Degree Of Polymerization Values Research Articles

Preparation of microcrystalline cellulose directly from wood under microwave radiation

The influence of the composition of solutions of peracetic acid on a change in the characteristics of cellulose during the oxidative-hydrolytic destruction of aspen and pine wood under microwave radiation was investigated. Samples of the prepared cellulose were characterized by viscometry, X-ray diffraction and IR spectroscopy. It was found that the main factor determining the rate of destruction of cellulose to a low degree of polymerization values in an acid medium at the initial concentration of peracetic acid not exceeding 15% and initial concentration of hydrogen peroxide no more than 3 mol/dm3 is the concentration of sulfuric acid. The disordering effect of microwave radiation on the crystallites of cellulose during preparation from pine wood in the presence of sulfuric acid in a concentration of 0.06 mol/dm3 and increased duration of oxidative-hydrolytic treatment from 1 to 2 h was revealed. It was shown that the characteristics of the products obtained from aspen and pine wood by oxidative-hydrolytic treatment with 15% peracetic acid under microwave radiation, the duration of the process of 1.5–2 h and the sulfuric acid concentration of 0.3–0.7 mol/dm3 correspond to partially oxidized microcrystalline cellulose.

Damage function for historic paper. Part II: Wear and tear

As a result of use of library and archival documents, defined as reading with handling in the context of general access, mechanical degradation (wear and tear) accumulates. In contrast to chemical degradation of paper, the accumulation of wear and tear is less well studied. Previous work explored the threshold of mechanical degradation at which a paper document is no longer considered to be fit for the purpose of use by a reader, while in this paper we explore the rate of accumulation of such damage in the context of object handling. The degree of polymerisation (DP) of historic paper of European origin from mid-19th–mid-20th Century was shown to affect the rate of accumulation of wear and tear. While at DP > 800, this accumulation no longer depends on the number of handlings (the process is random), a wear-out function could be developed for documents with DP between 300 and 800. For objects with DP < 300, one large missing piece (i.e. such that contains text) developed on average with each instance of handling, which is why we propose this DP value as a threshold value for safe handling. The developed model of accumulation of large missing pieces per number of handlings of a document depending on DP, enables us to calculate the time required for an object to become unfit for use by readers in the context of general access. In the context of the average frequency of document use at The UK National Archives (Kew), this period is 60 years for the category of papers with DP 300, and 450 years for papers with DP 500. At higher DP values, this period of time increases beyond the long-term planning horizon of 500 years, leading to the conclusion that for such papers, accumulation of wear and tear is not a significant collection management concern.

The Investigation on Thermal Aging Characteristics of Oil-Paper Insulation in Bushing

Bushing is the key link to connect outer and inner insulating systems and also the essential electric accessory in electric power system, especially in the high voltage engineering (AC 1000kV, DC 800kV). This paper presented the experimental research of thermal aging characteristic of oil- paper insulation used in bushing. A thermally accelerated aging experiment at 90℃ was performed. The bushing models containing five layers of paper were sealed into the aging vessels and further aged for 250 days. Then several important parameters associated with the aging were observed and evaluated. The results showed that the degree of polymerization (DP) of papers gradually decreased. The DP values of outermost layer and middle layer fit well into the second-order kinematic model and first-order kinematic model, respectively. Less deterioration speed of the inter-layer paper than outer layer was confirmed by the variation of DP. Hydrolysis was considered as the main cause to this phenomenon. In addition, the logarithm of the furfural concentrations in insulation oil was found to have good linear relationship with DP of papers. Interestingly, when the aging time is about 250 days and DP is 419, the aging process reaches an inflection point at which the DP approaches the leveling off degree of polymerization (LODP) value. Both tanδ and acid number of oils increased, while surface and volume resistivity of papers decreased. The obtained results demonstrated that thermal aging and moisture absorbed in papers brought great influence to the degradation of insulating paper, leading to rapid decrease of DP and increase of the tanδ . Thus, the bushing should be avoided from damp and real-time monitoring to the variation of tanδ and DP values of paper is an effective way to evaluate the insulation status of bushing.

