A review of the analysis and characterisation of polymeric glass fibre sizings

Glass fibre reinforcements form the backbone of a composites industry. Possibly the most critical component involved in the manufacture of glass fibres and their composites is the fibre sizing. Yet because of the intense level of secrecy surrounding size formulations there are few who have more than a superficial understanding of sizings. Composite developers and researchers have a growing need for practical tools which can assist with the understanding of the nature and role of sizings on the glass fibres which reinforce their composites. This work reviews some of the most relevant articles from the widely dispersed literature around the analysis and characterisation of these polymeric sizings. The review covers the analysis and characterisation of the polymeric sizing layer on the glass fibre surface using high vacuum surface analysis techniques, thermal analysis, atomic force microscopy based techniques, surface energy analysis, infrared methods, and combined multiple analysis techniques. The conclusions highlight the fragmented nature of the knowledge base on sizings and the lack of reliable and reproducible reference materials on which to build real progress in the understanding of this critical technology.     

Effect of carbon fiber surface functionality on the moisture absorption behavior of carbon fiber/epoxy resin composites

Polyacrylonitrile (PAN)‐based carbon fibers were electrochemically oxidized in aqueous ammonium bicarbonate with increasing current density. The electrochemical treatment led to significant changes of surface physical properties and chemical structures. The oxidized fibers showed much cleaner surfaces and increased levels of oxygen functionalities. However, it was found that there was no correlation between surface roughness and the fiber/resin bond strength, i.e. mechanical interlocking did not play a major role in fiber/resin adhesion. Increases in surface chemical functionality resulted in improved fiber/resin bonding and increased interlaminar shear strength (ILSS) of carbon fiber reinforced epoxy composites. The relationship between fiber surface functionality and the hydrothermal aging behavior of carbon fiber/epoxy composites was investigated. The existence of free volume resulted from poor wetting of carbon fibers by the epoxy matrix and the interfacial chemical structure were the governing factors in the moisture absorption process of carbon fiber/epoxy composites. Copyright © 2016 John Wiley & Sons, Ltd.     

Monitoring the glass transition temperature of polymeric composites with carbon nanotube buckypaper sensor

Carbon nanotube (CNT) Buckypapers can be infused with resin and easily incorporated into conventional fiber reinforced composites. In this paper, we propose to use Buckypaper (BP) as a new measuring method to determine the glass transition temperature of polymeric composites. The CNT-only BP was fabricated by spray-vacuum filtration method with monodispersion of multi-wall carbon nanotubes, and then co-cured with polymeric composites. After manufacturing, the glass transition temperature of polymeric composites could be obtained from the relationship between resistance and temperature of BP during the dynamic heating process. Experimental results show that the glass transition temperature of composite samples A and B monitored by BP sensors were 127 °C and 180 °C, while such temperatures obtained from a dynamical mechanical analyzer (DMA) were 128 °C and 184 °C respectively. This paper not only reveals the ability of BP as a sensor for monitoring the glass transition temperature of composite but also provides a new way to understand the glass transition phenomenon of composite.     

Mechanical behavior of basalt and glass textile composites at high strain rates: A comparison

The aim of this paper is to study and compare the mechanical behavior of woven basalt and woven glass epoxy composites at high strain rates, in order to assess the possibility of replacing glass fiber composites with basalt fiber composites for aircraft secondary structures, such as radomes, fairings, wing tips, etc. Both composites were produced using the same epoxy matrix, the same manufacturing technique, and with comparable densities, fiber volume fractions, and static stiffnesses. Dynamic tensile and shear experiments were performed using a split Hopkinson tension bar, in addition to reference quasi-static experiments to compare both material behaviors over a wide range of strain rates. Normalized results with respect to the material density and fiber volume fraction showed that basalt epoxy composite had higher elastic stiffness, ultimate tensile strength, ultimate tensile strain, and absorbed energy in tension compared to glass epoxy composite. This suggests a promising potential in replacing glass fibers composites with basalt fiber composites in aircraft secondary structures and, more generally, components prone to impact. However, for the basalt epoxy composite, improvements in the fiber-matrix adhesion and in the manufacturing technique are still required to enhance their shear properties compared to glass fiber composites, and fully exploit the potential of basalt epoxy composites in aeronautical applications.     

