A novel intumescent flame‐retardant system for flame‐retarded LLDPE/EVA composites

A new intumescent flame retardant (IFR) system consisting of ammonium polyphosphate (APP) and charing‐foaming agent (CFA) and a little organic montmorillonite (OMMT) was used in low‐density polyethylene (LLDPE)/ethylene‐vinyl acetate (EVA) composite. According to limiting oxygen index (LOI) value and UL‐94 rating obtained from this work, the reasonable mass ratio of APP to CFA was 3 : 1, and OMMT could obviously enhance the flame retardancy of the composites. Cone calorimeter (CONE) and thermogravimetric analysis (TGA) were applied to evaluate the burning behavior and thermal stability of IFR‐LLDPE/EVA (LLDPE/EVA) composites. The results of cone calorimeter showed that heat release rate peak (HRR‐peak) and smoke production rate peak (SPR‐peak) and time to ignition (TTI) of IFR‐LLDPE/EVA composites decreased clearly compared with the pure blend. TGA data showed that IFR could enhance the thermal stability of the composites at high temperature and effectively increase the char residue. The morphological structures of the composites observed by scanning electron microscopy (SEM) and X‐ray diffraction (XRD) demonstrated that OMMT could well disperse in the composites without exfoliation, and obviously improve the compatibility of components of IFR in LLDPE/EVA blend. The morphological structures of char layer obtained from Cone indicated that OMMT make the char layer structure be more homogenous and more stable. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Photodegradation and biodegradation by bacteria of mulching films based on ethylene‐vinyl acetate copolymer: Effect of pro‐oxidant additives

The photodegradation (432 h under irradiation of Xe‐Lamp‐solar filter) of an ethylene vinyl acetate (EVA) copolymer with vinyl acetate content of 9% was studied, and the effect of iron and calcium stearates was evaluated using different techniques such us attenuated total reflectance‐Fourier transform infrared spectroscopy (ATR‐FTIR), gel permeation chromatography (GPC), and thermal analysis methods (DSC and TGA). A re‐arrangement in crystallization and consequent decrease in thermal stability were found through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), which were in agreement with the chain scission tendency. The presence of Ca and Fe pro‐oxidants additives in EVA films increased the ketone carbonyl formation and decreased the ester absorption band of the acetate respect to the pure EVA, as it was evidenced by the significant changes in Carbonyl Indexes found by FTIR. The activity of stearates has been also evaluated by chemiluminescence, where the temperature‐ramping tests under nitrogen showed the formation of a peroxide peak at lower temperature. The lower stability of the films containing pro‐oxidants was evidenced by the values of oxidation induction time (OIT) determined by DSC. The results were supported by GC‐MS, where the concentration of extracted products identified in the EVA containing pro‐oxidants was significant and a much greater decrease in molecular weight was determined by GPC, which confirmed the development of degradation for EVA with Ca and Fe stearates in comparison to pure EVA. Biodegradation of photodegraded EVA films were studied at 45°C during 90 days using a mixture of Bacillus (MIX) (B. cereus, B. megaterium, and B. subtilis) and, in parallel, by Brevibacillus borstelensis as reference strain. Biodegradation of EVA‐films was studied by Chemiluminescence, ATR‐FTIR and GC‐product analysis and the data confirm more efficient biodegradation on the materials containing pro‐oxidants. The chemiluminescence emissions due to decomposition of oxidation species was observed at lower temperatures on the biodegraded samples. Also, the drastic decrease of carbonyl index and the disappearance of photogenerated low molecular products with biodegradation were more efficient on the biodegraded films containing pro‐oxidants. EVA mineralization was evaluated by carbon dioxide measurement using indirect impedance technique. Biodegradation by B. borstelensis and MIX at 45°C was similar and exhibited a pronounced difference between the pure photodegraded EVA film (around 15% of mineralization) and the corresponding photodegraded films containing Ca and Fe stearates where biodegradation extent reached values of 23‐26% of biodegradation after 90 days. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Triple‐shape‐memory polymer films created by forced‐assembly multilayer coextrusion

