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Paper derived from lignocellulose has great advantages over plastics as packaging material, nevertheless, the poor water- and oil-resistances of paper-derived products limited their application in high-end field. Herein, novel dimer acid-based waterborne polyurethanes (DWPUs) with different content of dimer acid-based polyester polyol (DG) were prepared and used as water- and oil-resistant coating for paper substrate. The effects of DG contents on water- and oil-resistances, mechanical properties and thermal stability of DWPUs coated papers were systematically investigated. When the content of DG reached up to 7 wt% (based on polyester glycol), the paper coated by DWPU exhibited 88.06% decrease in Cobb 60 value, 8.7 times increase in kit rating compared with uncoated paper. Meanwhile, DWPUs coated papers showed good mechanical properties and thermal stability. These improvements are attributed to the flexible long-alkyl chain, and six-ring structure of DWPUs as well as the continuous and homogeneous DWPU-derived membrane on the surface of paper. This study provides a new framework for the preparation of high quality, multifunctional, environmentally friendly water- and oil-resistant coatings for paper substrates.

To study the influence of different concentrations of zinc oxide (ZnO)/silicon dioxide (SiO2) composite coating on hydrophobic property and mechanical stability of paper mulch film, three kinds of ZnO/SiO2 composite coating paper mulch films (2%, 4%, 6%) with different coating substance contents were prepared by brush coating method. Through particle size analysis, contact angle, rolling angle and mechanical stability test, combined with scanning electron microscope, three-dimensional morphology and roughness measuring instrument, the optimal concentration of ZnO/SiO2 composite coated paper mulch film was screened out. Through acid-base salt corrosion test, silver mirror reaction and surface self-cleaning, the optimal concentration of composite coated paper mulch film was compared with the original paper mulch film to prove its excellent chemical stability and hydrophobicity. The results show that the paper mulch film with 4% coating material has excellent hydrophobicity and mechanical stability, can effectively reduce the surface roughness of paper mulch film, and has remarkable effects in resisting acid, alkali and salt and self-cleaning.

Sustainable and low-cost cellulose-based metallisation is the prerequisite for wearable and disposable electronics fabrication. In this paper, to realize the simplified, low-cost and high efficient metallisation, a new method had been proposed without both the noble metal activators and the corrosive chemicals. The modified electroless plating processes had been employed in activation and deposition procedure. The nickel ions were first physiadsorbed on the cellulose paper (CP) fibers and then reduced into clusters by reducing agent which can act as the seeds to initiate the electroless plating process. The gold galvanic displacement was conducted further to modify the nickel surface. Via these processes, the cellulose paper was metallised with Ni-P and Au/Ni-P successfully. The morphological and microstructural properties of the resulted Ni-P/CP and Au/Ni-P/CP hybrids were evaluated. The Ni-P/CP composites had a low surface resistance below 0.5 Ω sq-1 while the Au/Ni-P/CP composites are below 0.1 Ω sq-1. The relationship between the mechanical and electrical properties with the plating parameters is discussed. The results indicated that Au/Ni-P/CP had good electrical conductivity and mechanical flexibility. Finally, the application demonstration for supercapacitor with the modified metallisation method was exhibited. This work offers a facile and non-toxic path to develop high-performance metallisation for functional cellulose-based materials.

Enzyme use has provided boost to the technoeconomics of many industrial processes. In this chapter, we summarize different cellulase-based industrial processes for preparation of paper, pulp, brewing products, and different foods. This review presents a brief chemistry and mechanism of cellulose degradation by the cellulase enzyme. Also, cellulase production abilities of many microbial species have been addressed in this chapter. Cellulase plays a major role in production of good-quality paper and pulp. It’s used to debark the biomass and to remove lignocellulosic part. This enzyme also has application in recycling of used paper by deinking and biobleaching. Cellulase enhances freeness and drainage ability of the fibers without compromising the brightness of the fibers. In brewing industry, cellulase in combination of other enzymes is used to extract the more sugar for better-quality alcohol production. Cellulases have a wide range of potential applications in food and beverage processing, production of fruit and vegetable juices, and improvement of methods for extraction, clarification, and stabilization.