Effects of plasma treatment of carbon fibers on interfacial properties of BMI resin composites

High performance continuous fiber surface modification by inductively coupled RF plasma (ICP) and dielectric barrier discharge (DBD) low temperature plasma were conducted. X-ray photoelectron spectroscopy (XPS) and other analytical testing methods systematically studied plasma treatment time, discharge power, discharge pressure, etc, on fiber surface state, surface composition, and surface shape changes in the appearance and wetting properties. The results show that after plasma treatment the surface of the fiber is grafted with a large number of polar functional groups such as carboxyl groups and hydroxyl groups. The surface roughness increases, the surface free energy increases, and the fiber wetting property is significantly improved, resulting in improvement in interlaminar shear strength (ILSS) between the fiber and the resin matrix. Finally, the surfaces of the fibers and its relationship with interfacial properties of fiber reinforced bismaleimide composites are also discussed.     

A novel dynamic constitutive micromechanical model to predict the strain rate dependent mechanical behavior of glass/epoxy laminated composites

In the present research, a novel dynamic constitutive micromechanical (DCM) model was developed to predict the strain rate dependent mechanical behavior of laminated glass/epoxy composites. The present model is an integration of the generalized strain rate dependent constitutive model as a constitutive model for the neat polymer, the plasticity model of Huang as a micromechanical model, and dynamic progressive failure criteria. This model is able to predict the longitudinal and transverse tensile and in-plane shear behaviors of unidirectional glass/epoxy composites with arbitrary fiber volume fractions at arbitrary strain rates. The present model can also predict the stress-strain behavior of laminated composites with different layups and fiber volume fractions at arbitrary strain rates. A comparison between the results predicted by the present model and the available experimental data showed that the model predicts the strain rate dependent mechanical behavior of glass/epoxy composites with very good accuracy.     

Surface treatment of Basalt fiber for use in automotive composites

Balancing the performance, durability and safety requirements of automotive systems with the regulatory landscape in an environment of climate change has accelerated the search for sustainable fiber reinforced polymer composites for automobile structures. Glass fiber reinforced thermoplastic polymer composites (GFRP) are widely used in certain structures like front end modules and liftgate; However, they cannot be used in more demanding applications due to their low mechanical properties. Carbon fiber reinforced thermoplastic polymer composites (CFRP) are promising candidates for applications like bonnet, but their use is constrained by cost. Basalt fiber reinforced thermoplastic polymer composites (BFRP) are sustainable materials that can be positioned between GFRP and CFRP in terms of performance and cost-effectiveness. The mechanical performance of the BFRP depend on the quality of the fiber-matrix interface that aids in efficient load transfer from the matrix to the fiber. Typically, basalt fibers are inert in nature and need treatments to improve its adhesion to polymeric matrices. The major chemical treatments that are reviewed in this article include matrix functionalization, silane treatment, functionalized nanomaterial coating and plasma polymerization. The physical treatments reviewed include plasma treatment and milling. It is evident that chemically treating the basalt fiber with a functionalized nanomaterial yields BFRP with a good stiffness – toughness balance that can be used for challenging metal replacements as also in new emerging areas like sensing and 3D printing.     

A convection–diffusion porous media model for moisture transport in polymer composites: Model development and validation

Moisture may cause many detrimental effects to polymers and their composites, thus inhibiting the applications of polymeric materials in hot and humid environments. In this article, a convection–diffusion porous media model is derived to better characterize rapid moisture transport in polymer composites at high temperatures. The model considers both continuum diffusion in solid and high‐pressure convection taking place in the pore network. Coupling of convection and diffusion is achieved by combining the law of conservation of mass, Darcy's law, the liquid–vapor chemical equilibrium, and the ideal gas law. The presented model is validated by conducting experimental tests on an epoxy compound. It is found that the proposed convection–diffusion model is more effective than diffusion‐only and convection‐only models for interpreting rapid desorption tests at high temperatures. A numerical study is also performed to predict maximum vapor pressure during a rapid heating process. Vapor pressure is found to be as high as 6.5 MPa at a heating rate of 10 K/s. It is concluded that the convection–diffusion model is able to capture both vapor dynamics and diffusion mechanism in porous polymeric materials, and can be potentially used to further investigate polymer‐moisture interactions. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1440–1449     

Durability and integrity studies of environmentally conditioned interfaces in fibrous polymeric composites: Critical concepts and comments

Fibre reinforced polymer (FRP) composites are the most promising and elegant material of the present century. Their durability and integrity in various service environments can be altered by the response of its constituent i.e. fibre, polymer matrix, and the existing interface/interphase between the fibre and polymer matrix, in that particular environment. The interphase is generally manifested by chemical bonding, molecular segregation and also by van der Waals bonding. The sizing of fibres generally influences the chemistry and character of the interface/interphase and might generate structural gradient in the polymer matrix. Their susceptibilities to degradation are dependent of the nature of environments and each of the constituents' responds differently and uniquely. Amongst the three constituents, the interface/interphase has a very critical role to play on the performance and reliability of FRP composites. The reduced glass transition temperature of the interphase may induce low modulus area, which subsequently affects fracture toughness and local stresses of the composite. These result in high fracture toughness at ambient temperatures, but significantly reduced performance at high temperatures.     

