Accelerated Ageing of Unidirectional Flax Fibers Reinforced Recycled Polypropylene Composites

Over the last decades, worldwide environmental awareness has grown due to the depletion of raw material resources and global warming. This awareness has prompted the development of new products more environmentally friendly. Among these products are biocomposite materials reinforced with natural fibers. The main challenge in developing the use of biocomposites in exterior applications is the lack of knowledge about their durability and the evolution of their mechanical and physicochemical properties in the long term. The aim of this work is to study the photooxidation of unidirectional (UD) composites based on recycled matrix. For this purpose, UD flax fiber composites based on recycled polypropylene were prepared by thermocompression. An accelerated aging test was carried out using a xenon arc WeatherOmeter. The consequences of UV exposure on the chemical composition and morphology of the surface of composites as well as on their tensile mechanical properties have been reported. The results showed that accelerated aging had a significant effect on the surface of these composites while it had little impact on their mechanical properties.

Development of Nondestructive Imaging Analysis Method Using Muonic X-Ray with a Double-Sided Silicon Strip Detector

In recent years, a nondestructive elemental analysis method based on muonic X-ray measurements has been developed and applied for various samples. Muonic X-rays are emitted after the formation of a muonic atom, which occurs when a negatively charged muon is captured in a muon atomic orbit around the nucleus. Because muonic X-rays have a higher energy than electronic X-rays due to the muon mass, they can be measured without being absorbed by a material. Thus, estimating the two-dimensional (2D) elemental distribution of a sample became possible using an X-ray imaging detector. In this work, we report a non-destructive imaging experiment using muonic X-rays at Japan Proton Accelerator Research Complex. The irradiated target consisted of a polypropylene material, and a double-sided silicon strip detector, which was developed as an imaging detector for astronomical obervation, was employed. A peak corresponding to muonic X-rays from the carbon atoms in the target was clearly observed in the energy spectrum at an energy of 14 keV, and 2D visualizations were successfully reconstructed to reveal the projection image from the target. This result demonstrates the potential of the nondestructive elemental imaging method that is based on muonic X-ray measurement. To obtain a higher position resolution for imaging a smaller target, a new detector system will be developed to improve the statistical analysis in further research.

Sustainable Development of Medium Strength Concrete Using Polypropylene as Aggregate Replacement

Plastic as an environmental burden is a well-rehearsed topic in the research area. This is due to its global demand and destructive impacts on the environment, which has been a significant concern to the governments. Typically, the use of plastic in the construction industry is seen across low-density, non-structural applications due to its diverse range of benefits including high strength-to-weight ratios, manipulability and durability. It can be said that with the level of plastic consumption experienced in the construction industry, an ongoing responsibility is shown for this sector to continually innovate alternatives for application of recycled plastic waste such as using plastic made replacement from polyethylene, polystyrene, polyvinyl and polypropylene in the concrete mix design. In this study, the impact of partially replaced fine aggregate with polypropylene in the concrete mix design was investigated to evaluate the concrete’s compressive strength by conducting an experimental work which comprises of six concrete mix batches with polypropylene replacements ranging from 0.5 to 3.0%. The results demonstrated a typical decline in the compressive strength with the addition of plastic aggregate, despite this reduction generally mitigated as the level of plastic in the concrete mix increased. Furthermore, two of the six plastic-containing concrete mixes tested in the current study exceeded the ST5 standardised prescribed concrete mix compressive strength requirement at 28-days containing 1.50% and 2.50% plastic aggregates, which demonstrated the potential for use of recycled polypropylene in structural applications, as a partial by mass, fine aggregate replacement in the concrete mix.

A Dynamic Mechanical Thermal T-Peel Test Approach to Characterize Interfacial Behavior of Polymeric Textile Composites