Triple‐shape‐memory polymers are capable of memorizing two temporary shapes and sequentially recovering from the first temporary shape to the second temporary shape and eventually to the permanent shape upon exposure to a stimulus. In this study, unique three‐component, multilayered films with an ATBTA configuration [where A is polyurethane (PU), B is ethylene vinyl acetate (EVA), and T is poly(vinyl acetate) (PVAc)] were produced as a triple‐shape‐memory material via a forced‐assembly multilayer film coextrusion process from PU, EVA, and PVAc. The two well‐separated thermal transitions of the PU–EVA–PVAc film, the melting temperature of EVA and the glass‐transition temperature of PVAc, allow for the fixing of the two temporary shapes. The cyclic thermomechanical testing results confirm that the 257‐layered PU–EVA–PVAc films possessed outstanding triple‐shape‐memory performance in terms of the shape fixity and shape‐recovery ratios. This approach allowed greater design flexibility and simultaneous adjustment of the mechanical and shape‐memory properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44405.     

Study on the morphology and properties of metallocene polyethylene and ethylene/vinyl acetate blends

Two commercial polymer materials, metallocene linear low density polyethylene (m‐LLDPE) and ethylene/vinyl acetate copolymer (EVA) have been used to form binary blends of various compositions. The mechanical properties, morphology, rheological behavior, dynamic mechanical properties, and crystallization of m‐LLDPE/EVA blends were investigated. It was found that with the addition of EVA, the fluidity and processability of m‐LLDPE were significantly improved, and the introduction of polar groups in this system showed no significant changes in mechanical properties at lower EVA content. As verified by morphology observation and differential scanning calorimetry analysis, miscible blends were formed within certain weight ratios. Dynamic mechanical property studies showed that flexibility of the blends was enhanced in comparion with pure m‐LLDPE, where the peak value of loss modulus shifted to lower temperature and its intensity was enhanced as EVA content increased, indicating the existence of more amorphous regions in the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 905–910, 2004     

LLDPE‐based mono‐ and multilayer blown films: Property enhancement through coextrusion

In this study we investigated the performance of multilayer coextruded linear low‐density polyethylene (LLDPE) blown films. Five‐layer films were compared with monolayer dry‐blended films, and the effects of layer composition and layout on the end‐use properties of the coextruded films were highlighted. Three different LLDPEs were used: a conventional Ziegler‐Natta LLDPE gas phase butene copolymer, an advanced Ziegler‐Natta LLDPE solution octene copolymer, and a single‐site LLDPE solution octene copolymer. Numerous five‐layer coextruded structures comprising the single‐site resin and the other two Ziegler‐Natta resins were produced. The coextruded structures composed of the LLDPE butene and the single‐site resin yielded improved end‐use properties relative to the monolayer‐blended films. This result was ascribed to the presence of interfacial transcrystalline layers. Also, blends of the single‐site LLDPE and the advanced Ziegler‐Natta LLDPE octene resins within selected layers of coextruded films showed slightly enhanced tear resistance. Finally, it was found that haze was significantly reduced when the outside layers were composed of the single‐site resin. POLYM. ENG. SCI., 45:1222–1230, 2005. © 2005 Society of Plastics Engineers     

Rheological behavior of ethylene–vinyl acetate copolymer and fabrication of micropyramid arrays by roll‐to‐roll hot embossing on its thin films

Films of ethylene–vinyl acetate (EVA) copolymer with different vinyl acetate (VA) contents were adopted as flexible substrates for fabrication of micropyramid arrays by roll‐to‐roll (R2R) hot embossing at roller temperatures 40–80 °C. An empirical relationship between rheological behavior of EVA in rubbery state and demolding performance of the films was explored. Dependence of average forming height of micropyramid arrays on VA content and roller temperatures was investigated. Our study showed that both viscosity and relaxation behavior of EVA can be related to the ultimate forming height of micropyramids. The relationships can provide references for experimental research and industrial manufacture on R2R hot embossing. Retroreflection of micropyramid arrays was observed and transmittances of the two sides of embossed films were studied. Transmittances of the VA28 film embossed at 60 °C were 97.9% (the embossed side) and 41.8% (the smooth side), which showed potential applications in reflective film and antireflective film fields. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45228.     