During recent years, the socio political pressure to develop suitable technologies capable of treating wastewater from the paper and pulp industry has increased due to strict environmental regulations. System closure could potentially lead to substantial operating and discharge cost savings. This study evaluates the potential of combining an aerobic moving bed biofilm reactor (MBBR) (biological) and a Fenton-like system (advanced oxidation processes) for treating recycle mill effluent (RME). The performance of the moving bed biofilm reactor (MBBR) was evaluated at three different hydraulic residence times (HRT). The HRT used were 24, 16 and 5 h and the corresponding total chemical oxygen demand (COD) removals were 55, 49 and 43% respectively. The volatile organic acids (VOA) removals were 63.5, 58.7 and 53% respectively. The Kincannon-Stover model was used to describe the kinetic behaviour of the MBBR. The calculated KB and Umax parameters for the COD were 26.37 g.L−1.d−1 and 15.06 g.L−1.d−1 respectively. For the VOA, the KB and Umax parameters were 11.81 g.L−1.d−1 and 8.87 g.L−1.d−1. The Fenton-like experiments were carried out in batch runs. The first experiments were carried out to determine the optimal reaction parameters. Maximum COD removals were found to be at a pH of 3.33, Fe3+ dosage of 1,000 mg/L and H2O2 of 14.55 mM. Pseudo-first order reaction kinetics was used to describe the kinetic characteristics of the Fenton-like treatment system. The calculated kinetic parameters ηmax (%) and kCOD (min−1) were 53.8% and 0.112 min−1 respectively at a pH of 3.24, Fe3+ dosage of 250 mg/L and a H2O2 dosage of 77 mM. Keywords: Moving bed biofilm reactor (MBBR), Fenton-like system, Recycle mill effluent (RME)

D0bleaching wastewater from E. globulus Kraft pulping industry was treated by Fenton and photo-Fenton processes. The aim was to optimize the operational conditions for adsorbable organic halides (AOX) removal, namely oxidant concentration, [H2O2], catalyst concentration, [Fe2＋], and treatment time, using the central composite experimental design (CCED) tool. Temperature and pH were set at 60 ºC and 2, respectively, which are similar to the natural values of the D0bleaching wastewater. Both processes showed potential to remove AOX from D0with 177 - 178 mM H2O2 and 10 min reaction time. Maximum AOX removal was 85 % for the Fenton process with 8.5 mM Fe2＋, and 95 % for the photo-Fenton process with 2.0 mM Fe2＋ and UV irradiance 142 W.m− 2. For both methods, the only statistically significant variable (p=0.05) was the concentration of oxidant, [H2O2]. Keywords: AOX, Bleaching wastewater, CCED, Fenton, Photo-Fenton, Pulp and paper industry

Fly ash (FA) from biomass combustion and biological sludge (S), both wastes from the pulp and paper industry, were granulated in different proportions (90% FA + 10% S, and 70% FA + 30% S w/w, dry weight basis, dw) and used to recover the functionality of soils affected by mining activities (Aljustrel, Iberian Pyrite Belt), with and without the application of municipal solid waste compost (MSWC). Application doses of both mixtures were 2.5, 5.0 and 10% (w/w, dw). These materials corrected soil acidity to circumneutral values and increased extractable P and K concentrations. A significant increase in soil organic matter (from 0.6 to 0.8–1.5% w/w, dw) and N content (from 0.04 to 0.09–0.12% w/w, dw) was also observed, but only when MSWC was applied. The soil was already heavily contaminated with Cu, Pb and Zn and the application of amendments did not increase their pseudo-total concentrations. The CaCl2 extractable fractions of both Cu and Zn decreased to very low values. The improvement in soil quality, compared to fertilizer only treatment, was further evidenced by the increase in some soil enzymatic activities (dehydrogenase, β-glucosidase and cellulase), with a better response for the granules with the higher proportion of biological sludge, as well as by the decrease in the soil-water extract toxicity towards different organisms (Daphnia magna, Thamnocephalus platyurus, and Pseudokirchneriella subcapitata). Agrostis tenuis germinated and grew during the first month only in the amended pots, but, after that, a considerable phytotoxic effect was evident. This was mainly attributed to salt stress or to some specific ionic toxicity. In conclusion, to establish a long-term plant cover in mining soils amended with biomass ash-based materials, the selection of plants with higher resistance to salinity and/or the stabilization of the amendments, to reduce their soluble salt content, is recommended.

