the morphology differed. The linear polyester phase separated into particles with a larger average diameter and also possessed some phase‐inverted regions. End group effects were studied by modifying the hydroxy‐terminated HBP to unreactive nitrophenyl, phenyl, and acetyl end groups. The nitrophenyl‐terminated HBP did not phase separate from the thermoset, whereas the nonpolar phenyl‐ and acetyl‐terminated HBP phase separated to form small (≤1 μm and ∼ 2 μm, respectively) spherical domains. Some comparisons were made to other results with HBP thermoplastics in BMI and epoxy thermosets. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1065–1076, 1999     

Experimental testing of the polymer–filler gel formation theory. II.

In Part I of the present article predictions of the polymer–filler gel formation theory were tested experimentally using fine-particle silica in natural rubber (NR) and in styrene–butadiene rubber (SBR). Part II brings a more detailed experiment–theory comparison using carbon blacks differing in specific surface area and structure, graphitized blacks, fume silica, and surface-modified (hydrophobized) fume silica. In the region of low and medium filler concentration c, the c-dependence of the fraction G of polymer in polymer–filler gel, of the fraction B of total filler-bound polymer, of the fraction w_disp of solvent-dispersed filler particles were found to be correctly predicted by the theory. The effect of filler characteristics and of the method of its incorporation into the polymer on the values of the adjustable parameters of the theory (filler surface adsorptivity, D, and filler particles connectivity, f) was determined and is discussed. In the region of very high c increasing positive deviations of D from the low-c behavior were observed and an explanation for this effect is proposed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 95–107, 1998     

Compatibilization of acrylic polymer–silk fibroin blend fibers. I. Graft copolymerzation of acrylonitrile onto silk fibroin

To synthesize effective compatibilizers for the compatibilization of acrylic polymer–silk fibroin blend fibers, the homogeneous graft copolymerization of acrylonitrile onto silk fibroin, initiated by potassium persulfate–sodium bisulfite redox system in 60 wt % ZnCl₂ aqueous solution was investigated. The percentage graft, percentage efficiency, and molecular weight of the grafted polyacrylonitrile increase with the increase of the concentration of initiator, the concentration of acrylonitrile, and the temperature to optimum values, respectively, and then decrease. With the increase of reaction time, the percentage graft and percentage efficiency increase, whereas the molecular weight of the grafted polyacrylonitrile decreases. The influence of the reactionconditions on the molecular architecture of the graft copolymers is also discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1089–1097, 1998     

Rheological characterization of the gel point in polymer‐modified asphalts

In this work, the rheological characterization of the gel point in polymer‐modified asphalts is carried out. The viscoelastic properties of polymer‐modified asphalts, in which the polymer is styrene–ethylene butylene–styrene (SEBS) with grafted maleic anhydride (MAH), were measured as a function of MAH concentration. The crosslinking reaction that leads to gelation is characterized by power‐law frequency‐dependent loss and storage modulus (G″ and G′). The relaxation exponent n (a viscoelastic parameter related to the cluster size of the gel) and gel strength S (related to the mobility on the crosslinked chain segments) were determined. The value of the power‐law exponents depends on the composition of polymer, ranging from 0.30 to 0.56, while the value of the rigidity modulus at the gelation point (S) increases with the amount of reactive groups of the modifier polymer. Both n and S are temperature‐dependent in the blends. The blends containing gels present a coarse morphology, which is related to the rheological properties of the matrix and dispersed phase. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Use of Flory–Huggins parameters in the characterization of polymer–filler compositions

Any quantitative information on the strength of interactions between an inorganic filler and polymer is substantial for the future application of the composite. The magnitude of adhesion of two phases may be deduced from results collected by various experimental techniques. A Flory–Huggins interaction parameter (χ₂₃^′) was earlier successfully used in the characterization of polymer blends. We propose to express the magnitude of modified filler/polymer interactions by using χ₂₃^′. It was calculated from retention data of test solutes during an inverse gas chromatography (IGC) experiment. IGC is an extension of conventional gas chromatography in which a nonvolatile material to be investigated is immobilized on a column. Parameters determined during IGC experiments may be successfully used in the characterization of polymers and their blends, composites, fillers, and other materials and the quantification of the interactions between the components of polymer mixtures, including the interactions between polymeric components and filler surfaces. Here this method is applied to the characterization of a series of poly(ether urethane)/modified carbonate–silicate filler systems containing different amounts of a filler (5, 10, and 20 wt %). The possibilities and limitations of the IGC method are shown. The usefulness of some methods for minimizing the Δχ effect (the dependence of χ₂₃^′ on the type of test solute) is examined and discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008