Extraction,purification and characterization of wax from flax (Linum usitatissimum) straw

The chemical composition and selected physical parameters of wax extracted from flax straw with supercritical CO₂ (SC‐CO₂) and hexane have been determined. From the GC/MS results, clear variations in composition and component distributions were observed between SC‐CO₂‐ and hexane‐extracted samples. The major components of the SC‐CO₂ and hexane extracts from three flax cultivars were: fatty acids (36–49%), fatty alcohols (20–26%), aldehydes (10–14%), wax esters (5–12%), sterols (7–9%) and alkanes (4–5%). Purification of SC‐CO₂‐extracted wax with silica gel chromatography yielded 0.4–0.5% (dry matter) and was composed primarily of wax esters (C₄₄, C₄₆ and C₄₈) and alkanes (C₂₇, C₂₉ and C₃₁). UV‐Vis scans of the purified wax samples exhibited two main peaks indicating the presence of conjugated dienes and carotenoids or related compounds. Fourier transform infrared results showed prominent peaks at 2918 (‐C‐H), 2849 (‐C‐H), 1745 (‐C=O), 1462 (‐C‐H), 1169 (‐C‐O) and 719 cm^–1 (‐(CH₂)_n‐), with NorLin wax showing a slightly deviating pattern compared to the other samples. Thermal analysis by differential scanning calorimetry revealed a mean melting point of 55–56 °C and oxidation temperatures of 146–153 °C for purified wax from flax straw processed using different procedures.     

Swelling and electrical properties of rubber vulcanizates loaded with paraffin wax

The influence of the concentration of paraffin wax on the penetration rate, P, and the average diffusion coefficient, D, of kerosene in an SBR–NR composite and also on the coefficient of viscosity were investigated. All decreased with the addition of wax. Also, the effect of the concentration of paraffin wax on both the current–voltage characteristics and the temperature dependence of the dc electrical conductivity were studied. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3169–3177, 2001     

Production of middle distillate through hydrocracking of paraffin wax over Pd/SiO2–Al2O3 catalysts

Pd/SiO₂–Al₂O₃ catalysts (Pd/SA-X) with different SiO₂ contents (X, wt%) were prepared for use in the production of middle distillate (C₁₀–C₂₀) through hydrocracking of paraffin wax. The effect of SiO₂ content of Pd/SA-X catalysts on their physicochemical properties and catalytic performance in the hydrocracking of paraffin wax was investigated. High surface area and well-developed mesopores of Pd/SA-X catalysts improved the dispersion of Pd species on the SiO₂–Al₂O₃ support. Acidity of Pd/SA-X catalysts determined by NH₃-TPD experiments showed a volcano-shaped trend with respect to SiO₂ content. Conversion of paraffin wax increased with increasing acidity of the catalyst, while selectivity for middle distillate decreased with increasing acidity of the catalyst. Yield for middle distillate showed a volcano-shaped curve with respect to acidity of the catalyst. This indicates that acidity of Pd/SA-X catalysts played an important role in determining the catalytic performance in the hydrocraking of paraffin wax. Among the catalyst tested, Pd/SA-69 with moderate acidity showed the highest yield for middle distillate.     

The effect of the dry glass transition temperature on the synthesis of paraffin microcapsules obtained by suspension‐like polymerization

PRS® paraffin wax was encapsulated by means of suspension‐like copolymerization of methyl methacrylate (MMA) with butyl acrylate (BA). The effects of the polymeric shell dry glass transition temperature (T_g) and the reaction temperature (T_r) were then studied. Additionally, the evolution of particle diameter, molecular weight, conversion, and T_g during polymerization was also researched. The chemical properties of the shell material (acrylic polymer), together with those found in the core material (PRS® paraffin wax), for instance: polarity and interfacial tensions, largely determine whether the morphology of the microcapsules will be thermodynamically favored or not. The high polarity of MMA (γ₀ = 18 mN m^?1) and BA (γ₀ = 24 mN m^?1) should provide a thermodynamic driving force to cover the paraffin wax droplet which would result in a core/shell thermodynamically favored structure. However, most systems are defined by kinetics rather than thermodynamics such as the monomers dry T_g and T_r. It was observed that penetration of polymer radical chains was severely limited when the dry T_g was ≥10°C above the reaction temperature, resulting in irregular and undifferentiated particles. However, penetration did occur when the copolymeric shell dry T_g was ～10°C below the reaction temperature which led to uniform and spherical particles being synthesized. POLYM. ENG. SCI., 54:208–214, 2014. © 2013 Society of Plastics Engineers     