This work is concerned with the electrochemical detection of new psychoactive substances (NPSs), in particular 2,5-dimethoxy-N-(2-methoxybenzyl) phenethylamine structures (NBOMes) and the analogous 2,5-dimethoxy phenethylamine structures (2C-X group) on boron-doped diamond (BDD) electrodes. Fast square-wave voltammetry was used to identify the substances in question. The antifouling properties of the BDD surface resulted in stable, repeatable, sensitive and unique voltammetric responses for these NPSs, producing different voltammetric signatures. Different NBOMes were identified by voltammetric methods in blotting paper seized from the drug market, without any interference from LSD, another psychedelic drug distributed via blotting paper. The proposed method achieved detection limits lower than 0.1μmolL−1 with high precision (RSD

The process of bioconversion of solid organic wastes through vermicomposting justifies the environmental message for sustainability such as reduce, recycle and reuse of wastes. In the present study, wastes derived from two different types of paper mill sludge (primary and secondary), was used for their bioconversion through the vermicomposting process using an indigenous species of earthworm (Perionyx excavatus). The maturity and stability stage of vermicompost production was assessed using FT-IR, GC-MS and TG analyses. During vermicomposting, different biochemical functional groups present in the wastes have shown differential chemical alteration and turnover as revealed by FT-IR spectroscopy. This study has also confirmed the trend of biodegradation of complex substances like lignin, cellulose, proteins etc. and thereby demonstrates the extent of mineralization. TG spectral analysis had revealed a mass loss of 80% and 71% in vermicompost produced from primary and secondary sludge respectively. GC-MS studies have also shown the presence of several humic acids like octadecanoic acid, heptadecanoic acid etc. in the decomposing substances demonstrating as an indicator of the maturity of products. This was further confirmed by the decrease of humification index which focuses the combined action of both earthworms and microbes in the degradation of organic wastes. The present study has highlighted the role of an indigenous earthworm in converting specific industrial wastes especially by recording the point of maturation using humic acids an indicator of the quality of decomposing of wastes following several instrumental applications.

For the first time the feasibility of using an alkaline wastewater coming from the pulp and paper industry as an activator, partially (50 vol%) replacing commercial sodium hydroxide, in the production of cork-based activated carbons was evaluated. The activated carbons showed the highest value of specific surface area ever reported for cork-based activated carbons (1670 m2/g), surpassing several other commercial and waste-based ones. These eco-friendly cork and paper waste-based activated carbons were then evaluated as methylene blue adsorbent materials. The influence of contact time, methylene blue initial concentration and adsorbent amount on the methylene blue removal efficiency by the activated carbons was studied. Extremely fast (>99.9% removal in 5 min) and efficient methylene blue adsorption (uptake of 350 mg/g) by the cork and paper waste-based adsorbents was achieved, which demonstrates the huge potential of these innovative adsorbents. These activated carbons were produced using two unexplored industrial by-products (alkaline wastewater and cork) and, therefore, may be an inexpensive source of activated carbons, which can be used for the effective removal of dyes from wastewaters. Furthermore, despite the very large surface area and high removal efficiency this is not a nano material (being around 30–50 μm in size), its capabilities being due to its unique cork-derived microstructure, and hence it can be handled and removed/filtered much more easily than nanocarbons, and without any associated health or environmental risks. This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT Ref. UID/CTM/50011/2013), financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. R.C. Pullar wishes to thank FCT grant IF/00681/2015 for supporting this work, and R.M. Novais wishes to thank FCT project H2CORK (PTDC/CTM-ENE/6762/ 2014). published

