Cellulose swelling by protic solvents: which properties of the biopolymer and the solvent matter?

The question posed in the title has been addressed by studying the swelling of celluloses at 20 C by twenty protic solvents, including water; linear- and branched-chain aliphatic alcohols; unsaturated aliphatic alcohols, and alkoxyalcohols. The biopolymers investigated included microcrystalline cellulose, MC, native and never-dried mercerized cotton cellulose, cotton and M-cotton, and native and never-dried mercerized eucalyptus cellulose, eucalyptus and M-eucalyptus, respectively. In most cases, better correlations with the physico-chemical properties of the solvents were obtained when the swelling was expressed as number of moles of solvent/anhydroglucose unit, nSw, rather than as % increase in sample weight. The descriptors employed in these correlations included, where available, Hildebrand`s solubility parameters, Gutmann`s acceptor and donor numbers, solvent molar volume, V(S), as well as solvatochromic parameters. The latter, employed for the first time for correlating the swelling of biopolymers, included empirical solvent polarity, E(T)(30), solvent ""acidity"", alpha(S), ""basicity"", beta(S), and dipolarity/polarizability, pi(S)*, respectively. Small regression coefficients and large sums of the squares of the residues were obtained when values of nSw were correlated with two solvent parameters. Much better correlations were obtained with three solvent parameters. The most statistically significant descriptor in the correlation equation depends on the cellulose, being pi(S)* for MC, cotton, and eucalyptus, and V(S) for M-cotton and M-eucalyptus. The best correlations were obtained with the same set of four parameters for all celluloses, namely, solvent pKa (or alpha(S)) beta(S), pi(S)*, and V(S), respectively. These results indicate that the supra-molecular structure of the biopolymer, in particular the average sizes of crystallites and micro-pores, and the presence of its chains in parallel (cellulose I) or anti-parallel (cellulose II) arrangements control its swelling. At least for the present biopolymer/solvent systems, use of solvatochromic parameters is a superior alternative to Hildebrand`s solubility parameters and/or Gutmann`s acceptor and donor numbers. The relevance of these results to the accessibility of the hydroxyl groups of cellulose, hence to its reactivity, is briefly discussed.

Acetylation of cellulose in LiCl-N,N-dimethylacetamide: first report on the correlation between the reaction efficiency and the aggregation number of dissolved cellulose

The acylation of three cellulose samples by acetic anhydride, Ac(2)O, in the solvent system LiCl/N,N-dimethylacetamide, DMAc (4 h, 110 A degrees C), has been revisited in order to investigate the dependence of the reaction efficiency on the structural characteristics of cellulose, and its aggregation in solution. The cellulose samples employed included microcrystalline, MCC; mercerized cotton linters, M-cotton, and mercerized sisal, M-sisal. The reaction efficiency expresses the relationship between the degree of substitution, DS, of the ester obtained, and the molar ratio Ac(2)O/AGU (anhydroglucose unit of the biopolymer); 100% efficiency means obtaining DS = 3 at Ac(2)O/AGU = 3. For all celluloses, the dependence of DS on Ac(2)O/AGU is described by an exponential decay equation: DS = DS(o) - Ae(-[(Ac2O/AGU)/B]); (A) and (B) are regression coefficients, and DS(o) is the calculated maximum degree of substitution, achieved under the conditions of each experiment. Values of (B) are clearly dependent on the cellulose employed: B((M-cotton)) > B((M-sisal)) > B((MCC)); they correlate qualitatively with the degree of polymerization of cellulose, and linearly with the aggregation number, N(agg), of the dissolved biopolymer, as calculated from static light scattering measurements: (B) = 1.709 + 0.034 N(agg). To our knowledge, this is the first report on the latter correlation; it shows the importance of the physical state of dissolved cellulose, and serves to explain, in part, the need to use distinct reaction conditions for MCC and fibrous celluloses, in particular Ac(2)O/AGU, time, temperature.

Probing the dependence of the properties of cellulose acetates and their films on the degree of biopolymer substitution: use of solvatochromic indicators and thermal analysis

