Mechanical properties of in-situ composites based on partially miscible blends of glass-filled polyetherimide and liquid crystalline polymers

The use of inorganic (glass) fiber reinforcement to enhance the mechanical properties and reduce the anisotropy of in situ composites based on blends of liquid crystalline polymers (LCPs) with polyetherimide (PEI) is discussed. It was found that the tensile and flexural moduli are increased and the anisotropy is reduced with increasing grass content (when compared at equivalent LCP weight fractions). The creep compliance of the PEI/LCP composites is reduced upon the addition of glass fibers. However, the disadvantage is that the processability worsens upon addition of glass fibers to the PEI/LCP in situ composites. The effect of adding glass reinforcement on the ultimate tensile strength is less clear, because the data do not show any consistent trend. Similarly, the elongation at break and toughness do not show any consistent improvement upon addition of glass reinforcement. Morphological studies show that there is considerable difference between the size and texture of the reinforcing glass fibers and LCP microfibrils.     

Surface characterization of silane-treated industrial glass fibers

The adsorption of silane coupling agents onto glass fiber surfaces has been investigated. The type of adsorption was elucidated using electron spectroscopy for chemical analysis (ESCA or XPS). The surface charging was recorded using streaming potential analysis. The silane bond strength was tested by boiling the silanized fibers in water for 2 h. Thereafter the conductivity of the water was measured in order to estimate the capability of the silane surface film to prevent ion dissolution from the glass. ESCA provided information on the amount adsorbed and indicated that substantial rearrangement in the surface film structure occurred as a function of the silane concentration. The aminosilane produced a strong positive charge on the glass fibers, while the nonionic silanes were only partly condensed, giving rise to a substantial enhancement of the negative charge. The conductivity measurements indicated that the silane films were present as a loose patchlike silane network on the surface of the E-glass fibers. This conclusion is in accordance with the results obtained with all the techniques used.     

Studies on compatibilization of blends of polypropylene and a thermotropic liquid crystalline polymer

Thermotropic liquid crystalline polymers, LCPs, are frequently blended with thermoplastics to achieve an in situ composite structure. Significant mechanical reinforcement is obtained for the matrix polymer in the direction of the LCP fibers, but the transversal properties are often inferior because of the incompatibility of the components. Blends of LCP with polypropylene, and with three related matrix polymers, and PP/LCP blends with added potential compatibilizers were prepared and studied for their mechanical properties and morphology. A notable improvement in impact strength was achieved when a small amount of ethylene-based terpolymer was added as compatibilizer. © 1993 John Wiley & Sons, Inc.     

原位聚合连续纤维增强聚甲基丙烯酸甲酯复合材料的界面及性能研究

通过选用含不同官能团的硅烷偶联剂3-甲基丙烯酰氧丙基三甲氧基硅烷(MPS)、γ-氨丙基三甲氧基硅烷(APS)和γ-氯丙基三甲氧基硅烷(CPS)处理玻璃纤维,然后通过原位聚合的方法制造了连续纤维增强的聚甲基丙烯酸甲酯(PMMA)复合材料。研究结果表明,经过这三种偶联剂处理的玻璃纤维与基体树脂在界面分别形成了化学键、范德华力和氢键。红外、动态力学分析和扫描电镜研究表明,复合材料的界面粘接强度顺序为:MPS>CPS>APS。MPS处理的复合材料具有最高的弯曲强度,而CPS处理的复合材料具有最佳的冲击韧性和断裂伸长率。     

The structure of γ‐glycidoxypropyltrimethoxysilane on glass fiber surfaces: Characterization by FTIR,SEM, and contact angle measurements

The purpose of this article is to determine the structure of γ‐glycidoxypropyltrimethoxysilane (γ‐GPS) on glass fiber surfaces. The interfacial adhesion of glass fiber–polymer can be improved by the silane treatment of the glass fiber. To change the composition of the glass and regenerate to the hydroxyl groups, activation pretreatment of heat cleaned woven glass fabric was performed using a 10% (v/v) hydrochloric acid aqueous solution for different durations before silane treatment. The treatment of silanization of heat cleaned and acid activated glass fibers with (γ‐GPS) were conducted at various time intervals. These fibers would be used to quantify the relationship between contact angle of glass fiber surface and the interfacial shear strength of the fiber–polymer interface. The effect of acid activation on glass surface and the interaction between glass fibers and silane coupling agent were examined using Fourier transform infrared spectroscopy. The experiments, in conjunction with electron photomicrographs of glass surfaces treated with coupling agent, are interpreted in an attempt to explain the stability of coupling agent‐glass interfaces. From SEM analysis, it was clearly observed that agglomerations of silane agent in the cavities among the heat cleaned fibers are available. However, this case was not observed for the silanization of acid activated glass fibers. In addition, contact angle measurements on glass fibers were performed to evaluate surface structure. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Processability of LCP‐nylon‐glass hybrid composites