Effects of high‐energy electron beam on low‐density polyethylene materials containing EVA

A series of low‐density polyethylene (LDPE) blends with different amounts of ethylene–vinyl–acetate (EVA) was prepared and irradiated with 10 MeV electron beam in the range of 0–250 kGy at room temperature in air. EVA was used as a compatibilizer and softener in four different amounts: 5, 10, 20, and 30 wt %, based on polyethylene (PE). The crosslinking of the samples was studied on the basis of gel‐content measurements as well as some thermal and mechanical properties of the specimens. The results indicated that the LDPE and LDPE–EVA blends could be crosslinked by a high‐energy electron beam, of which their thermal and mechanical properties changed effectively, however, because of EVA content of the polymer; the blends were more sensitive to lower doses of radiation. These studies were carried out to obtain a suitable compound for heat‐shrinkable tubes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1049–1052, 2004     

Non‐Isothermal Crystallization Kinetics of an Ethylene‐Vinyl‐Acetate. II. Time‐Temperature‐Crystallinity‐Superposition

Ethylene vinyl acetate (EVA) is a random copolymer of ethylene and varying amounts of vinyl acetate that interfere with poly‐ethylene chain packing reducing crystallinity, thus improving transparency and lowering the melting temperature to 40°C–60°C. The material viscoelastic properties in its working conditions may thus depend on the crystallinity degree. The crystallization process is here rheologically studied in non‐isothermal conditions and the frequency spectra are measured at different temperatures to investigate the viscoelasticity of EVA. Coupling the crystallization kinetics and the viscoelastic spectra at different temperatures, that is, at different degree of crystallinity, we here determine two independent shift factors, one for the time‐crystallinity shift, the other for the time‐temperature shift, so to propose a new time‐temperature‐crystallinity‐superposition to reconcile all the data on a single master curve. In this way, the experimentally observable frequency range has been widened significantly so to detect all the relaxation times of the material from the shortest to the largest ones. POLYM. ENG. SCI., 59:2550–2556, 2019. © 2019 Society of Plastics Engineers     

Dynamic–mechanical properties of modified poly(ethylene‐co‐vinyl acetate)

To study the relationship among relaxation peaks observed in dynamic mechanical experiments and the structure of poly(ethylene‐co‐vinyl acetate) (EVA), EVA copolymers with different substitution in the carbonyl group were synthesized. EVA was hydrolyzed to obtain poly (ethylene‐co‐vinyl alcohol) and was subsequently reacted with formic, hexanoic, and octanoic acids. The copolymers synthesized were characterized by infrared spectroscopy. Analysis of the DMA spectra of the copolymers showed that their relaxation behavior depends on the vinyl acetate concentration. The α‐ and β‐transitions were observed in EVA copolymers with 8 and 18 wt % of functional groups, and the relationship among relaxation process with the structure of polymer was investigated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1371–1376, 2005     

Optimization of engineering and solvent resistive behavior of high vinyl acetate content EVA‐modified poly(ethylene‐co‐1‐octene) interpenetrating network blends using taguchi orthogonal array

Process parameters of poly (ethylene‐co‐vinyl acetate) (EVA)‐modified poly (ethylene‐co‐1‐octene) (POE)‐interpenetrating, double network blend was designed through Taguchi L9 orthogonal array as a novel approach for complete optimization of engineering and solvent‐swelling properties. Influence of different factors like EVA and peroxide concentrations, blending temperature, and blending time on gel content, tensile modulus, tensile strength, ultimate elongation were statistically calculated. Results showed good correlation between mathematical and physical inferences. Stress relaxation, hysteresis and other physico‐mechanicals like total elongation, solvent‐swelling, etc., were interestingly depended upon the nature of dominantly crosslinked phase instead of net crosslinking of the network hybrids. Sorption, on the other hand, depended on the hydrophobic‐hydrophilic property of the surfaces. The series of data produced finally helped to select the best process parameters under which a particular POE‐EVA blend composition yielded most balanced physico‐mechanicals. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mechanical changes of electron beam irradiated ethylene–vinyl acetate copolymer (EVA) film (I)