This work demonstrates a stand-alone power source that integrates a paper-based hydrogen fuel cell with a customized chemical heater that produces hydrogen in-situ upon the addition of a liquid. The presented approach operates by capillary action and takes advantage of the hydrogen released as a by-product of an exothermic reaction used in point-of-care diagnostics. The paper-based fuel cell produces a maximum power of 25.8 mW (103.2 mW cm−2), which is suitable for powering a diversity of electrical devices such as commercially available digital pregnancy tests and glucometers. While device shape and dimensions can be customized, here it is shown that the fuel cell can be designed in a compact form factor and footprint comparable to a lateral flow test while providing a remarkable power output. This approach holds great promise for powering portable diagnostics, as the generated electric power could enable device functionalities required for advanced assays, such as device timing, actuation, and signal quantification. Part of the same liquid sample that is to be analyzed (urine, saliva, water, etc) could be used to trigger the hydrogen generation and start the fuel cell operation., J.P. Esquivel acknowledges support from Marie Curie International Outgoing Fellowship (APPOCS - GA.328144) within the 7th European Community Framework Programme. J. Buser and P. Yager were supported by a grant from DARPA DSO/BTO--HR0011-11-2-0007, awarded to Yager at the University of Washington. P. Yager was supported in part by funds from the Department of Bioengineering at the University of Washington. S. Rojas acknowledges financial support from project ENE2013-42322R. N. Sabaté would like to thank financial support received from ERC Consolidator Grant (SUPERCELL - GA.648518).

In this work, several cellulose board grades, including waste board, fluting, and waste milk container board, were pretreated with green choline chloride-urea deep eutectic solvent (DES) and nanofibrillated using a Masuko grinder. DES-treated bleached chemical birch pulp, NaOH-swollen waste board, and bleached chemical birch pulp were used as reference materials. The properties of the nanofibrils after disc grinding were compared with those obtained through microfluidization. Overall, the choline chloride-urea DES pretreatment significantly enhanced the nanofibrillation of the board pulps in both nanofibrillation methods—as compared with NaOH-treated pulps—and resulted in fine and long individual nanofibrils and some larger nanofibril bunches, as determined by field emission scanning electron microscopy and transmission electron microscopy. The nanofibril suspensions obtained from the DES pretreatment had a viscous, gel-like appearance with shear thinning behavior. The nanofibrils maintained their initial crystalline structure with a crystallinity index of 61%–47%. Improved board handsheet properties also showed that DES-treated and Masuko-ground waste board and paper nanocellulose can potentially enhance the strength of the board. Consequently, the DES chemical pretreatment appears to be a promising route to obtain cellulose nanofibrils from waste board and paper.

Two organic–inorganic hybrid sol–gel coatings were developed in order to modify the surface energy and moisture behaviour of the commercial impregnated paper. The surface characteristics of the paper samples were studied by scanning electron microscopy (SEM), confocal laser scanning microscopy (CLSM), atomic force microscopy (AFM), attenuated total reflectance Fourier transform infrared spectrometry (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectroscopy (ToF-SIMS). It was found that the applied sol–gel coatings as well as the curing process changed the surface structural and chemical properties of the impregnated paper. The chemical bonding between the hydroxyl groups present on paper surface and silanol groups from sol–gel coatings was confirmed by the FTIR spectra. The measured surface energies divided into polar and dispersive components indicated that the coating B resulted in less polar surface than did the coating A which was more polar than the reference (the impregnated paper with water and heat treatment). Coating B brought about the lowest total surface energy. It was obtained that the water repellence of the impregnated paper was improved by both coatings and the curing process.