A hybrid composite consisting of rubber toughened nylon 6,6, short glass fibers and thermotropic LCP was investigated by varying the content of LCP. It was found that a hybrid composite offered better processability over the glass fiber reinforced polymers alone. The total torque in melt mixing increased with short glass fiber addition but decreased with an increase in LCP content. The thermal stability of the glass fiber reinforced composite was improved by blending with LCP. However, a minimum of 15 wt% LCP was required to realize reinforcement effect from the hybrid composite. The fracture morphology was examined using SEM techniques. Some LCP fibrils could be observed on the tensile fracture surface.     

New Coupling Agents as Adhesion Promoters at the Poly(Phenylene Sulfide)/Glass Interface-Studies with Micro and Macro Composites

Carboxy-functionalized poly(phenylene sulfide) having different molar masses and amount of the functional group were prepared in order to be used with γ-aminopropyltriethoxysilane as surface treatment of E-glass fibers. These grafted polymer chains act as connecting chains in order to improve the interfacial shear strength of the PPS-glass interface. According to their chemical nature, which is the same as the PPS matrix, and their ability to crystallize in the same crystalline form as the pure PPS, a continuum of bonding from the fiber surface to the bulk matrix is achieved. A chemical linkage is established at the glass surface by means of hydrolyzed ethoxysilane groups of the γ-APS and from the formation of amide units resulting from the reaction of amine functions of the silane and the carboxylic groups of the modified PPS. A “physical” linkage is expected between the grafted PPS and the PPS chains by means of entanglements and co-crystallization. A large improvement of the interfacial shear strength measured from the microdroplet test is observed when a modified-PPS having a medium molar mass and a low amount of functional groups is used in comparison with untreated or silane-treated glass fibers. This improvement is also observed for short glass fibers/PPS composite materials. In fact, a large improvement is obtained on mechanical properties such as the tensile, flexural, and impact strengths.     

The Effect of Surface Treatment on the Strength and Adhesion Characteristics of Phoenix dactylifera-L(Date Palm) Fibers

ABSTRACT

There is a growing interest in the use of natural/bio-fibers as reinforcing components for thermoplastics and thermosets. However, they do suffer from a few limitations, such as lower compatibility with relatively hydrophobic polymer matrixes. Thus, improvement of the interface and interphase interactions in natural fiber–polyester composites is essential. In this research date palm (Phoenix dactylifera-L) fibers were modified by surface treatment using chemical method in order to improve their adhesion to polyester matrixes. Alkaline treatment, as an example of dissolution and treatment with silane coupling agents were performed. Furthermore, a combination treatment of alkaline and silane coupling agents was also carried out. Fiber modifications were monitored by Scanning Electron Microscopy (SEM). In addition to that, the improvement of adhesion and strength between date palm–modified fibers and polyester matrix was investigated by single filament pull-out test as well as tensile tests. It was found, from interfacial shear strength values, that substantial improvements in fiber-matrix compatibility have been achieved. According to single filament pull-out test results, interfacial shear strength increased for all treated fibers as compared to non-treated fibers. Particularly, combination of alkaline and silane coupling agents resulted in substantial adhesion improvement to the polyester matrix in comparison to the untreated fibers and fibers treated by alkaline and silane methods only.     