Viscoelastic properties of branched polyacrylate melts

The viscoelastic properties of poly(n‐butyl acrylate), poly(ethyl acrylate) and poly(methyl acrylate) melts have been studied using samples that varied in both molar mass and the mol% branched repeat units, these properties having been previously determined by gel permeation chromatography and ¹³C NMR spectroscopy, respectively. Poly(n‐butyl acrylate) was studied most extensively using seven samples; one sample of poly(n‐butyl acrylate), two samples of poly(ethyl acrylate) and one sample of poly(methyl acrylate) were used to study the effect of side‐group size. Storage and loss moduli were measured over a range of frequency (1 × 10^?3 to 1 × 10² rad s^?1) at temperatures from T_g + 20 °C to T_g + 155 °C and then shifted to form master curves at T_g + 74 °C through use of standard superposition procedures. The plateau regions were not distinct due to the broad molar mass distributions of the polyacrylates. Hence, the upper and lower limits of shear storage modulus from the nominal ‘plateau’ region of the curves for the seven poly(n‐butyl acrylate) samples were used to calculate the chain molar mass between entanglements, M_e, which gave the range 13.0 kg mol^?1 < M_e < 65.0 kg mol^?1. The Graessley–Edwards dimensionless interaction density and dimensionless contour length concentration were calculated for poly(n‐butyl acrylate) using the mean value of plateau modulus (1.2 × 10⁵ Pa) and three different methods for estimation of the Kuhn length; the data fitted closely to the Graessley–Edwards universal plot. The Williams–Landel–Ferry C₁ and C₂ parameters were determined for each of the polyacrylates; the data for the poly(n‐butyl acrylate) samples indicate an overall reduction in C₁ and C₂ as the degree of branching increases. Although the values of C₁ and C₂ were different for poly(n‐butyl acrylate), poly(ethyl acrylate) and poly(methyl acrylate), there is no trend for variation with structure. Thus the viscoelastic properties of the polyacrylate melts are similar to those for other polymer melts and, for the samples investigated, the effect of molar mass appears to dominate the effect of branching. © 2001 Society of Chemical Industry     

Synthesis and characterization of chlorinated paraffin wax-bound paraphenylenediamine antioxidant and its application in natural rubber

p-Phenylenediamine was chemically attached to low molecular weight chlorinated paraffin wax. The polymer-bound p-phenylenediamine was characterized by vapor-phase osmometry (VPO), proton magnetic resonance spectroscopy (¹H-NMR), infrared spectroscopy (IR), and thermogravimetric analysis (TGA). The efficiency and permanence of the polymer-bound p-phenylenediamine as an antioxidant was compared with a conventional amine-type antioxidant in natural rubber vulcanizates. The vulcanizates showed improved aging resistance in comparison to vulcanizates containing a conventional antioxidant. The presence of liquid polymer-bound p-phenylenediamine also reduces the amount of the plasticizer required for compounding. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2183–2189, 2001     

Phase Transformation and Rheological Behaviour of Highly Paraffinic “Waxy” Mixtures

An experimental investigation was undertaken for the rheology and phase transformation of prepared solutions comprising a paraffin wax dissolved in n‐dodecane or n‐hexadecane. The liquid‐solid phase transformation in wax‐solvent mixtures was investigated through the measurement of wax appearance/disappearance temperature (using cross polar microscopy, differential scanning calorimetry, viscometry and a visual method), pour point temperature and crystallization temperature. The results were utilized to prepare a temperature‐composition phase diagram for the wax+n‐C₁₆H₃₄ pseudo‐binary system. The effects of composition, temperature, cooling rate and shear rate were studied on the rheology of wax‐solvent mixtures. A correlation was developed for the apparent viscosity of wax‐solvent mixtures.     

Factors affecting analytical values of beeswax and detection of adulteration

Various factors that could affect analytical values for beeswax, and so also detection of adulteration, have been investigated. Ester value determination was checked using synthetic monoesters. Gas liquid chromatographic analysis of overheated wax confirmed that free acids decreased on heating and also showed loss of unsaturated hydrocarbons and of monoesters. The saponification cloud point detected as little as 1% of a paraffin mp 83 C (chain length C₂₀–C₆₀) but only 6% or more of a paraffin mp 53 C (chain length C₂₀–C₃₅). Gas liquid chromatographic analysis of the hydrocarbon fraction of waxes containing these paraffins detected 1% of either paraffin, but only the low melting paraffin was estimated accurately. The presence of 2.5% of carnauba wax in beeswax was detected and estimated by gas liquid chromatography. Issued as NRCC No. 13173.     