Although cellulose acetates, CAs, are extensively employed there is scant information about the systematic dependence of their properties on their degree of substitution, DS; this is the subject of the present work. Nine CAs samples, DS from 0.83 to 3.0 were synthesized; their films were prepared. The following solvatochromic probes have been employed in order to determine the empirical polarity, E (T)(33); ""acidity, alpha""; ""basicity, beta"", and ""dipolarity/polarizability, pi*"" of the casted films: 2,6-dichloro-4-(2,4,6-triphenyl-pyridinium-1-yl) phenolate, WB; 4-nitroaniline; 4-nitroanisole; 4-nitro-N,N-dimethylaniline; 2,6-diphenyl-4-(2,4,6-triphenyl-pyridinium-1-yl)phenolate, RB. Additionally, two systems, ethanol plus ethyl acetate (EtOH-EtAc), and cellulose plus cellulose triacetate, CTA, were employed as models for CAs of different DS. Regarding the model systems, the following was observed: (i) For EtOH-EtAc, the dependence of all solvatochromic parameters on the ""equivalent-DS"" of the binary mixture was non-linear because of preferential solvation; (ii) The dependence of E (T)(33) on equivalent DS of the cellulose-CTA films is linear, but the slope is smaller than that of the corresponding plot for CAs. This is attributed to the more efficient hydrogen bonding in the model system, a conclusion corroborated by IR measurements. The dependence of solvatochromic parameters of CAs on their DS is described by the simple equations; a consequence of the substitution of the OH by the ester group. The thermal properties of bulk CAs samples were investigated by DSC and TGA; their dependence on DS is described by simple equations. The relevance of these data to the processing and applications of CAs is briefly discussed.

Self-reinforced composites obtained by the partial oxypropylation of cellulose fibers. 2. Effect of catalyst on the mechanical and dynamic mechanical properties

This work describes the partial oxypropylation of filter paper cellulose fibers, employing two different basic catalyst, viz., potassium hydroxide and 1,4-diazabicyclo [2.2.2] octane, to activate the hydroxyl groups of the polysaccharide and thus provide the anionic initiation sites for the ""grafting-from"" polymerization of propylene oxide. The success of this chemical modification was assessed by FTIR spectroscopy, X-ray diffraction, scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis and contact angle measurements. The study of the role of the catalyst employed on the extent of the modification and on the mechanical properties of the ensuing composites, after hot pressing, showed that both the Bronsted and the Lewis base gave satisfactory results, without any marked difference.

Biobased films prepared from NaOH/thiourea aqueous solution of chitosan and linter cellulose

In the present study, films based on linter cellulose and chitosan were prepared using an aqueous solution of sodium hydroxide (NaOH)/thiourea as the solvent system. The dissolution process of cellulose and chitosan in NaOH/thiourea aqueous solution was followed by the partial chain depolymerization of both biopolymers, which facilitates their solubilization. Biobased films with different chitosan/cellulose ratios were then elaborated by a casting method and subsequent solvent evaporation. They were characterized by X-ray analysis, scanning electron microscopy (SEM), atomic force microscopy (AFM), thermal analysis, and tests related to tensile strength and biodegradation properties. The SEM images of the biofilms with 50/50 and 60/40 ratio of chitosan/cellulose showed surfaces more wrinkled than the others. The AFM images indicated that higher the content of chitosan in the biobased composite film, higher is the average roughness value. It was inferred through thermal analysis that the thermal stability was affected by the presence of chitosan in the films; the initial temperature of decomposition was shifted to lower levels in the presence of chitosan. Results from the tests for tensile strength indicated that the blending of cellulose and chitosan improved the mechanical properties of the films and that an increase in chitosan content led to production of films with higher tensile strength and percentage of elongation. The degradation study in a simulated soil showed that the higher the crystallinity, the lower is the biodegradation rate.

Kinetics of autocatalytic acid hydrolysis of cellulose with crystalline and amorphous fractions

The acid hydrolysis of cellulose with crystalline and amorphous fractions is analyzed on the basis of autocatalytic model with a positive feedback of acid production from the degraded biopolymer. In the condition of low acid rate production compared with hydrolysis rate, both fraction of cellulose decrease exponentially with linear and cubic time dependence, and the normalized number of scissions per cellulose chain follows a sigmoid behavior with reaction time. The model predicts that self generated acidic compounds from cellulose accelerate the degradation of the biopolymer. However, if the acidic compounds produced are volatile species, then their release under low pressure will reduce the global rate of degradation of cellulose toward its intrinsic rate value determined by the residual acid catalyst present in the starting material.

Agro-Based Biocomposites for Industrial Applications

Leaf fibers are fibers that run lengthwise through the leaves of most monocotyledonous plants such as pineapple, banana, etc. Pineapple (Ananas comosus) and Banana (Musa indica) are emerging fiber having a very large potential to be used for composite materials. Over 150,000 ha of pineapple and over 100,000 ha of banana plantations are available in Brazil for the fruit production and enormous amount of agricultural waste is produced. This residual waste represents one of the single largest sources of cellulose fibers available at almost no cost. The potential consumers for this fiber are pulp and paper, chemical feedstock, textiles and composites for the automotive, furniture and civil construction industry.