New Coupling Agents as Adhesion Promoters at the Poly(Phenylene Sulfide)/Glass Interface-Studies with Micro and Macro Composites

Carboxy-functionalized poly(phenylene sulfide) having different molar masses and amount of the functional group were prepared in order to be used with γ-aminopropyltriethoxysilane as surface treatment of E-glass fibers. These grafted polymer chains act as connecting chains in order to improve the interfacial shear strength of the PPS-glass interface. According to their chemical nature, which is the same as the PPS matrix, and their ability to crystallize in the same crystalline form as the pure PPS, a continuum of bonding from the fiber surface to the bulk matrix is achieved. A chemical linkage is established at the glass surface by means of hydrolyzed ethoxysilane groups of the γ-APS and from the formation of amide units resulting from the reaction of amine functions of the silane and the carboxylic groups of the modified PPS. A “physical” linkage is expected between the grafted PPS and the PPS chains by means of entanglements and co-crystallization. A large improvement of the interfacial shear strength measured from the microdroplet test is observed when a modified-PPS having a medium molar mass and a low amount of functional groups is used in comparison with untreated or silane-treated glass fibers. This improvement is also observed for short glass fibers/PPS composite materials. In fact, a large improvement is obtained on mechanical properties such as the tensile, flexural, and impact strengths.     

In situ composite fibers: Blends of liquid crystalline polymer and poly (ethylene terephthalate)

To augment the concept of in situ composites as alternatives to fiber-reinforced composites, polyblends of a thermotropic liquid crystalline polymer (LCP) and poly(ethylene terephthalate) (PET) were prepared. Fiber-spinning of the blends was performed on a piston-driven plastorneter. Blends of LCP and a low-intrinsic-viscosity PET resin showed poor mechanical performance, which was attributed to their processing behavior. Blends of LCP and a high intrinsicviscosity PET manifested an almost additive behavior with regard to tensile modulus and strength. Elongation of the blends, however, displayed a radical decline, which is reminiscent of fiber-reinforced composites. Heat treatment of the blend fibers modestly increased the tensile properties of the LCP-rich compositions. Blend fibers from PET-rich compositions exhibit a moderate decline in tensile properties owing to thermal relaxation of PET. The data demonstrate that in situ composites or blends of thermotropic LCPs and isotropic polymers present challenging alternatives to fiber-reinforced composite systems because of their ease of processing.     

Drawing behavior of polyblend fibers from polypropylene and liquid crystal polymers

Polyblend fibers were made from mixtures of polypropylene (PP) and thermotropic liquid crystal polymers (LCPs). The as-spun fibers were drawn to produce the oriented structure for the PP matrix. The LCPs were found to exist in thin and long fibrils in the as-spun fibers; after drawing, they were split into short fragments. From a simplified model whereby a single LCP fibril is embedded in a PP matrix fiber, it was calculated out that the length of the LCP fibril in the drawn fiber is directly proportional to the fibril diameter and tenacity, and is reversely proportional to the compressional stress on the fibril and the friction coefficient between the fibril and the surrounding matrix. With regard to the drawing conditions, it was found that a long length of the LCP fibrils can be preserved by increasing the drawing temperature, or by reducing the draw rate. The effect of two-stage drawing on the LCP phase morphology was also studied in the present work. © 1994 John Wiley & Sons, Inc.     

Interfacial properties of polycarbonate/liquid‐crystal polymer and polystyrene/high‐impact polystyrene polymer pairs under shear deformation

We developed an energy model derived from the first principle for multilayer configurations to enhance our understanding of the interfacial property between two polymers under shear deformation. We carried out specific experiments satisfying the boundary and loading conditions of the model to obtain the energy dissipation factor (β), which characterized and quantified the interfacial property. Two polymer pairs, the miscible system polystyrene (PS)/high‐impact polystyrene (HIPS) and the immiscible system polycarbonate (PC)/liquid‐crystal polymer (LCP), were investigated. As expected, β was zero for PS/HIPS, reflecting the strong interaction at the PS/HIPS interface. For PC/LCP, the value of β could be significant, and its behavior was complex; it reflected the thermal sensitivity and thermal history effect of the PC/LCP interface. A positive value of β also indicated the possibility of slip at the interface and provided an explanation for the negative deviation from the rule of mixture. This complex behavior of the interface was attributed to the changes in the phases and microstructure of LCPs and, therefore, the LCP/PC interface as thermal cycling was carried out in the melting/nematic range of LCPs. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 258–269, 2003     

Rheological,mechanical, and adhesive properties of thermoplastic-LCP blends filled by glass fibers