Determination of the degree of polymerisation of fructans from ryegrass and chicory using MALDI-TOF Mass Spectrometry and Gel Permeation Chromatography coupled to multiangle laser light scattering

This study is concerned with the determination of the degree of polymerisation (DP) of fructans from chicory and rye-grass (Lolium perenne L.) using Gel Permeation Chromatography coupled to multiangle laser light scattering and refractive index detectors (GPC/MALLS) and Matrix-Assisted Laser Desorption/Ionisation Time of Flight Mass Spectrometry (MALDI-TOF MS). The results show that fructans isolated from ryegrass have a DP in the range 2–>100 and the commercially produced fructans derived from chicory have a DP in range 2–61. It has been demonstrated that MALDI-TOF MS is particularly effective at determining the DP of low molar mass material but is less effective for detecting the presence of high DP molecules. On the other hand GPC/MALLS is able to provide a much broader range of DP values although it is less sensitive at very low DP. It has been shown that the two techniques give complementary information thus providing a more accurate estimate of the overall DP of the fructan molecules.

Preparation of Well‐Defined Poly(2‐hydroxyethyl methacrylate) Macromonomers via Atom Transfer Radical Polymerization

A series of six near-monodisperse methacrylic macromonomers is prepared via atom transfer radical polymerization (ATRP) of 2-hydroxyethyl methacrylate using a tertiary amine-functionalized initiator at 50 °C, followed by quaternization with excess 4-vinylbenzyl chloride at 20 °C. GPC analyses indicate polydispersities of around 1.20 and their mean degrees of polymerization (DP) range from 20 to 70, as judged by both (1) H NMR and UV spectroscopy. The former technique is more convenient but the latter proved more accurate for the higher DP values, provided that an appropriate model compound is utilized for calibration. Finally, these new macromonomers are used to prepare sterically stabilized polystyrene latexes with relatively narrow size distributions via alcoholic dispersion polymerization.

Postmortem Investigation of Power Transformers—Profile of Degree of Polymerization and Correlation With Furan Concentration in the Oil

In this paper, postmortem aging investigations on insulation material of power transformers are presented. A methodology for taking paper samples in a systematical manner and a scheme for calculating an average degree of polymerization (DP) for the entire transformer out of the DP values of the individual paper samples will be shown. The typical DP profile in the axial direction of transformer coils will be explained using calculated distribution of losses within the coils of a 740-MVA generator stepup transformer. Further, correlations between the furan (2-FAL) concentration in the oil and the average DP of the investigated German GSU transformers and grid transformers are derived and compared with existing correlations.

Effects of paper-aged state on space charge characteristics in oil-impregnated paper insulation

Oil-paper compound insulation has been widely used in power transformers for quite a long time because of its good performance. The paper insulation degrades under the combined stresses of thermal, electrical and chemical stresses during routine operations, resulting in the reduction of its degree of polymerization (DP) and hence its mechanical and electrical strength. Space charges in a dielectric material have a close relation to its electrical performance. Therefore, in this work, the effect of paper-aged states (with different DP values) on the space charge behavior in oil-impregnated paper insulation is investigated, and the pulsed electro-acoustic (PEA) method is used for the space charge distribution measurement. In order to achieve this purpose, new oil-impregnated paper samples are thermally-accelerated aged for different time interval to obtain different DP values, and then the residual oil in each sample is removed, and the Kraft paper samples are dried in a vacuum dry oven. After that, all paper samples are impregnated with new oil, and PEA measurements are performed at room temperature. The experimental results show that, when the external dc voltage is applied on the oil-paper sample, homo-charge injection occurs for all samples. The samples with different aging states exhibit quite different space charge characteristics for both voltage-on and voltage-off conditions. When the aged states are worse, for voltage-on condition, more charges are induced at cathode and anode, as well as more space charges are accumulated in the bulk. For voltage-off condition, the space charge decay rate shows no obvious change for different aged samples.