Synthesis,Characterization and Properties of <Emphasis Type="Italic">N</Emphasis>-Alkyl-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-di(2-hydroxyethyl) Amine Oxides

N‐Dodecyl‐N,N‐di(2‐hydroxyethyl) amine oxide (C₁₂DHEAO) and N‐stearyl‐N,N‐di(2‐hydroxyethyl) amine oxide (C₁₈DHEAO) were synthesized with N‐alkyl‐diethanolamine and hydrogen peroxide. Their chemical structures were confirmed using ¹H‐NMR spectra, mass spectral fragmentation and FTIR spectroscopic analysis. It was found that C₁₂DHEAO and C₁₈DHEAO reduced the surface tension of water to a minimum value of approximately 28.75 mN m^?1 at concentration of 2.48 × 10^?3 mol L^?1 and 32.45 mN m^?1 at concentration of 5.21 × 10^?5 mol L^?1, respectively. The minimum interfacial tension (IFT_min) and the dynamic interfacial tension (DIT) of oil–water system were measured. When C₁₈DHEAO concentration was in the range of 0.1–0.5%, the IFT_min between liquid paraffin and C₁₈DHEAO solutions all reached the ultra‐low interfacial tension. Furthermore, their foam properties were investigated by Ross‐Miles method, and the height of foam of C₁₂DHEAO was 183 mm. It was also found that they showed strong emulsifying power.     

Identification of Unique Aldehyde Dimers in Sorghum Wax Recovered after Fermentation in a Commercial Fuel Ethanol Plant

Sorghum wax can be extracted from the surface of sorghum (Sorghum bicolor) kernels. It is composed mostly of a mixture of unsaturated C₂₈ and C₃₀ alkanes, fatty acids, fatty alcohols, and fatty aldehydes. Like carnauba wax, sorghum wax is a hard wax with a high melting point and it has potential edible and industrial applications. The yield of sorghum wax from the surface of sorghum kernels is 0.2–0.5 g of wax per 100 g of kernels. Sorghum wax can also be recovered from the “distillers oil” which is obtained after fermentation of sorghum (milo) or sorghum/corn blends in dry grind fuel ethanol plants. This distillers sorghum wax can potentially be obtained in yields of up to 10% by chilling the distillers oil to precipitate the wax and then recovering it via centrifugation or filtration. Like sorghum kernel wax, distillers sorghum wax is mainly composed of C₂₈ and C₃₀ alkanes, alcohols, and aldehydes in the molecular weight (MW) range of 350–450. However, we found that 7–49% w/w of distillers sorghum wax is composed of larger wax components with MW of 799–912. Analysis via high-resolution atmospheric pressure chemical ionization mass spectrometry (APCI) and gas chromatography with electron ionization mass spectrometry (GC/MS-EI) resulted in exact mass data and fragmentation patterns that suggested that these high MW compounds are monounsaturated fatty aldehyde dimers, likely formed by aldol condensation. Further confirmation supporting the GC/MS data for the aldol reaction was obtained by comparison with similar aldol products.     

New synthetic method for soluble starlike C60‐bonding polymers

Novel starlike C₆₀‐bonding polymers were synthesized by using the iniferter technique. The fullerene C₆₀ with pendent N,N‐diethyldithiocarbamate groups (C₆₀–SR) was used as polyfunctional photoiniferter. The effects of UV‐irradiation time and ambient temperature on the molecular weight of polymer were investigated. The photopolymerization with C₆₀–SR proceeded via a living‐radical mechanism, and gave soluble polyfunctional polymers (photoiniferters). Multiple polymer arms were attached to the C₆₀ core and the polymers obtained by C₆₀–SR could also be used as excellent crosslinking agents. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1286–1290, 2001     

Molecular analysis of intact preen waxes of Calidris canutus (Aves: Scolopacidae) by gas chromatography/mass spectrometry

The intact preen wax esters of the red knot Calidris canutus were studied with gas chromatography/mass spectrometry (GC/MS) and GC/MS/MS. In this latter technique, transitions from the molecular ion to fragment ions representing the fatty acid moiety of the wax esters were measured, providing additional resolution to the analysis of wax esters. The C₂₁−C₃₂ wax esters are composed of complex mixtures of hundreds of individual isomers. The odd carbon-numbered wax esters are predominantly composed of even carbon-numbered n-alcohols (C₁₄, C₁₆, and C₁₈) esterified predominantly with odd carbon-numbered 2-methyl fatty acids (C₇, C₉, C₁₁, and C₁₃), resulting in relatively simple distributions. The even carbon-numbered wax esters show a far more complex distribution due to a number of factors: (i) Their n-alcohol moieties are not dominated by even carbon-numbered n-alcohol moieties are not dominated by even carbon-numbered n-alcohols esterified with odd carbon-numbered 2-methyl fatty acids, but odd and even carbon-numbered n-alcohols participate in approximately equal amounts; (ii) odd carbon-numbered methyl-branched alcohols participate abundantly in these wax ester clusters; and (iii) with increasing molecular weight, various isomers of the 2,6-, 2,8-, and 2,10-dimethyl branched fatty acids also participate in the even carbon-numbered wax esters. The data demonstrate that there is a clear biosynthetic control on the wax ester composition although the reasons for the complex chemistry of the waxes are not yet understood.     