The numerical simulation of the mechanical failure behavior of shear thickening fluid/fiber composites: A review

This study reveals the finite element modeling of mechanical failure behavior of shear thickening fluid (STF)/fiber composites under impact. Numerical analysis and finite element modeling of the rheological properties of non-Newtonian fluid, STF are introduced. This review summarizes the model coupling methods in finite element modeling and the mechanical failure behavior prediction models of STF/fiber composites under impact. Further, the influencing factors on the accuracy of mechanical failure simulation models are analyzed. Factors such as the friction between fibers, shear rate, filler particles in the fibers, hysteresis effect and the boundary conditions should be considered in simulating the shear thickening effect of the composites.     

A novel fiber-grafting-sensing testing method for temperature deformation of piezoelectric composites

The deformation of piezoelectric composite has many deadly effects on the transducers and the sonar systems, but the relative testing method never been focused. Here we developed a novel fiber-grating-sensing method for the study of temperature deformation of the piezoelectric composites for the first time. With the increase of temperature, the deformations of the piezoelectric composite in three dimensions increased, and the increasing speeds (all speeds means slop of fitted line) were 1.4 × 10⁻³ (length), 1.8833 × 10⁻⁴ (width) and 3.1439 × 10⁻⁵ (thickness), respectively. After adding the deform information the data for the frequency constant and dielectric constant were revised. The decreasing speed of frequency constant lowered from −2.0373 to −2.0263. The increasing speed of dielectric constant lowered from 2.6779 to 2.6580 in the range of 25 °C–75 °C, and from 1.9647 to 1.9559 in the range of 75 °C–125 °C.     

A new ultrasonic measurement system for the cure monitoring of thermosetting resins and composites

Measurements of the ultrasonic sound speed of thermosetting resins and composites can be used as an in-process cure monitoring technique. Ultrasonic measurements have an advantage over other in-process techniques in that ultrasonic sensors do not make contact with the part (thus leaving no imbedded sensor or witness mark) and can make true bulk measurements of the part. A new commercially available ultrasonic cure monitoring system has been developed which easily enables ultrasonic measurements to be made in compression molding, resin transfer molding, and autoclave processes. Advancements in ultrasonic sensor technology enable the sensor to maintain good coupling to the part during thermal cycling to 260C. Data is presented showing the change in ultrasonic sound speed during the compression molding of a graphite-epoxy prepreg. The data shows a good relationship to the ionic conductivity and resistivity data collected via dielectric cure monitoring.This effort was sponsored by the Manufacturing Technology Directorate, Wright Laboratory (WL/MTX), Air Force Material Command, USAF, under cooperative agreement award(s) to NCMS. The U. S. Government is authorized to reproduce and distribute reprints for Governmental purposes notwithstanding any copyright notation thereon. The views and conclusions contained herein are those of the authors and should not be interpreted as necessarily representing the official policies or endorsements, either expressed or implied, of Wright Laboratory or the U.S. Government.     

A modified polymethylsilane as the precursor for ceramic matrix composites

A novel SiC precursor, A-PMS, was synthesized through a reaction of polymethylsilane (PMS) with SbCl₃, where the Si-H in PMS reacts with Sb-Cl to form Si-Sb bond with HCl evaporated. A-PMS was used as a precursor to prepare C_f/SiC ceramic matrix composites (CMCs) via polymer infiltration and pyrolysis (PIP) process. It is evident that SbCl₃ plays a very important role in promoting chain crosslinking, transforming of the Si-Si into Si-C bonds and stabilizing PMS from very high oxidation trend of the active Si-H bonds. A-PMS keeps liquid at room temperature that is suitable for the infiltration in the absence of any solvent. A-PMS can be cured into a fully crosslinked structure at 320 °C that leads to a very high ceramic yield up to 91% and an Si/C ratio near 1.12 after pyrolysis. The resulted CMCs samples reached a density of 1.76 g cm⁻³ and a flexural strength of 381 MPa after only four infiltration-pyrolysis cycles.     