Quantitative analysis of ageing condition of oil-paper insulation by frequency domain spectroscopy

Frequency domain spectroscopy (FDS) has been used to assess the ageing condition of oil-paper insulation used in transformers. To further understand the ageing process, the reduction in degree of polymerization (DP) of cellulosic paper in itself on the dielectric response was investigated first. It has been found that the reduction in DP itself can alter the dielectric characteristics. The oil-paper insulation was thermally accelerated aged at 110 °C for up to 154 days according to the procedure described in IEEE Guide. Then dielectric characteristics of the thermally aged samples were obtained at different measurement temperatures. The results reveal that the relative permittivity (er') plots of oil impregnated pressboards increase with the reduction in cellulose polymer chain length. er' and tanδ values of oil impregnated pressboards shifts upwards in the lower frequency range (10-3 Hz -10-1 Hz) with different ageing condition, indicating the possibility of utilizing the characteristics of er' and tanδ values at lower frequencies (10-3 Hz-10-1 Hz) to quantitatively characterize ageing condition of oil impregnated pressboard. The parameters including DP, er' and tanδ values at the three characteristic frequencies (10-3 Hz, 10-2 Hz, 10-1 Hz) have been analyzed as a function of the ageing time, showing an exponential relationship based on the best fit. In addition, the er' and tanδ curves of aged oil impregnated pressboard have been observed to be shifted upwards to higher values at lower frequencies when the measurement temperature is increased. A shifting factor αT which describes the relationship between frequency and temperature has been defined. It allows one to shift the master curve of impregnated pressboard with DP obtained at reference temperature to other testing temperatures.

Detailed Characterization of Proanthocyanidins in Skin, Seeds, and Wine of Shiraz and Cabernet Sauvignon Wine Grapes (Vitis vinifera)

The distribution of proanthocyanidin (PA) polymer lengths, proanthocyanidin concentration at each polymer length, and polymer composition were determined in the seed, skin, and wine of Shiraz and Cabernet Sauvignon grape berries grown in southeast Australia. PA was fractionated by semipreparative high performance liquid chromatography (HPLC) and analyzed by phloroglucinolysis and HPLC to report the degree of polymerization (DP), concentration, and composition at 11 DP values in seed and wine and 21 DP values in skin. In skin, the highest PA concentration was observed at a DP of 31 in Shiraz and 29 in Cabernet Sauvignon representing 15% of the total PA in both varieties. The distribution of seed PA had the highest concentration at a DP of 7 in Shiraz and 6 in Cabernet Sauvignon representing around 30% of the total PA. In the wine PA distribution, the highest concentration was observed at a DP of 11 in Shiraz and 9 in Cabernet Sauvignon representing around 26 and 32% of the distribution, respectively. A second peak in wine PA concentration was observed at the largest DP of 18 in Shiraz and 15 in Cabernet Sauvignon representing around 20% of the distribution. The composition in wine did not vary at different DP, but the proportion of epicatechin gallate varied in seed PA less than 4 DP. The proportion of epigallocatechin increased with increasing DP in skin PA. Wine PA had a DP range and composition similar to the distribution of skin PA between DP 4 and 18 suggesting that larger skin PAs are not extracted into wine. This study provides information that could be used to target the important PA fractions in grapes that need to be measured to understand (or predict) PA extraction into wine and eventual mouthfeel.

Significance of cellulose power transformer condition assessment

Power transformers are designed to withstand system abnormalities such as over voltages and external short-circuits. Transformer monitoring and diagnostics are the effective techniques in preventing the eventual failures and contribute to ensure the plant's reliability. Transformer life mainly depends on the integrity of its solid insulation (cellulose). The solid insulation in transformers degrades with time at rates which depend on the temperature and the amount of moisture, oxygen and acids in the insulation system. Moisture and oxygen cause the paper insulation to decay much faster than normal. Moisture in a transformer accelerates the aging process and causes severe deterioration in the mechanical and electrical properties of insulation system. The aging of paper insulation is irreversible. The degree of polymerization value is a main relation between insulation deterioration and formation of aging products. To predict a failure or an unusual behavior, an accurate interpretation of monitoring, diagnostics and maintenance data is required. The monitoring of insulation system and verification of core and winding mechanical integrity allow optimization of the lifecycle management of an asset. This paper presents an investigation and condition assessment of 152 MVA, 512 kV, 1-phase, 2-winding generator step-up transformer having a history of combustible gases.