Electron beam irradiation of ethylene-vinyl acetate copolymer (EVA) film results in a marked depression of sorption of flavour compounds. This effect is presumed to be brought about by radical reactions, following changes in the structure. The crosslinking density and gel fraction increased with irradiation dose, and the maximum percent gel reached 70% for 20 Mrad-50g kg^?1 EVA film, 35% for 20 Mrad-95g kg^?1 EVA film and 50% for 10 Mrad-150g kg^?1 EVA film. In calculating the ratio of scission to crosslinking events, it was found that EVA film is a polymer of the scission type. The degree of crystallinity, X_c decreased significantly with increasing irradiation dose in all irradiated films. For unirradiated films, X_c decreased with increase in vinyl acetate content, which suggests that crystalline regions of EVA film are primarily composed of ethylene units. Therefore, the scission reaction may predominantly take place in the crystalline region, resulting in the formation of methyl or end vinyl groups. This was supported by measuring the film density, peak melting temperature and stress at yield.     

Foaming of poly(ethylene‐co‐vinyl acetate) and poly(ethylene‐co‐vinyl acetate‐co‐carbon monoxide) and their blends with carbon dioxide

Poly(ethylene‐co‐vinyl acetate) (EVA‐25) and poly(ethylene‐co‐vinyl acetate‐co‐carbon monoxide) (EVACO‐2410) and their blends with EVACO:EVA ratios of 80:20, 60:40, 40:60, and 20:80 were foamed using CO₂. These foams are of interest for applications ranging from footwear to medical devices. Foaming experiments were carried out using 1 mm thick melt‐extruded films in CO₂ at a range of pressures (100, 200, and 300 bar) and temperatures (30, 40, 50, and 60 °C). Foamability of the polymers was explored both under isothermal and gradient temperature conditions. Foams of EVACO‐2410 displayed high initial expansions followed by postfoaming relaxation and shrinkage while foams generated from EVA‐25 showed more dimensional stability. Blending EVACO‐2410 with EVA‐25 was explored as an approach to reduce postfoaming relaxation and shrinkage. The surfaces of the foamed samples displayed blistering that was linked to CO₂ bubble entrapment and coalescence at the surface. Scanning electron micrographs of the foams generated from blends displayed distinct morphologies reflecting whether the sections were representing the machine‐ or cross‐machine direction of extruded films. In going from EVACO‐2410 to EVA‐25, the cell densities ranged from about 10⁶ to 10¹⁰ cells/cm³. Foams with low bulk densities of about 0.11 g/cm³ could be generated. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45841.     

Structural analysis of electron beam irradiated ethylene-vinyl acetate copolymer (EVA) film (II)

The crosslinked structure of irradiated ethylene-vinyl acetate copolymer (EVA) film was examined by means of ESR, IR and pyrolysis-gas chromatography. The ESR spectrum of 35 Mrad irradiated EVA film with 95g kg^?1 vinyl acetate content consisted of a three-line component with an intensity ratio of 1:2:1, a hyperfine structure coupling of 22.4 G and g factor of 2.0049. Therefore, the spectrum was assigned to the methylene radical with two α protons on the same plane; this radical is formed by loss of a hydrogen atom from the acetoxymethyl group. In pyrolysing EVA films at 500°C, the yield of acetic acid from 10 Mrad-150 g kg^?1 film significantly decreased compared with that of unirradiated film, and it decreased with increasing crosslinking density. By measuring the IR spectra of methanolysed EVA films, the following results were obtained: the absorbances at 1740, 1250 and 1050cm^?1, attributed to the C?O, O?C? O? R and C? O? C groups, respectively, had a marked decrease, whereas the three peaks for 20Mrad film were much stronger than those of unirradiated film. On the basis of these findings, it is suggested that the crosslinking reaction in electron beam irradiated EVA film with lower doses takes place between the acetoxy groups and the main chains.     