Basic understanding of interfacial mechanisms is of importance for the development of polymer composites. For this purpose, we need techniques to analyze the quality of interphases, their chemical and physical interactions and their strength and fracture resistance. In order to investigate the interfacial phenomena in detail, advanced characterization techniques are favorable. Dynamic mechanical thermal analysis (DMTA) using a rheological system is a sensitive tool. T-peel tests were performed with this system, to investigate the temperature-dependent peel behavior of woven textile composites. A model system was made of polyamide (PA) woven fabric laminated with films of polypropylene (PP) or PP modified by grafting with maleic anhydride (PP-g-MAH). Firstly, control measurements were performed with solely PP matrixes. Polymer melt investigations, as well as the extensional stress, extensional viscosity and extensional relaxation modulus at -10°C, 100 °C and 170 °C, demonstrate similar viscoelastic behavior for films made of PP-g-MAH and its non-modified PP-control. Frequency sweeps have shown that PP-g-MAH has a zero phase viscosity of around 1600 Pa·s and PP-control has a similar zero phase viscosity of 1345 Pa·s. Also, the gelation points are similar at 2.42*104 Pa (118 rad/s) and 2.81*104 Pa (161 rad/s) for PP-control and PP-g-MAH, respectively. Secondly, the textile composite was analyzed. The extensional stress of PA66 fabric laminated with either PP-control or PP-g-MAH at -10 °C, 25 °C and 170 °C for strain rates of 0.001 – 1 s-1 was investigated. The laminates containing the modified PP need more stress for T-peeling. However, the strengthening effect due to the modification decreases by increasing temperature and at 170 °C, just above the melting temperature of the matrix, the difference disappears. Independent of the matrix used in the textile composite, there is a decrease of extensional stress by increasing temperature. It appears that the more viscous is the matrix, the weaker the laminar adhesion. Possibly, the measurement is influenced by the fact that the laminate becomes stiffer at lower temperatures. Adhesive lap-shear testing at room temperature supports the findings obtained with the T-peel test. Additional analysis of the textile composite at the microscopic level ensures that the fibers are well embedded in the matrix. Atomic force microscopy (AFM) imaging of a cross section of the composite shows no gaps between the fibers and matrix. Measurements of the water contact angle show that the MAH grafted PP is more polar than the virgin-PP, and that suggests a more favorable chemical interaction of PP-g-MAH with PA, compared to the non-modified PP. In fact, this study indicates that T-peel testing by DMTA is a technique to achieve more insights into polymeric textile composites.

Fire Resistance of High Alumina Cement and Slag Based Ultra High Performance Fibre-Reinforced Cementitious Composites

Fibre-reinforced polymer (FRP) strengthened reinforced concrete (RC) structures are susceptible to intense deterioration when exposed to elevated temperatures, particularly in the incident of fire. FRP has the tendency to lose bond with the substrate due to the low glass transition temperature of epoxy; the key component of FRP matrix.  In the past few decades, various types of high performance cementitious composites (HPCC) were explored for the protection of RC structural members against elevated temperature. However, there is an inadequate information on the influence of elevated temperature on the ultra high performance fibre-reinforced cementitious composites (UHPFRCC) containing ground granulated blast furnace slag (GGBS) as a replacement of high alumina cement (HAC) in conjunction with hybrid fibres (basalt and polypropylene fibres), which could be a prospective fire resisting material for the structural components. The influence of elevated temperatures on the compressive as well as flexural strength of UHPFRCC, made of HAC-GGBS and hybrid fibres, were examined in this study. Besides control sample (without fibres), three other samples, containing 0.5%, 1% and 1.5% of basalt fibres by total weight of mix and 1 kg/m3 of polypropylene fibres, were prepared and tested. Another mix was also prepared with only 1 kg/m3 of polypropylene fibres. Each of the samples were retained at ambient temperature as well as exposed to 400, 700 and 1000 °C followed by testing after 28 and 56 days of conventional curing. Investigation of results disclosed that the use of hybrid fibres significantly helped to improve the ambient temperature compressive and flexural strength of UHPFRCC, which was found to be 80 and 14.3 MPa respectively. However, the optimum residual compressive strength was marked by UHPFRCC-CP (with polypropylene fibres only), equally after both curing days (28 and 56 days), i.e. 41%. In addition, the utmost residual flexural strength, after 28 and 56 days of curing, was marked by UHPFRCC– CP and UHPFRCC– CB2 (1 kg/m3 of PP fibres + 1% of basalt fibres) i.e. 39% and 48.5% respectively.