Optimization of Transglutaminase Cross-linking of Pumpkin Oil Cake Globulin; Improvement of the Solubility and Gelation Properties

Enzymatic cross-linking of hull-less pumpkin oil cake globulin was studied using microbial transglutaminase. Response surface methodology was employed to study the effect of enzyme/substrate ratio, temperature, and reaction time on protein cross-linking reaction, measured by degree of polymerization (DP) as a response. The second-order polynomial model showed good fit with the experimental data since the coefficient of determination was R2 = 0.9297. Reaction time of 39.2 min, E/S ratio of 1/4.9 (w/w) and temperature of 28 °C were found to be optimal conditions to achieve the highest value of DP (69%). The solubility and gelation properties of the cross-linked proteins with different values of DP were assessed for improvement. The solubility of polymerized proteins was increased over the pH range 5.0–8.0 and affected with increase of DP, at each pH value studied. The highest solubility was achieved at DP of 60%, at pH 7.0 and was 24-fold higher than solubility of unmodified protein. Gelation properties of cross-linked protein were also improved and the highest decrease of least gelation concentration was achieved at pH 9.0.

Characterization of Alginase and Elicitor-Active Oligosaccharides from Gracilibacillus A7 in Alleviating Salt Stress for Brassica campestris L.

Alginase was purified from Gracilibacillus A7 and evaluated for its ability to produce elicitor-active oligosaccharides. The optimum conditions for the alginase reaction are as follows: temperature, 40 °C; pH, 8.0; alginate content, 0.3-0.7%; and the presence of Na(+) and Mg(2+) metal ions. The degree of polymerization (DP) decreased as the reaction time of the alginase progressed, achieving values of 5.4 and 3.3 after 240 and 300 min, respectively. The relative root length (RRL) of the Brassica campestris L. increased with the addition of oligosaccharides with reduced DP values. The oligosaccharides with lower DP values are effective in reducing the effect of salt stress on the activity of the superoxide dismutase (SOD) and guaiacol peroxidase (POD), and oligosaccharides with moderate DP values can reduce the increase in lipid peroxidation activities (as malondialdehyde content) induced by salt stress. These results suggest that oligosaccharides may act as osmoprotective agents during the plant germination process.

The effect of the distance between neighboring vinyl groups on template polymerization

Intra-molecular polymerization of methacrylate type multi-vinyl monomer of Noria (Noria-MVM) was investigated from the viewpoint of the structure of Noria-MVM. Noria-MVM was polymerized by atom transfer radical polymerization (ATRP) with different reaction time, temperature, and monomer concentration. Polymerized sequences were derived from polymerized Noria-MVM by hydrolysis and methylation. The degree of polymerization (DP) of polymerized sequence was determined by matrix-assisted laser desorption/ionization time-of-flight mass (MALDI-TOF mass) analyses. The DP values were odd value in a range of 3–23. The distance from radical to the next vinyl group was influenced by the structure of Noria. When the distance was shorter than 5 Å, the polymerization did not terminate. When the distance was longer than 5 Å, the termination tended to occur.