Rheological, mechanical, and adhesive properties have been studied of two-phase polymer blends containing a liquid crystal copolyester of poly(ethylelene terephthalate) and p-hydroxybenzoic acid plus isotactic polypropylene (PP) with varying compositions and concentrations of glass fibers. Perfect fibrillation of the disperse LC-phase into the PP-matrix in capillary flow was observed at LCP concentrations >20 wt% and temperatures >488 K. This effect leads to a decrease of blend viscosity and a reinforcing of the extrudate's mechanical characteristics. At the same time, more essential reinforcement is achieved by the simultaneous addition of the reinforcing agents both of the LCP and glass fibers. Processing of PP is not impaired. It was found that the adhesive strength increases substantially when the amount of LCP in the blend exceeds a definite level, corresponding to a phase inversion. The results are explained by the formation near the interface of two adhesion layers: the first is composed of pure LCP having a higher surface tension, whereas the second layer represents the blend of various compositions. At small amounts of LCP, the adhesion failure proceeds in the interphase between the LCP and the blend. After the phase inversion, where adhesion strongly increases, the failure of adhesion joints proceeds near the interface between LCP and the glass.     

Evaluation of surface treatments for glass fibers in composite materials

The thermomechanical stability of a number of organosilane surface treatments for glass fibers was evaluated for use in a fiber reinforced epoxy resin. All of the silane coatings were found to improve the tensile strength of E-glass filaments, particularly at large gauge lengths. A phenylamino silane and an amino silane were particularly effective in this regard. The fiber/matrix interface was evaluated as a function of temperature and after exposure to boiling water using a single-fiber composite test. All silane coatings transmitted a higher interfacial shear stress than obtained in composites with no coatings, and in all cases the shear stress transmission was considerably higher than would be expected from the yield properties of the resin. Measurements of the glass transition temperature of the epoxy resin, as well as Fourier-Transform Infra-Red analysis, indicated modification of resin properties in a zone around the glass fibers. Each of the silane coatings provided more stable thermomechanical properties than those obtained with uncoated glass, at least until the silanes were irreversibly degraded by boiling water. A phenylamino silane provided the most thermally stable properties. Finally, unidirectional E-glass fiber reinforced laminae were fabricated and the measured values of longitudinal strength were compared favorably to theoretical predictions.     

Transport and adhesion properties of an unlined and a liquid‐crystalline polymer–lined vinyl ester thermoset exposed to severe environments

The application of liquid‐crystalline polymers (LCP) as lining materials for fiber‐reinforced plastics was investigated. The lining consisted of one uniaxially and one biaxially oriented LCP and, for comparison, a fluorinated ethylene propylene copolymer. The lining was attached to a glass‐fiber–reinforced vinyl ester thermoset. The laminates were examined with respect to their chemical resistance, transport/barrier properties, and lining/matrix adhesion behavior. The transport properties were determined by gravimetric desorption measurements and cup tests. It was shown that the LCP was suitable as a lining in organic solvent and nonoxidizing acid environments. Diffusivities, equilibrium concentrations, and transmission rates of water, methanol, toluene, and trichloroethylene were obtained in the LCP, the fluorinated ethylene propylene copolymer, and also, in the case of the vinyl ester, of hydrochloric acid. In general, the diffusivity and transmission rate in the LCP were one to several orders of magnitude lower than those of the fluorinated ethylene propylene copolymer and the vinyl ester. The reinforcement in the glass‐fiber–reinforced plastic led to an increase in the water and methanol diffusivities and transmission rates, which was probably attributable to liquid capillary diffusion. The lap‐shear bonding strength between the LCP and the vinyl ester was poor, but it was improved almost sixfold by a combined abrasive and oxygen plasma treatment. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 797–806, 2005     

Immiscible polymer blend electrorheological fluids: Composition dependence

We investigated the composition dependence of the electrorheological properties of immiscible polymer blends which consist of liquid crystalline polymers (LCPs) and polydimethylsiloxane (DMS). We used two different kinds of LCPs, designated as A and B polymers. We observed that for a fixed ratio of an LCP and DMS (LCP:DMS = 2:1) the electrorheological properties change from type I to type II as the fraction of the A polymer is reduced. Microscopic observations indicate that the change in the electrorheological properties is associated with the structural change; in type I, LCP droplets are dispersed in DMS, while in type II, DMS droplets are dispersed and, furthermore, that the structural change is associated with the miscibility between DMS and the LCPs; the A polymer is partially miscible with DMS, while the B polymer is hardly miscible with DMS. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3673–3680, 2002     

Debond behavior of copper fibers in thermoset matrices and their effect on fracture toughening