A novel approach for preparation of conductive hybrid elastomeric nano‐composites

Since the discovery of carbon nanotubes (CNTs) and intrinsically conductive polymers, such as polyaniline (PANI) some research has focused on the development of novel hybrid materials by combining CNT and PANI to achieve their complementary properties. Electrically conductive elastomer nano‐composites containing CNT and PANI are described in the present investigation. The synthesis procedure includes in‐situ inverse emulsion polymerization of aniline doped with dodecylbenzene sulfonic acid in the presence of CNT and dissolved styrene‐isoprene‐styrene (SIS) block copolymer, followed by a precipitation–filtration step. The synthesis step is carried out under ultrasonication. The resulting uniform SIS/CNT/PANI dispersions are stable for long time durations. The incorporation of CNT/PANI in the SIS elastomeric matrix improves thermal, mechanical and electrical properties of the nano‐composites. The formation of continuous three‐dimensional CNT/PANI network, assumed to be responsible for enhancement of the resulting nano‐composite properties, is observed by HRSEM. A relatively low percolation threshold of 0.4 wt.% CNT was determined. The Young's modulus of the SIS/CNT/PANI significantly increases in the presence of CNT. High electrical conductivity levels were obtained in the ternary component systems. Copyright © 2013 John Wiley & Sons, Ltd.     

New method for the quantification of dequalinium cations in pharmaceutical samples by absorption and fluorescence diode array thin-layer chromatography

A diode array HPTLC method for dequalinium chloride in pharmaceutical preparations is presented. For separation a Nano TLC silica gel plate (Merck) is used with the mobile phase methanol—7.8% aqueous NH₄⁺CH₃COO⁻ (17:3, v/v) over a distance of 6 cm. Dequalinium chloride shows an R_F value of 0.58. Pure dequalinium chloride is measured in the wavelength range from 200 to 500 nm and shows several by-products, contour plot visualized in absorption, fluorescence and using the Kubelka–Munk transformation. Scanning of a single track in absorption and fluorescence measuring 600 spectra in the range from 200 to 1100 nm takes 30 s. As a sample pre-treatment of an ointment it is simply dissolved in methanol and can be quantified in absorption from 315 to 340 nm. The same separation can also be quantified using fluorescence spectrometry in the range from 355 to 370 nm. A new staining method for dequalinium chloride, using sodium tetraphenyl borate/HCl in water allows a fluorescence quantification in the range from 445 to 485 nm. The linearity range of absorption and fluorescence measurements is from 10 to 2000 ng. Sugar-containing preparations like liquids or lozenges with a reduced sample pre-treatment can be reliably quantified only in fluorescence. The total for the quantification of an ointment sample (measuring four standards and five samples), including all sample pre-treatment steps takes less than 45 min!     

Transcrystallization of PTFE fiber/PP composites. II. Effect of transcrystallinity on the interfacial strength

It has been found that transcrystallinity of polypropylene (PP) develops easily on the polytetrafluoroethylene (PTFE) fiber surface in spite of the low surface energy of the fiber. Effect of the transcrystallinity on the interfacial strength has been extensively investigated using a single-fiber pull-out test. By controlling the crystallization temperature, range 25–130°C, the thickness of the transcrystalline layer varied from 0 to 175 μm for thick specimens, ca. 1 mm thick. Measurements of the adhesive fracture energy, the interfacial shear strength and the frictional stress were carried out for specimens with different embedded fiber lengths. Results show that interfacial strength and fracture energy are independent of the transcrystalline thickness. The calculated value of interfacial shear strength is 3.6 MPa, and the fracture energy for debonding is 2.1 J/m². The presence of transcrystallinity does not promote the level of adhesion in PTFE/PP composites. However, the frictional stresses at the debonded fiber/matrix interface increase with transcrystalline thickness. It is attributed to the residual stresses which arise from shrinkage when specimens are cooled from crystallization temperature to room temperature. © 1996 John Wiley & Sons, Inc.     

Interfacial Studies for improving the adhesion of Cr/Al films on composites

The composites, such as CFRP and GFRP, have been widely applied in spaceflight, for their low specific gravity, low cost, and additional structural stability. However, the high resistivity of the composites severely inhibits their further applications. Therefore, Cr/Al films with low resistivity and high adhesion were deposited on composites by cathodic arc technique. The films were characterized by pull test, Dektak 8 Stylus Profilometer, SEM, XPS, XRD and Z‐82 standard four probes. Results show that the aluminum film of fcc structure is compact and uniform, with resistivity as low as bulk Al. The adhesion between Cr buffer layer and composite substrate was greatly enhanced because of the formation of the chemical bonds, such as Cr? C, Cr? O and Cr? N, at the Cr/composite interface. Copyright © 2011 John Wiley & Sons, Ltd.