Papermaking deposits can be classified as being organic, inorganic, or microbiological. Most paper machine deposits contain a combination of some or all of these major component types. Although inorganic deposits tend to be more of a problem in the stock and flow-piping systems of the paper mill, organic deposits tend to be more problematic in the headbox, wet end, and press section of the paper machine. These contaminants form tacky deposits that can plug forming fabrics and wet press felts. Microorganisms in paper mill systems take two forms: planktonic and sessile. Planktonic organisms do not readily cause problems in the system; however, in the sessile form, these same organisms can become problematic. Inorganic and organic deposits offer a readily available food source for sessile organisms, which attach themselves to deposit surfaces. Several of these organisms classified as slime formers are able to secrete a protective polysaccharide coating around themselves known as biofilm. The slime formers, in combination with inorganic and organic process additives and contaminants, can form deposits that coat process equipment and create sheet quality and runnability problems. In addition to slime formers, anaerobic bacteria can form under deposits. The most common type of anaerobic bacteria found in paper mills is sulfate-reducing bacteria, which is capable of converting sulfate in the system to highly corrosive hydrogen sulfide.

Company profiles of major pulp and paper chemical suppliers such as Kemira, Akzo Nobel NV, Eka Chemicals AB, Ashland, Inc., BASF, Buckman Laboratories International, Inc., Clariant, and Nalco Chemicals are presented. Major and niche enzyme suppliers—Novozymes, Enzymatic Deinking Technologies, Genencor, AB enzymes, DSM (Netherlands), Diversa (USA), Kao (Japan), and Tritex etc.—are also presented.

Pick-up felts and deposits in wet end splash areas and in storage tanks of paper machines contained large amounts of thiosulfate (80– 16 000 mg kg −1 , wet weight) and oxalate (20– 2300 mg kg −1 , wet weight). These anions were absent ( mg l −1 ) in process water and found in raw materials only in low concentrations (5– 10 mg kg −1 , wet weight). Similar and larger amounts of thiosulfate, sulfite and oxalate were generated de novo from sulfate and sheets of chemical pulp in a splash area simulator fed with artificial paper machine white water in the laboratory. Stainless steel UNS S30400 coupons placed in the simulator developed significant corrosion pits within 4 weeks. Pitting was most extensive under or vicinal to patches where large amount of thiosulfate and oxalate accumulated in the pulp sheet. Pitting of UNS S31600 occurred only vicinal to the pulp sheet. The pitted steel surfaces accumulated large amounts of silicon containing material. The biogenic conversion of sulfate into compounds of lower oxidation states occurred more extensively on stainless steel UNS S30400 than on UNS S31600.

The closure of water circuits within pulp and paper mills has resulted in a higher contamination load of the final mill effluent, which must consequently be further treated in many cases to meet the standards imposed by the legislation in force. Different treatment strategies based on advanced oxidation processes (ozonation and TiO2-photocatalysis), and their combination with biological treatment (MBR), are herein assessed for effluents of a recycled paper mill and a kraft pulp mill. Ozone treatment achieved the highest efficiency of all. The consumption of 2.4 g O3 L−1 resulted in about a 60% COD reduction treating the effluent from the kraft pulp mill at an initial pH = 7; although it only reached about a 35% COD removal for the effluent of the recycled paper mill. Otherwise, photocatalysis achieved about a 20–30% reduction of the COD for both type of effluents. In addition, the effluent from the recycled paper mill showed a higher biodegradability, so combinations of these AOPs with biological treatment were tested. As a result, photocatalysis did not report any significant COD reduction improvement whether being performed as pre- or post-treatment of the biological process; whereas the use of ozonation as post-biological treatment enhanced COD removal a further 10%, summing up a total 90% reduction of the COD for the combined treatment, as well as it also supposed an increase of the presence of volatile fatty acids, which might ultimately enable the resultant wastewater to be recirculated back to further biological treatment.