Approximate solution of the autocatalytic hydrolysis of cellulose

Depolymerization of cellulose in homogeneous acidic medium is analyzed on the basis of autocatalytic model of hydrolysis with a positive feedback of acid production from the degraded biopolymer. The normalized number of scissions per cellulose chain, S(t)/nA degrees A = 1 - C(t)/C(0), follows a sigmoid behavior with reaction time t, and the cellulose concentration C(t) decreases exponentially with a linear and cubic time dependence, C(t) = C(0)exp[-at - bt (3)], where a and b are model parameters easier determined from data analysis.

Solar PV Powered Air Conditioner Analysis for an Office/Classroom in a Tropical Climate

This thesis focuses on using photovoltaic produced electricity to power air conditioners in a tropical climate. The study takes place in Surabaya, Indonesia at two different locations the classroom, located at the UBAYA campus and the home office, 10 km away. Indonesia has an average solar irradiation of about 4.8 kWh/m²/day (PWC Indonesia, 2013) which is for ideal conditions for these tests. At the home office, tests were conducted on different photovoltaic systems. A series of measuring devices recorded the performance of the 800 W PV system and the consumption of the 1.35 kW air conditioner (cooling capacity). To have an off grid system many of the components need to be oversized. The inverter has to be oversized to meet the startup load of the air conditioner, which can be 3 to 8 times the operating power (Rozenblat, 2013). High energy consumption of the air conditioner would require a large battery storage to provide one day of autonomy. The PV systems output must at least match the consumption of the air conditioner. A grid connect system provides a much better solution with the 800 W PV system providing 80 % of the 3.5 kWh load of the air conditioner, the other 20 % coming from the grid during periods of low irradiation. In this system the startup load is provided by the grid so the inverter does not need to be oversized. With the grid-connected system, the PV panel’s production does not need to match the consumption of the air conditioner, although a smaller PV array will mean a smaller percentage of the load will be covered by PV. Using the results from the home office tests and results from measurements made in the classroom. Two different PV systems (8 kW and 12 kW) were simulated to power both the current air conditioners (COP 2.78) and new air conditioners (COP 4.0). The payback period of the systems can vary greatly depending on if a feed in tariff is awarded or not. If the feed in tariff is awarded the best system is the 12 kW system, with a payback period of 4.3 years and a levelized cost of energy at -3,334 IDR/kWh. If the feed in tariff is not granted then the 8 kW system is the best choice with a lower payback period and lower levelized cost of energy than the 12 kW system under the same conditions.

Energieffektivisering av klimatskal i tropiskt klimat : Fallstudie av en byggnad i Surabaya, Indonesien

Studien omfattar en undersökning av en byggnad i Surabaya, Indonesien belägen på universitet UBAYA. Användningen av luftkonditionering ökar kraftigt i utvecklingsländer. Detta gör att behovet av förbättringar i såväl klimatanläggningar som i byggnader kommer att vara nödvändiga för att inte orsaka ytterligare påfrestningar på miljön genom ökad energianvändning Syftet med studien är att hitta energibesparande åtgärder på byggnadens klimatskal med hänsyn till det tropiska klimatet utan att orsaka fuktproblem i ingående byggnadsdelar. Byggnaden fungerar i dagsläget bra ur fuktsynpunkt och har inga direkt synliga skador orsakade av fuktproblem i konstruktionen. Däremot påvisar det höga uvärdet för byggnaden dess ineffektivitet gällande energibehov. Fyra olika åtgärdsförslag med utgångspunkt i den nuvarande konstruktionen presenteras i studien. Åtgärdsförslagen utvärderas ur fuktsynpunkt med programmet WUFI samt ur ett energimässigt perspektiv med programmet Polysun. Resultatet visar att störst energibesparing kan ske genom att isolera taket då det visar sig vara en stor värmekälla till byggnaden. Denna åtgärd innebär samtidigt en viss risk för fuktproblem på grund av höga relativa fukthalter och temperaturer. Även en tätning av de nuvarande läckagen i byggnaden påverkar energiförbrukningen i stor utsträckning, vilket gör dessa två åtgärder till den bästa kombinationen för att sänka energiförbrukningen. Att byta ut nuvarande englaskassetter mot tvåglas samt isolera de befintliga ytterväggarna är de åtgärder som påverkar energibehovet minst. Några av de slutsatser som dras ur studien är att totalt sett kan byggnadens energiförbrukning sänkas med 50 % om samtliga åtgärdsförslag genomförs. Fuktriskerna ökar vid isoleringsåtgärder men är genomförbara.