Friction Properties of Poly(vinyl alcohol) Hydrogel: Effects of Degree of Polymerization and Saponification Value

In this study, the friction of eight kinds of poly(vinyl alcohol) hydrogel (PVA-H) samples has been studied under various load and velocity conditions to elucidate the effects of PVA factors such as the degree of polymerization (DP) and the saponification value (SV) on the tribological behavior of PVA-H. Results showed the variations of the friction properties due to the PVA factors in the two friction conditions found for the hydrogels: elastic friction and hydrodynamic lubrication. In the elastic friction, the larger frictions were induced by the higher values of DP and SV. In the hydrodynamic lubrication, on the other hand, PVA-Hs with lower SV showed larger friction. The results can then be used to adjust the parameters of PVA-H in order to get given friction properties, for instance for the friction between catheter or scalpel and PVA-H, which can be used as a biomodel material of artery or oral mucosa, for the training of surgeons.

Synthesis and characterization of functional fluorinated telomers

AbstractThe synthesis and characterizations of fluorinated telomers based on vinylidene fluoride (VDF) by iodine transfer polymerization (ITP) are presented. These telomers were prepared in the presence of ω‐iodoperfluorinated functional chain transfer agents, C6F13I or C4F9I. ITPs were initiated by thermal decomposition of bis(4‐tert‐butylcyclohexyl) peroxydicarbonate (BBCHPDC), in solution (in the presence of acetonitrile). The obtained telomers were characterized by different analyses such as elemental analyses, nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy, size exclusion chromatography, X‐ray diffraction (XRD), and finally by thermal analyses such as differential scanning calorimetry (DSC) and thermogravimetric analyses. These technical analyses enabled one to assess their chemical structures, various thermal properties, and their crystalline forms. The assignments of the characteristic signals obtained by 19F NMR spectroscopy enabled one to calculate the average degrees of polymerization (DPn) and percentages of CH2CF2I end group functionalities that depend on the initiator and the fractionation process after reaction. A good control of polymerization was shown by the absence of reversed CH2CF2CF2CH2 (VDF–VDF dyads) and narrow polydispersity indices (&lt;1.2). The XRD and DSC evidenced the influence of the chain length of the telomers on the crystallinity rate (&gt;70%) and indicated two crystalline forms, α and β, that depended on DPn values. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

The Lewis Acid‐Catalyzed Synthesis of Hyperbranched Oligo(glycerol–diacid)s in Aprotic Polar Media

AbstractThe Lewis acid, titanium (IV) butoxide [15% (w/w; catalyst/reactants)], was used to catalyze the condensation of 0.05 mol glycerol with 0.10 mol of succinic acid, glutaric acid, and azelaic acid to produce oligomers. The reactions were refluxed in dilute solutions of dimethylsulfoxide (DMSO) or dimethylformamide (DMF) for 24 h. The oligomers were obtained, on average, in 84% yield and were soluble in polar organic solvents. Analysis by gel permeation chromatography determined that the oligomers had a number of average molecular weights (Mn) ranging from 2,118 to 3,245 g/mol, with degrees of polymerization (DOP) ranging from 12.2 to 13.4 repeat units. The oligomers had low polydispersities (Mw/Mn) that averaged ≈1.33. Degrees of branching were determined by one‐dimensional and two‐dimensional 1H NMR and 13C NMR and varied from 25 to 80%. Like Mn and the DOP values, the degrees of branching were dependent on the aliphatic chain length of the diacid. MALDI‐TOF mass spectrometry was used to detect ionated species that were unique to branched molecules. It was also used to validate NMR studies that suggested that some diacids were terminated with dimethylamine, generated from the hydrolysis of DMF, by as much as 36%.

Crosslinking reactions of oxidized cellulose fiber. I. Reactions between dialdehyde cellulose and multifunctional amines on lyocell fabric