Stress-Strain Relation for Hybrid Fiber Reinforced Concrete at Elevated Temperature

The performance of concrete structures in fire depends on several factors which include, among others, the change in material properties due to the fire. Today, fiber reinforced concrete (FRC) belongs to materials which have been widely used for various structures and elements. While the knowledge and experience with FRC behavior under ambient temperature is well-known, the effect of elevated temperature on its behavior has to be deeply investigated. This paper deals with an experimental investigation and stress‑strain relations for hybrid fiber reinforced concrete (HFRC) which contains siliceous aggregates, polypropylene and steel fibers. The main objective of the experimental investigation is to enhance a database of mechanical properties of concrete composites with addition of fibers subject to elevated temperature as well as to validate existing stress-strain relations for HFRC. Within the investigation, a unique heat transport test, compressive test and splitting tensile test were performed on 150 mm cubes heated up to 200, 400, and 600 °C with the aim to determine a time period for uniform heat distribution in test specimens and the mechanical properties of the investigated concrete composite, respectively. Both findings obtained from the presented experimental test as well as experimental data collected from scientific papers so far served for validating the computational accuracy of investigated stress-strain relations for HFRC which have been developed during last few years. Owing to the presence of steel and polypropylene fibers, HFRC becomes a unique material whose structural performance differs from conventional plain concrete when exposed to elevated temperature. Polypropylene fibers in HFRC lower the risk of concrete spalling as the fibers burn out shortly with increasing temperature due to low ignition point and as a consequence pore pressure decreases. On the contrary, the increase in the concrete porosity might affect the mechanical properties of the material. To validate this thought requires enhancing the existing result database which is very limited and does not contain enough data. As a result of the poor database, only few stress-strain relations have been developed so far to describe the structural performance of HFRC at elevated temperature. Moreover, many of them are inconsistent and need to be refined. Most of them also do not take into account the effect of both a fiber type and fiber content. Such approach might be vague especially when high amount of polypropylene fibers are used. Therefore, the existing relations should be validated in detail based on other experimental results.

Triplet Shear Tests on Retrofitted Brickwork Masonry Walls

The main objective of this experimental study is to assess the shear strength and the crack behavior of the triplets built of perforated brickwork masonry elements. In order to observe the influence of shear resistance and energy dissipating before and after retrofitting applications by using the reinforcing system, static-cyclic shear tests were employed in the structural mechanics laboratory of Sakarya University. The reinforcing system is composed of hybrid multiaxial seismic fabric consisting of alkali resistant glass and polypropylene fibers. The plaster as bonding material used in the specimen’s retrofitting consists of expanded glass granular. In order to acquire exact measuring data about the failure behavior of the two mortar joints under shear stressing, vertical load-controlled cylinder having force capacity of 50 kN and loading rate of 1.5 mm/min. with an internal inductive displacement transducers is carried out perpendicular to the triplet specimens. In this study, a total of six triplet specimens with textile reinforcement were prepared for these shear bond tests. The three of them were produced as single-sided reinforced triplets with seismic fabric, while the others were strengthened on both sides. In addition, three triplet specimens without retrofitting and plaster were also tested as reference samples. The obtained test results were given in the manner of force-displacement relationships, ductility coefficients and shear strength parameters comparatively. It is concluded that two-side seismic textile applications on masonry elements with relevant plaster have considerably increased the sheer force resistance and the ductility capacity.

Extended Shelf Life of Chicken Meat Using Carboxymethyl Cellulose Coated Polypropylene Films Containing Zataria multiflora Essential Oil

The purpose of the present study was to evaluate carboxymethyl cellulose (CMC) coated polypropylene (PP) films containing Zataria multiflora (ZEO) essential oils (4%) as an antimicrobial packaging for chicken breast stored at 4 °C. To increase PP film hydrophilicity, it was treated by atmospheric cold plasma prior to coating by CMC. Then, different films including PP, PP/CMC, PP/CMC containing 4% of ZEO were used for the chicken meat packaging in vapor phase. Total viable count and pseudomonads population and oxidative (TBA) changes of the chicken breast were analyzed during shelf life. Results showed that the shelf life of chicken meat kept in films containing ZEO improved from three to nine days compared to the control sample without any direct contact with the film. Study of oxygen barrier properties of bilayer film without essential oils (0.096 cm3 μm/m2 d kPa) in comparison with PP film (416 cm3 μm/m2 d kPa) shows that coating of PP with CMC significantly reduces oxygen permeation of the obtained packaging (P

Functionalization of Polypropylene with Chiral Monomer for Improving Hemocompatibility