Effects of peroxide crosslinking on the mechanical and morphological properties of poly(ethylene‐co‐vinyl acetate)/zeolite composites

Uncrosslinked and chemically crosslinked ethylene‐vinyl acetate copolymers (EVAs) with 5–25 volume percentages of zeolite were prepared in a melt‐mixing process and then compression‐molded on a hot‐press machine according to standard test specifications. The mechanical properties measured by tensile test showed a reduction in tensile strength and elongation at break with increasing zeolite content. However, an increasing trend was observed for tensile modulus with addition of zeolite. Experimental results for ultimate stress were compared with those from Pukanszky equation. The experimental data showed a good fit to the Pukanszky model. The improvement in the interfacial interaction for crosslinked composites was also confirmed by this model. Morphological changes of EVA/zeolite composites were analyzed by scanning electron microscopy (SEM). The fractured surface of the composites indicated more complex morphology at higher zeolite loading. The influence of crosslinking induced by 2 wt% of dicumyl peroxide on the properties of EVA/zeolite composites was also investigated. The crosslinked composites showed better tensile properties than the uncrosslinked ones, a result which might be an indication of enhanced interaction between the EVA and zeolite. Density measurements, gel content determinations, and Fourier transform infrared analyses were also performed to evaluate the crosslink content of the composites. The changes in the properties of chemically crosslinked EVA/zeolite composites were observed. Meanwhile, SEM micrographs of the crosslinked EVA/zeolite composites showed better interfacial strength between zeolite and the EVA matrix as compared to that of the uncrosslinked composites. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers     

Production of polymeric membranes made of polypropylene,poly(ethylene‐co‐vinyl acetate), and poly(vinyl alcohol)

In this study, we prepared and characterized membranes containing polypropylene, poly(ethylene‐co‐vinyl acetate) (EVA), and poly(vinyl alcohol) (PVA). The production process involved blend extrusion and calendering followed by solvent extraction by toluene and water of the EVA and PVA phases. Morphology studies involving scanning electron microscopy determined the pore size distribution at the surface and in the internal regions of the membrane. The resulting membrane properties were related to the processing variables (extension rate, process temperature, and solvent extraction methods) and blend composition. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3275–3286, 2004     

Antimicrobial‐releasing films and coatings for food packaging based on carvacrol and ethylene copolymers

Efficiency in antimicrobial packages based on the release of active agents depends on their retention into the packaging materials and on the extent and rate of their release to the package headspace. In this work, the effects of polymer chemical composition and matrix morphology on the release of carvacrol were explored. Films and coatings containing carvacrol, and manufactured from four polyolefin latexes of a range of polarities (ethylene–octene (LLDPE) < ethylene–vinyl acetate (EVA) < < ethylene–methacrylic acid (EMA) ≈ ethylene–alkaline methacrylate (ION)), were characterized in terms of their active and functional properties. Scanning electron microscopy images evidenced that films presented heterogeneous structures caused by an incomplete coalescence of their polymeric particles. Consequently, different film structures of decreasing heterogeneity, porosity and roughness (LLDPE > EVA > > ION > EMA) were obtained, exhibiting morphologies generally correlated with the melting temperatures and active behaviours of the polymers. LLDPE and EVA, the most heterogeneous polymers, were generally more permeable, less resistant, more deformable, less transparent and more wettable than EMA and ION, of coalesced structure. For carvacrol, LLDPE and EVA yielded higher values of the diffusion coefficient, in agreement with their permeability results, whereas EMA and ION showed higher solubilities, according to their greater affinity for the active molecule, as derived from their ionic nature. The evolution of the release of carvacrol from the studied films was experimentally measured and theoretically predicted through determination of its solubility and diffusivity parameters. Excellent agreement between both experimental and predicted data was finally observed. © 2015 Society of Chemical Industry     

Correlation between the morphology and dynamic mechanical properties of ethylene vinyl acetate/linear low‐density polyethylene blends: Effects of the blend ratio and compatibilization