The oxygen electrodes in unitized regenerative fuel cells (URFC) must have high activities towards oxygen reduction reaction (ORR) as well as oxygen evolution reaction (OER), thus requiring high loading of noble metal electrocatalysts. In this study, porous Pt/IrO2/carbon paper (CP) electrocatalysts were developed to reduce the metal loading. The Pt/IrO2/CP electrodes were fabricated by sequential formation of IrO2 layers (loading 0.1 mg cm−2) and porous Pt layers (0–0.3 mg cm−2) on CP substrates by electrodeposition and spraying techniques, respectively. The fuel cell (FC) performances increased linearly up to 0.69 A cm−2 with increasing Pt loading (up to ~0.3 mg cm−2) at 0.6 V, whereas the water electrolysis (WE) activity was highest at Pt loading of 0.2 mg cm−2. The current densities in the FC and WE modes and round-trip efficiency of the developed Pt/IrO2/CP electrodes with the oxygen electrocatalysts loadings of 0.3 and 0.4 mg cm−2 were higher or comparable to previously reported values with higher loading (1.5–4.0 mg cm−2). These high performances with low loading are probably due to the facile oxygen and water transport through well-developed macropores originating from the open CP structures, providing effective utilization of the IrO2 and Pt electrocatalysts towards OER and ORR, respectively. Keywords: Unitized regenerative fuel cell, Oxygen electrode, Platinum, Iridium oxide

The paper and pulp industry manufactures pulp and paper from wood or recycled fiber. This chapter identifies the chemicals involved in the process of production and provides general guidance on hazardous waste mitigation. This industry is the largest industrial process water user in the United States. Its manufacturing activities result in the release of many toxic substances into the surrounding communities that pollute air, water, and land, mainly in the pulping and bleaching stages. The process of pulping consists of initial processing, washing, and bleaching. Pulping is classified as chemical, mechanical, or semi-chemical, and of the chemical pulping methods, the kraft and sulfite processes are the most widely used. Bleaching is accomplished through elemental chlorine, elemental chlorine free, or totally chlorine free bleaching. The waste stream from bleaching contains chlorine compounds and organics that result in the formation of dioxins, furans, and chlorinated organics. This waste stream of toxic air and water pollutants does not get treated at water treatment plants, accumulating in the discharge body of water. The paper and pulp sector is subject to the same environmental regulations as other industry sectors, but the most significant recent rule-making activities affecting the pulp and paper sector are referred to collectively as the Cluster Rules, a set of air and water rules that were issued simultaneously.

International audience; A fluorescent chitosan derivative was deposited layer-by-layer onto conventional paper sheets and its distribution, in terms of both spreading and penetration, was assessed by SEM observations and emission measurements. The results showed that, on the one hand the surface distribution was highly homogeneous and, on the other hand, the penetration of chitosan within the paper pores ceased after a three layer deposit, beyond which any additional coating only produced an increase in its overall thickness and film-forming aptitude. These results show that this modified chitosan can be used as probe to optimize and understand the mechanism of the deposition of chitosan onto paper and other substrates.

Production of porous anorthite ceramics from mixtures of paper processing residues and three different clays are investigated. Suitability of three different clays such as enriched clay, commercial clay and fireclay for manufacturing of anorthite based lightweight refractory bricks was studied. Porous character to the ceramic was provided by addition of paper processing residues (PPR). Samples with 30–40 wt% PPR fired at 1200–1400 °C contained anorthite (CaO·Al 2 O 3 ·2SiO 2 ) as major phase and some minor secondary phases such as mullite (3Al 2 O 3 ·2SiO 2 ) or gehlenite (2CaO·Al 2 O 3 ·SiO 2 ), depending on the calcite to clay ratio. Anorthite formation for all clay types was quite successful in samples with 30–40 wt% of paper residues fired at 1300 °C. A higher firing temperature of 1400 °C was needed for the fireclay added samples to produce a well sintered product with large pores. Gehlenite phase occurred mostly at lower temperatures and in samples containing higher amount of calcium (50 wt% PPR). Compressive strength of compacted and fired pellets consisting of mainly anorthite ranged from 8 to 43 MPa.