Polypropylene (PP) is one of the most commonly used plastics because of its low density, outstanding mechanical properties, and low cost. However, its drawbacks such as low surface energy, poor dyeability, lack of chemical functionalities, and poor compatibility with polar polymers and inorganic materials, have restricted the application of PP. To expand its application in biomedical materials, functionalization is considered to be the most effective way. In this study, PP was functionalized with a chiral monomer, (S)-1-acryloylpyrrolidine-2-carboxylic acid ((S)-APCA), by free-radical grafting in the solid phase. The grafting degree of PP-g-APCA was determined by chemical titration method, and the chemical structure of functionalized PP was characterized by FTIR spectroscopy, which confirmed that the chiral monomer (S)-APCA was successfully grafted onto PP. Static water contact angle results suggested that the surface hydrophilicity of PP was significantly improved by solid phase grafting and assistance of surface water treatment. Protein adsorption and platelet adhesion results showed that hemocompatibility of PP was greatly improved by grafting the chiral monomer.

A Comparative Study on Air Permeability Properties of Multilayered Nonwoven Structures

Air permeability plays an important role for applications such as filtration, thermal and acoustic insulation. The study discussed in this paper was conducted in an attempt to investigate air permeability property of various combinations of nonwovens. The PROWHITE air permeability tester was used for the measurement of the air permeability of the samples in accordance with the relevant standards and a comparative study of the results were made. It was found that the fabric mass per unit area was closely related to the air-permeability. The air permeability decreased with the increase in mass per unit area. Additionally, the air permeability of nonwoven fabrics decreased with the increase in thickness. Moreover, air permeability of multilayered SMS nonwoven structures was lower than those of single layered ones.

A Numerical Study on Micromechanical Aspects in Short Fiber Composites

This study focused on the contribution of micro-mechanical parameters on the macro-mechanical response of short fiber composites, namely polypropylene matrix reinforced by glass fibers. In the framework of this paper, an attention has been given to the glass fibers length, as micromechanical parameter influences the overall macroscopic material’s behavior. Three dimensional numerical models were developed and analyzed through the concept of a Representative Volume Element (RVE). Results of the RVE-based approach were compared with analytical Halpin-Tsai’s model.

Time Temperature Dependence of Long Fiber Reinforced Polypropylene Manufactured by Direct Long Fiber Thermoplastic Process

In order to reduce fuel consumption, the weight of automobiles has to be reduced. Fiber reinforced polymers offer the potential to reach this aim because of their high stiffness to weight ratio. Additionally, the use of fiber reinforced polymers in automotive applications has to allow for an economic large-scale production. In this regard, long fiber reinforced thermoplastics made by direct processing offer both mechanical performance and processability in injection moulding and compression moulding. The work presented in this contribution deals with long glass fiber reinforced polypropylene directly processed in compression moulding (D-LFT). For the use in automotive applications both the temperature and the time dependency of the materials properties have to be investigated to fulfill performance requirements during crash or the demands of service temperatures ranging from -40 °C to 80 °C. To consider both the influence of temperature and time, quasistatic tensile tests have been carried out at different temperatures. These tests have been complemented by high speed tensile tests at different strain rates. As expected, the increase in strain rate results in an increase of the elastic modulus which correlates to an increase of the stiffness with decreasing service temperature. The results are in good accordance with results determined by dynamic mechanical analysis within the range of 0.1 to 100 Hz. The experimental results from different testing methods were grouped and interpreted by using different time temperature shift approaches. In this regard, Williams-Landel-Ferry and Arrhenius approach based on kinetics have been used. As the theoretical shift factor follows an arctan function, an empirical approach was also taken into consideration. It could be shown that this approach describes best the time and temperature superposition for glass fiber reinforced polypropylene manufactured by D-LFT processing.

Effect of Chemical Modifier on the Properties of Polypropylene (PP) / Coconut Fiber (CF) in Automotive Application

Chemical modifier (Acrylic Acid) is used as filler treatment to improve mechanical properties and swelling behavior of polypropylene/coconut fiber (PP/CF) composites by creating more adherent bonding between CF filler and PP Matrix. Treated (with chemical modifier) and untreated (without chemical modifier) composites were prepared in the formulation of 10 wt%, 20 wt%, 30 wt%, and 40 wt%. The mechanical testing indicates that composite with 10 wt% of untreated composite has the optimum value of tensile strength, and the composite with chemical modifier shows the tensile strength was increased. By increasing of filler loading, elastic modulus was increased while the elongation at brake was decreased. Meanwhile, the swelling test discerned that the increase of filler loading increased the water absorption of composites and the presence of chemical modifier reduced the equilibrium water absorption percentage.