Single fiber pullout experiments were conducted to determine the adhesion quality, debond behavior and subsequent matrix fracture behavior for a variety of end-modified copper fibers. The matrices were: two different epoxy resins, polyester and polyurethane; the end-modified copper fibers were: straight, flat end-impacted, flat end-impacted with release agent applied and straight end-oxidized. The goal was to determine how the bonding and debonding behavior as well as the pullout behavior of the various fiber-matrix combinations affected the composite fracture toughness increment (ΔG). Results indicate that the greatest improvement in the calculated ΔG occurred with a fiber-matrix combination that had a moderate interface bond strength with an interfacial bond failure, minor matrix damage during fiber pullout and moderate post-debond interface friction. Selective oxidation of the fiber end was performed to determine if chemical anchoring of the fiber end could be as effective as mechanical (end-shaping) anchoring of the fiber into the matrix. Improvement in the adhesion bond strength as a result of the chemical anchoring resulted in a significantly lower ΔG compared to the end-impacted fibers because interfacial failure was not possible. This indicates that for the materials tested, mechanical anchoring of the fiber was better than chemical anchoring in improving ΔG. To decrease the adhesion bond strength and allow the fibers to debond, a release agent was applied to the flat end-impacted fiber prior to embedment into the matrix. This resulted in a significantly lower ΔG compared to straight and flat end-impacted fibers for all matrices tested, because the resulting debonding force and friction were significantly reduced. Pullout curves showed that with release agent applied, the end-shape did not effectively anchor the fiber into the matrix. The reduction in the pullout work indicates that the friction at the fiber-matrix interface plays a crucial role in actively anchoring the end-shaped fiber into the matrix after debonding.     

液晶高聚物的合成及应用研究最近进展

液晶高聚物是一种新型的高分子材料 ,可用于高强度高模量纤维的制造、电流变流体、导电高分子材料等领域。本文介绍液晶聚合物的结构、性能、合成方法及应用领域等。综述了近年来国内外对液晶高聚物的研究进展。     

Surface modification of films of various high temperature resistant thermoplastics

The influence of different surface treatments on the physical and chemical surface properties of poly(etheretherketone) (PEEK), poly(phenylenesulfide) (PPS) and a liquid crystal polymer (LCP) was studied. For all the three polymers, the adhesion strength of an adhesively-bonded copper foil could be increased significantly by a chemical etching process using chromic sulphuric acid or a low pressure air-plasma treatment. However, for LCP the enhancement of adhesion by the surface treatments was lower than for the other polymers. Peel tests were employed for determining the adhesion strength of the copper foil. The physical surface properties were investigated by laser scanning microscopy (LSM). Contact-angle measurements and X-ray photoelectron spectroscopy (XPS) provided detailed information on the chemical surface properties. The detailed XPS analyses revealed different chemical mechanisms of the surface treatments depending on the polymer investigated. In all cases an incorporation of oxygen containing groups by the surface treatments was found to be responsible for a better adhesion of the copper foil on the treated polymer films compared to the untreated.     

Effect of compounding on the properties of short fiber reinforced injection moldable thermoplastic composites

The mechanical properties of short-fiber-reinforced thermoplastic composites depend on the degree of interfacial bond strength between the fibers and polymer matrix. This interfacial bond strength can be increased by appropriate coupling agents. This study shows, for example, that an amino silane coupling agent improves the bond strength of nylon-aluminum fiber composites, but not polycarbonate-aluminum fiber composites. For cases where appropriate coupling agents are not available it is important to maintain as high a fiber aspect ratio as possible in a molded part. This study shows that a single screw compounder does less damage to glass or carbon fibers than a twin screw compounder under similar processing conditions when the polymer is in the form of pellets. When the polymer is supplied as a powder, satisfactory dry blends can be produced and the twin screw compounder does less damage to the fibers. In both cases, however, fibers initially 6 mm long are reduced to an average length less than 0.5 mm. The greatest degree of fiber size retention was observed when extrusion coated fiber pellets were used in the injection molding machine. The relationship between a fiber's tensile strength and the interfacial shear strength between a fiber and matrix yields a critical fiber aspect ratio below which the maximum reinforcing capability of the fibers are not being utilized. For the polymers investigated in this program, the critical aspect ratio for carbon fibers was found to be between 16 and 25 to 1. The polymers investigated include flame-retardant grades of acrylonitrile-butadiene-styrene (ABS) and poly(phenylene oxide)/polystyrene blend, nylon 6/6 and poly(phenylene sulfide).