The capitula of Cynara cardunculus contain hairs and pappi representing 7% of the total plant biomass. These low density biomass components could be mechanically separated without apparent losses using a whole-plant processing prototype. Hairs and pappi are filamentous structures made up of longitudinally aligned fibre cells, without intercellular voids or pitting, with the following dimensions regarding length, width and wall thickness: 1.35mm, 19.8, and 4.8 m for hairs and 1.78mm, 10.4, and 2.9 m for pappi. Chemically hairs and pappi have low content of ash (1.9% and 1.1%, respectively), extractives (5.4% and 6.0%) and lignin (10.6% and 17.8%), and high content of holocellulose (77.5% and 72.8%) and -cellulose (55.2% and 46.8%). Pulps could be produced using a conventional kraft process with high yields and low residual lignin, e.g. 63% at Kappa 7 for hairs and 48% at Kappa 11 for pappi, low coarseness values (0.04 and 0.03mgm−1) and adequate pulp properties for paper (40 and 42Nmg−1 tensile index; 3.6 and 3.4 kPam2 g−1 burst index in unrefined pulps of hairs and pappi, respectively). The results also indicated that there is scope for improving pulp quality by optimising pulping conditions to this type of new raw materials. The differences between hairs and pappi may also be further exploited namely the lower lignin content of hairs and the higher slenderness and wall thickness of pappi fibres. The utilization of hairs and pappi may strengthen the differentiated use of biomass fractions of the Cynara plant and its potential as a bioenergy crop.

Publisher Summary The papermaking process consists of several major steps: stock preparation, sheet forming, pressing, drying, and surface finishing. Starch is an important component of many paper grades. Starch consumption by weight in papermaking and paper conversion processes ranks third after cellulose fiber and mineral pigments. Starch is used as a flocculant and retention aid, as a bonding agent, as a surface size, as a binder for coatings, and as an adhesive in corrugated board, laminated grades, and other products. The major starch sources are corn, potato, waxy maize, wheat, and tapioca. Refined starches are supplied in powder form or as slightly aggregated pearl starch. Unmodified (native) starch is rarely used in the paper industry, except as a binder for laminates and in the corrugating process. Most starches for use in papermaking are specialty products that have been modified by controlled hydrolysis, oxidation, or derivatization. This chapter also covers various topics such as: application requirements for starch, dispersion of starch, environmental aspects of starch, starch analysis in paper, and use of starch in papermaking furnish, for surface sizing of paper, as a coating binder, as adhesive in paper conversion, and in newer specialty papers.

E-mail: delrio@irnase.csic.es (J.C. del Río), The chemical composition of the lipophilic extractives from jute (Corchorus capsularis) fibers, which are used for high-quality paper pulp manufacturing, was thoroughly studied. The extractives content was low (0.4%), and its composition was studied by gas chromatography-mass spectrometry. For a better characterization of the different homologous series and compounds present in minor amounts, the extract was also fractionated by solid-phase extraction. The most predominant lipophilic compounds present in jute fibers were high molecular weight ester waxes (24% of total extract), followed by free fatty acids (17%), free fatty alcohols (17%) and α-hydroxyfatty acids (14%). Additionally, significant amounts of alkanes (6%), ω-hydroxyfatty acids (6%), sterols (6%), steroid and triterpenoids ketones (3%) and steryl glycosides (1%) were also identified, together with minor amounts of mono- and diglycerides.