The Analysis of Defects Prediction in Injection Molding

This paper presents an evaluation of a plastic defect in injection molding before it occurs in the process; it is known as the short shot defect. The evaluation of different parameters which affect the possibility of short shot defect is the aim of this paper. The analysis of short shot possibility is conducted via SolidWorks Plastics and Taguchi method to determine the most significant parameters. Finite Element Method (FEM) is employed to analyze two circular flat polypropylene plates of 1 mm thickness. Filling time, part cooling time, pressure holding time, melt temperature and gate type are chosen as process and geometric parameters, respectively. A methodology is presented herein to predict the possibility of the short-shot occurrence. The analysis determined melt temperature is the most influential parameter affecting the possibility of short shot defect with a contribution of 74.25%, and filling time with a contribution of 22%, followed by gate type with a contribution of 3.69%. It was also determined the optimum level of each parameter leading to a reduction in the possibility of short shot are gate type at level 1, filling time at level 3 and melt temperature at level 3. Finally, the most significant parameters affecting the possibility of short shot were determined to be melt temperature, filling time, and gate type.

Antimicrobial Properties of SEBS Compounds with Zinc Oxide and Zinc Ions

The increasing demand of thermoplastic elastomers is related to the wide range of applications, such as automotive, footwear, wire and cable industries, adhesives and medical devices, cell phones, sporting goods, toys and others. These materials are susceptible to microbial attack. Moisture and organic matter present in some areas (such as shower area and sink), provide favorable conditions for microbial proliferation, which contributes to the spread of diseases and reduces the product life cycle. Compounds based on SEBS copolymers, poly(styrene-b-(ethylene-co-butylene)-b-styrene, are a class of thermoplastic elastomers (TPE), fully recyclable and largely used in domestic appliances like bath mats and tooth brushes (soft touch). Zinc oxide and zinc ions loaded in personal and home care products have become common in the last years due to its biocidal effect. In that sense, the aim of this study was to evaluate the effect of zinc as antimicrobial agent in compounds based on SEBS/polypropylene/oil/ calcite for use as refrigerator seals (gaskets), bath mats and sink squeegee. Two zinc oxides from different suppliers (ZnO-Pe and ZnO-WR) and one masterbatch of zinc ions (M-Zn-ion) were used in proportions of 0%, 1%, 3% and 5%. The compounds were prepared using a co-rotating double screw extruder (L/D ratio of 40/1 and 16 mm screw diameter). The extrusion parameters were kept constant for all materials. Tests specimens were prepared using the injection molding machine. A compound with no antimicrobial additive (standard) was also tested. Compounds were characterized by physical (density), mechanical (hardness and tensile properties) and rheological properties (melt flow rate - MFR). The Japan Industrial Standard (JIS) Z 2801:2010 was applied to evaluate antibacterial properties against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). The Brazilian Association of Technical Standards (ABNT) NBR 15275:2014 were used to evaluate antifungal properties against Aspergillus niger (A. niger), Aureobasidium pullulans (A. pullulans), Candida albicans (C. albicans), and Penicillium chrysogenum (P. chrysogenum). The microbiological assay showed a reduction over 42% in E. coli and over 49% in S. aureus population. The tests with fungi showed inconclusive results because the sample without zinc also demonstrated an inhibition of fungal development when tested against A. pullulans, C. albicans and P. chrysogenum. In addition, the zinc loaded samples showed worse results than the standard sample when tested against A. niger. The zinc addition did not show significant variation in mechanical properties. However, the density values increased with the rise in ZnO additives concentration, and had a little decrease in M-Zn-ion samples. Also, there were differences in the MFR results in all compounds compared to the standard.