Interpretation of High-Resolution Gas Chromatography and High-Resolution Gas Chromatography / Mass Spectrometry Data Acquired from Atmospheric Organic Aerosol Samples

Major chemical features of the solvent-soluble organic aerosol carbon fraction (i.e., carbon range C₈–C₃₆) are quantified and identified by high-resolution gas chromatography (HRGC) and high-resolution gas chromatography / mass spectrometry (HRGC / MS). Through these methods, bulk characteristics of the atmospheric aerosol are denned and reveal information relating to seasonal variations and specific source contributions to the atmospheric organics complex mixture. Fine aerosol samples from West Los Angeles, CA show lowest monthly average ambient concentrations of the total extractable organic carbon fraction during summer (e.g., 2.03 μg/m³) and highest levels during winter (e.g., 5.18 μg/m³), when sampled at 6-day intervals over the 1982 annual cycle. Absolute concentrations of the complex solvent-soluble organic acid fraction also indicate a similar pattern where a summer minimum and winter maximum are observed. Molecular marker characterizations are performed for the suite of n-alkanes (C₂₀–C₃₆) and for n-alkanoic acids (C₈–C₃₀). Carbon preference index (CPI) values and carbon number maxima (C_MAX) are generated for both homologue series. Petroleum residues constitute the major contribution to the organic aerosol, as indicated throughout the entire annual cycle by the low CPI values (1.02–1.83) and by the predominant C_MAX (C₂₅) of the n-alkanes. A minor presence of vascular plant wax is also demonstrated by the n-alkane data, where the highest contributions of vascular plant waxes to the fine particulate carbonaceous aerosol fraction occur during late summer and early fall. Biogenic residues contribute the major resolved organic acids present based on the n-alkanoic acid homologue data.     

Viscoelastic and pressure–volume–temperature properties of poly(vinylidene fluoride) and poly(vinylidene fluoride)–hexafluoropropylene copolymers

The relationship between the pressure, volume, and temperature (PVT) of poly(vinylidene fluoride) homopolymers (PVDF) and poly(vinylidene fluoride)–hexafluoropropylene (PVDF–HFP) copolymers was determined in the pressure range of 200–1200 bar and in the temperature range of 40°C–230°C. The specific volume was measured for two homopolymers having a molecular weight (M_w) of 160,000–400,000 Da and three copolymers containing between 3 and 11 wt % HFP with a molecular weight range of 320,000–480,000 Da. Differential scanning calorimetry (DSC) was used to simulate the cooling process of the PVT experiments and to determine the crystallization temperature at atmospheric pressure. The obtained results were compared to the transitions observed during the PVT measurements, which were found to be pressure dependent. The results showed that the specific volume of PVDF varies between 0.57 and 0.69 cm³/g at atmospheric pressure, while at high pressure (1200 bar) it varies between 0.55 and 0.64 cm³/g. For the copolymers, the addition of HFP lowered its melting point, while the specific volume did not show a significant change. The TAIT state equation describing the dependence of specific volume on the zero‐pressure volume (V₀,T), pressure, and temperature has been used to predict the specific volume of PVDF and PVDF–HFP copolymers. The experimental data was fitted with the state equation by varying the parameters in the equation. The use of the universal constant, C (0.0894), and as a variable did not affect the predictions significantly. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 230–241, 2001     

Structural changes of bulk polyethylene by stress impact as studied by solid‐state NMR

Solid‐state ¹³C‐ and ¹H‐NMR spectra of bulk high‐density polyethylene samples, cylindrical in form, to which stress impacts were applied with a home‐made stress‐impact apparatus, were measured. The fraction of the noncrystalline component increases with an increase in the stress‐impact strength. In the crystalline region, the monoclinic crystalline component appear with the stress impact, in addition to the major orthorhombic crystalline component. Furthermore, dynamic characterization was carried out on the basis of the observed values of the relaxation parameters ¹H T₂ and T_CH of the ¹H and ¹³C nuclei. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2268–2272, 2001     