AbstractFibrillation‐controlled lyocell fibers were developed by crosslinking reactions between dialdehyde cellulose (DAC) and multifunctional amines. DAC lyocell fibers were manufactured by partial oxidation with sodium metaperiodate and were successfully crosslinked with two multifunctional amines by Schiff‐base formation. The amorphous regions and the char formations, which were characterized by differential scanning calorimetry and thermogravimetric analysis, increased with the degree of oxidation. After the crosslinking reactions, an increase in the amorphous regions also appeared, whereas the thermal stability was somewhat improved by the chain crosslinking. These results were in good agreement with viscosity‐average degree of polymerization values in that they diminished with oxidation level and increased with the crosslinking reactions. The water retention value and moisture regain value decreased with the oxidation and crosslinking levels, which implied that the swellability of fibers and the water absorbency in characteristic sites decreased with them. The increase in the dry crease recovery angle also confirmed the presence of hemiacetal crosslinks in the DAC and amine crosslinks between the DAC and the amines. The fibrillation grade of the crosslinked fibers diminished with oxidation level and the amine concentration. In particular, the fibrillation properties of the crosslinked fibers with 4‐hydroxy‐2,4,6‐triaminopyrimidine sulfate salt were more easily controlled than those of the crosslinked fibers with 2,4,6‐triamino‐1,3,5‐triazine. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Enzymatic processing and antioxidant activity of agricultural waste autohydrolysis liquors

This paper presents the production of xylooligosaccharides from auto-hydrolysis liquors of wheat straw and sunflower stalk, as wells as the antioxidant activity of these autohydrolysis liquors. The autohydrolysis liquors (raw or refined by ultrafiltration) of both wastes were subjected to the action of two different endoxylanase to produce xylooligosaccharides with low degree of polymerization that are potentially useful as food additives. Trichoderma reseei xylanase led to the highest proportion of oligomers with degree of polymerization values in the range 1–3, while Aspergillus niger xylanase gave mainly oligomers with polymerization degree in the range 2-3. T reseei xylanase gave a higher increase in equivalent xylose concentration and produced more monosaccharide than A.niger xylanase. Membranes with a nominal MWCO 1 kDa did not reject antioxidant-related and other low molar mass compounds, and most of these compounds were recovered with monosaccharides in the permeate of the membrane.

Oxidation of bleached wood pulp by TEMPO/NaClO/NaClO2 system: effect of the oxidation conditions on carboxylate content and degree of polymerization

Oxidation of bleached wood pulp by the TEMPO/NaClO/NaClO2 system was carried out at pH 3.5–6.8 and 25°–60°C with different amounts of NaClO, and investigated in terms of effects of the reaction conditions on carboxylate content and degree of polymerization (DP) of the oxidized pulp. Oxidation was accelerated by the addition of NaClO, when carried out at pH 6.8 and 40°–60°C. Addition of NaClO of more than 0.5 mmol per gram of the pulp was effective to accelerate the oxidation. Carboxylate content of pulp oxidized under such conditions increased to approximately 0.6 mmol/g within 6 h. Although DP of the oxidized pulp gradually decreased with oxidation time, no significant differences in DP of oxidized pulps were found at oxidation temperatures between 25° and 60°C, and DP values of more than 900 were maintained after oxidation for 54 h at 60°C.

Fine structure characterization of amylopectins from grain amaranth starch

The aim of this study was to determine the fine structure of amylopectin from grain amaranth. Amaranthus amylopectin was hydrolyzed with α-amylase, and single clusters and a group of clusters (domain) were isolated by methanol precipitation. The domain and the clusters were treated with phosphorylase a and then β-amylase to remove all external chains, whereby the internal structure was obtained. The ϕ,β-limit dextrins were analyzed on Sepharose CL 6B. The average DP (degree of polymerization) and peak-DP values of fractions of clusters were 57 and 82, respectively; the values of the domain were 137 and 309, respectively. The unit chain length profiles were analyzed by high-performance anion-exchange chromatography with pulsed amperometric detector (HPAEC–PAD). The results showed that the domain fraction contained ∼2.2 clusters, and single clusters were composed of ∼13 chains. The ϕ,β-limit dextrins of the clusters were further hydrolyzed with α-amylase to characterize their building block composition. The average DP of the branched blocks was ∼11 and they contained on average ∼2.5 chains. Their average chain length, internal chain length, and degree of branching were approximately 4.3, 2.8, and 14, respectively. A cluster consisted of ∼6 branched blocks, and the internal chain length between the blocks was ∼6.8.