Studying the Effect of Nanoclays on the Mechanical Properties of Polypropylene/Polyamide Nanocomposites

Nanocomposites based on polypropylene/polyamide 66 (PP/PA66) nanoblends containing organophilic montmorillonite (OMMT) and maleic anhydride grafted polypropylene (PP-g-MAH) were prepared by melt compounding method followed by injection molding. Two different types of nanoclays were used in this work. DELLITE LVF is the untreated nanoclay and DELLITE 67G is the treated one. The morphology of the nanocomposites was studied using the XR diffraction (XRD). The results indicate that the incorporation of treated nanoclay has a significant effect on the impact strength of PP/PA66 nanocomposites. Furthermore, it was found that XRD results revealed the intercalation, exfoliation of nanaclays of nanocomposites.

Synthesis and Characterization of Recycled Isotactic Polypropylene Nanocomposites Containing Date Wood Fiber

Nanocomposites of isotactic polypropylene (iPP) and date wood fiber were prepared after modification of the host matrix by reactive extrusion grafting of maleic anhydride. Chemical and mechanical treatment of date wood flour (WF) was conducted to obtain nanocrystalline cellulose. Layered silicates (clay) were partially intercalated with date wood fiber, and the modified layered silicate was used as filler in the PP matrix via a melt-blending process. The tensile strength of composites prepared from wood fiber modified clay was greater than that of the iPP-clay and iPP-WF composites at a 6% filler concentration, whereas deterioration of mechanical properties was observed when clay and WF were used alone for reinforcement. The dispersion of the filler in the matrix significantly decreased after clay modification with cellulose at higher concentrations, as shown by X-ray diffraction (XRD) data.

Ultrasonic Pulse Velocity Investigation of Polypropylene and Steel Fiber Reinforced Concrete

Ultrasonic pulse velocity (UPV) method has been shown for some time to provide a reliable means of estimating properties and offers a unique opportunity for direct, quick and safe control of building damaged by earthquake, fatigue, conflagration and catastrophic scenarios. On this investigation hybrid reinforced concrete has been investigated by UPV method. Hooked end steel fiber of length 50 and 30 mm was added to concrete in different proportion 0, 0.25, 0.5, and 1 % by the volume of concrete. On the other hand, polypropylene fiber of length 12, 6, 3 mm was added to concrete of 0.1, 0.2, and 0.4 % by the volume of concrete. Fifteen different mixture has been prepared to investigate the relation between compressive strength and UPV values and also to investigate on the effect of volume and type of fiber on UPV values.

Effect of Modified Layered Silicate Nanoclay on the Dynamic Viscoelastic Properties of Thermoplastic Polymers Nanocomposites

This work aims to investigate the structure–property relationship in ternary nanocomposites consisting of polypropylene as the matrix, polyamide 66 as the minor phase and treated nanoclay DELLITE 67G as the reinforcement. All PP/PA66/Nanoclay systems with polypropylene grafted maleic anhydride PP-g-MAH as a compatibilizer were prepared via melt compounding and characterized in terms of nanoclay content. Morphological structure was investigated by scanning electron microscopy. The rheological behavior of the nanocomposites was determined by various methods, viz melt flow index (MFI) and parallel plate rheological measurements. The PP/PP-g-MAH/PA66 nanocomposites showed a homogeneous morphology supporting the compatibility improvement between PP, PA66, and nanoclay. SEM results revealed the formation of nanocomposites as the nanoclay was intercalated and exfoliated. In the ternary nanocomposites, the rheological behavior showed that, the complex viscosity is increased with increasing the nanoclay. The results showed that the use of nanoclay affects the variations of storage modulus (G′), loss modulus (G″) and the melt elasticity.

Effects of Coupling Agent on the Properties of Durian Skin Fibre Filled Polypropylene Composite

Durian skin is a newly explores natural fibre potentially reinforced polyolefin for diverse applications. In this work, investigation on the effect of coupling agent, maleic anhydride polypropylene (MAPP) on the mechanical, morphological, and thermal properties of polypropylene (PP) reinforced with durian skin fibre (DSF) was conducted. The presence of 30 wt% DSF significantly reduced the tensile strength of PP-DSF composite. Interestingly, even though the same trend goes to PP-DSF with the presence of MAPP, the reduction is only about 4% relative to unreinforced PP and 18% higher than PP-DSF without MAPP (untreated composite or UTC). The used of MAPP in treated composite (TC) also increased the tensile modulus, flexural properties and degradation temperature. The enhanced mechanical properties are consistent with good interfacial interaction as evidenced under scanning electron microscopy.