Correlation between current–voltage (I–V) characteristic in the electric–thermal equilibrium state and resistivity‐temperature behavior of electro‐conductive silicone rubber

In the electric–thermal equilibrium state the current–voltage (I–V) characteristics of conductive silicone rubbers above the percolation threshold are found to be nonlinear. A mathematic model as I = a₁U ± (a₂U² + C) has been built for the nonlinear I–V relations. Constant C and quadratic term a₂U² can be considered as deviation from Ohm's law. For the first time, a correlation is found for conductive silicone rubber between the I–V characteristic in the electric–thermal equilibrium state and the resistivity–temperature characteristic. Samples with positive temperature coefficient (PTC) resistivity effect exhibit negative deviation from linearity, with an I–V relation as I = a₁U ? (a₂U² + C). Samples with negative temperature coefficient (NTC) resistivity effect exhibit positive deviation, with an I–V relation as I = a₁U + (a₂U² + C). The higher the loaded voltage, the more pronounced the deviation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of paraffin microcapsules for energy-saving applications

A series of microencapsulated phase-change materials (PCMs) with styrene–divinyl benzene shells composed of an n-octadecane (OD or C₁₈)–n-hexadecane (HD or C₁₆) mixture as the core were synthesized by an emulsion polymerization method. The effects of the core/shell ratio (C/S) and surfactant concentration (C_surf) on the thermal properties and encapsulation ratios of the PCMs were investigated. The chemical structures and morphological properties of the microcapsules were characterized by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy analysis, respectively. The characteristic peaks of the paraffin mixtures and shell material located in the FTIR spectrum of the microencapsulated PCMs proved that the encapsulation of the PCM mixture was performed successfully. The thermal properties of the paraffin microcapsules were determined by differential scanning calorimetry (DSC) and thermogravimetric analysis. DSC analysis demonstrated that the microcapsules containing the maximum amount of paraffin mixture (C/S = 2:1) and the minimum C_surf (45 mmol/L) had the highest latent heat value of 88 kJ/kg and a latent heat of temperature of 21.06°C. Moreover, the maximum encapsulation ratio of the paraffin mixture was found to be 56.77%. With respect to the analysis results, the encapsulated binary mixture, which consisted of OD–HD with a poly(styrene-co-divinyl benzene) shell, is a promising material for thermal energy storage applications operating at low temperatures, such as in the thermal control of indoor temperatures and air-conditioning applications in buildings for desirable thermal comfort and energy conservation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47874.     

The influence of molecular weight of acid dyes on the yield stress of dyed nylon monofilament

The yield stress of nylon filament dyed with several acid dyes has been determined as a function of dye content and the molecular weight of acid dyes. The nylon filament dyes with acid dye has greater yield stress than undyed one. The relation between the increment of the yield stress (f) due to the adsorption of acid dye and the dye content (C) in the filament can be expressed by parameters A and B as log f = A log(C ? _C) + B, where C₀ is the dye content under which no contribution to the yield stress is observed and C₀ depends on the number of sulfonic groups in acid dye. It is found that these parameters A and B are expressed by M (the difference between the molecular weight of acid dye and the weight of SO₃Na groups in it) as A = 1 ? 100/M, B = k₁ M^k2, where k¹ and k² are the constants which depend on the parent chemical structure of dyes. The parameters A and B are expected to give available informations as to the physical state of adsorbed dye on nylon filament.     

Dynamic quenching of 5-(2′-ethyl-hexyloxy)-p-phenylene vinylene (MEH-PPV) by charge transfer to a C60 derivative in solution

The fluorescence of 5-(2′-ethyl-hexyloxy)-p-phenylene vinylene (MEH-PPV) quenched in solution in 1,2-dichlorobenzene by a soluble derivative of C₆₀ [1-(3-methoxycarbonyl)propyl-1-phenyl[6,6]C₆₁; [6,6]PCBM] is studied by changing the concentration of the quencher and by varying the temperature. For MEH-PPV and PCBM dissolved in 1,2-dichlorobenzene, the Stern–Volmer constant (K_SV) is 2 × 10³M⁻¹. At high temperature, K_SV is enhanced because thermal energy facilitates the diffusion of PCBM. The results show that dynamic quenching (rather than static quenching) is the basic mechanism. Comparison with data obtained from quenching studies of trans-stilbene indicates that a single acceptor in contact with an MEH-PPV macromolecule quenches the luminescence from hundreds of repeat units. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2553–2557, 2001