The effects of the blend composition and compatibilization on the morphology of linear low‐density polyethylene (LLDPE)/ethylene vinyl acetate (EVA) blends were studied. The blends showed dispersed/matrix and cocontinuous phase morphologies that depended on the composition. The blends had a cocontinuous morphology at an EVA concentration of 40–60%. The addition of the compatibilizer first decreased the domain size of the dispersed phase, which then leveled off. Two types of compatibilizers were added to the polymer/polymer interface: linear low‐density polyethylene‐g‐maleic anhydride and LLDPE‐g phenolic resin. Noolandi's theory was in agreement with the experimental data. The conformation of the compatibilizer at the blend interface could be predicted by the calculation of the area occupied by the compatibilizer molecule at the interface. The effects of the blend ratio and compatibilization on the dynamic mechanical properties of the blends were analyzed from ?60°C to +35°C. The experiments were performed over a series of frequencies. The area under the curve of the loss modulus versus the temperature was higher than the values obtained by group contribution analysis. The loss tangent curve showed a peak corresponding to the glass transition of EVA, indicating the incompatibility of the blend system. The damping characteristics of the blends increased with increasing EVA content because of the decrease in the crystalline volume of the system. Attempts were made to correlate the observed viscoelastic properties of the blends with the morphology. Various composite models were used to model the dynamic mechanical data. Compatibilization increased the storage modulus of the system because of the fine dispersion of EVA domains in the LLDPE matrix, which provided increased interfacial interaction. Better compatibilization was effected at a 0.5–1% loading of the compatibilizer. This was in full agreement with the dynamic mechanical spectroscopy data. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4526–4538, 2006     

Influence of crosslinking on crystallization,rheological, and mechanical behaviors of high density polyethylene/ethylene‐vinyl acetate copolymer blends

High density polyethylene (HDPE)/ethylene‐vinyl acetate copolymer (EVA) blends with selective crosslinking the EVA phase were prepared and the crystallization, rheological, and mechanical behaviors were studied. Selective crosslinking of EVA component could greatly improve both tensile and impact strengths of the HDPE‐rich blends and influence melting enthalpy at different annealing temperature in successive self‐nucleation and annealing procedure. Dynamic mechanical analysis reveals that glass transition temperatures of both the HDPE and EVA components are lowered upon blending and are raised upon crosslinking. The uncrosslinked HDPE/EVA blends are unstable in the melt and show increment in storage modulus (G′) and decay in loss tangent (tanδ) with annealing time associated with phase coarsening. However, morphology of selectively crosslinked blends in the melt state is highly unstable, characterized by a fast migration of uncrosslinked HDPE component out of the crosslinked EVA phase to the surface resulting in a rapid decay in G′ and an increment in tanδ at the early stage of annealing. POLYM. ENG. SCI., 54:2848–2858, 2014. © 2014 Society of Plastics Engineers     

Peroxide crosslinking of ethylene–vinyl acetate copolymer

The work reported here concerns the peroxide crosslinking of ethylene–vinyl acetate rubber. Calculated values for scission-to-crosslinking ratios are higher for EVA than for low-density polyethylene. In the temperature range from 150 to 200°C at a constant peroxide content, a rise in temperature results in a decrease in the obtained gel content. Some tensile and modulus–temperature results on crosslinked EVA samples are also reported on.     

Synthesis and properties of polymeric biocides based on poly(ethylene‐co‐vinyl alcohol)

Poly(ethylene‐co‐vinyl acetate) with 55 wt % vinyl acetate units (EVA55) was cryogenically ground and saponified in KOH/ethanol solution to obtain poly(ethylene‐co‐vinyl alcohol) (EVOH55). Polymeric antimicrobial agents were synthesized by reacting three antimicrobial agents, 4‐aminobenzoic acid (ABA), salicylic acid (SA), and 4‐hydroxy benzoic acid (HBA) with EVOH55. The polymers became more flexible and exhibited lower melting peak temperature and heat of fusion as the content of the chemically bound ABA, SA, and HBA units increased. These phenomena appeared more significant in the order of ABA < HBA < SA. S. aureus, Gram‐positive bacterium, was more susceptible to the polymeric antimicrobial agents than P. aeruginesa, Gram‐positive bacterium. The antimicrobial activity increased in the order of EVOH55‐HBA < EVOH55‐ABA < EVOH‐SA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 765–770, 2004