aDepartment of Molecular Microbiology, CIB, Consejo Superior de Investigaciones Científicas (CSIC), Velázquez 144, E-28006 Madrid, Spain; bDepartment of Textile and Paper Engineering, ETSII, Polytechnic University of Catalunya (UPC), Colón 11, E-08222 Terrassa, Spain; cDepartment of Biogeochemistry, IRNAS, CSIC, PO Box 1052, E-41080, Seville, Spain; dCelulosas de Levante SA (CELESA), Ctra. C-237, km 4.5, E-43500 Tortosa, Spain, High-quality flax pulp was bleached in a totally-chlorine-free (TCF) sequence using a laccase-mediator system. Three fungal laccases (from Pycnoporus cinnabarinus, Trametes versicolor and Pleurotus eryngii) and two mediators, 2,2´-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) and 1-hydroxybenzotriazole (HBT), were compared. P. cinnabarinus and T. versicolor laccases in the presence of HBT gave the best results in terms of high brightness and low lignin content (kappa number). The former laccase also resulted in the best preservation of cellulose and the largest removal of residual lignin as revealed by analytical pyrolysis, and was selected for subsequent TCF bleaching. Up to 90% delignification and strong brightness increase were attained after a laccase-mediator treatment followed by H2O2 bleaching. This TCF sequence was further improved by applying H2O2 under pressurized O2. In this way, we obtained up to 82% ISO brightness (compared with 37% in the initial pulp, and 60% in the peroxide-bleached control) and very low kappa number (near 1). Good results were also found when the laccase-mediator treatment was performed in a bioreactor under pressurized oxygen. The pulp properties obtained, which could not be attained by conventional TCF bleaching of flax pulp, demonstrate the feasibility of enzymatic bleaching to substitute chlorine-containing reagents in manufacturing of these high-price paper pulps., This study was supported by the European Commission (contract QLK3-99-590), the Spanish CICYT (FEDER project 2FD97-0896-C02, and projects AGL2002-00393, BIO2002-1166 and PPQ2000-1068-C02-02), the Comunidad de Madrid, and the CSIC network on “Bioremediation and Phytoremediation”.

Enzymatic versus chemical deinking is examined for MOW and photocopy prints. Several enzymatic preparations and two fibre/ink particle separation methods are tested. Deinking was monitored by image analysis and standard pulp and paper characterisation procedures. The effectiveness of the fibre/ink particle separation method depends on the ink particle’s size: for smaller particles a washing step is recommended whereas for larger particles, the use of flotation is necessary. The enzymatic treatment is a competitive alternative for MOW and photocopy paper deinking. However, the process requires the selection of an adequate enzymatic preparation for each paper grade.

Recombinant Cellulomonas fimi β-1,4-endoglucanases (Cel5A and Cel6A) and cellobiohydrolases (Cel6B and Cel48A) were assessed for their capacity to selectively modify the physical and optical properties of handsheets derived from a fully bleached, never-dried softwood pulp. The isolated binding domain (Cel6A CBD) and catalytic domain (Cel6A CD) were also evaluated. Treatment with endoglucanases, particularly Cel6A CD, caused substantial damage to the intrinsic fibre strength of the kraft furnish, and consequently compromised the physical handsheet properties. In contrast, treatment with Cel48A produced beneficial modifications, including improvements in handsheet tensile strength following mechanical refining and various degrees of wet pressing. Cel6B and Cel6A CBD had very limited effects on the fibre characteristics, and therefore did not alter the quality of the handsheets produced. An examination of carbohydrate solubilization and changes in the degree of polymerisation of the polysaccharides indicated that the capacity for Cel48A to beneficially modify pulp and paper characteristics seems to be related to its capacity to selectively degrade cellulose-hemicellulose linkages, and release and modify xylan moieties. Furthermore, this enzyme preparation demonstrated limited carbohydrate dissolution, indicating that the observed modifications were attained with very little yield loss. These results suggest that Cel48A, and enzymes with similar glycanase activity should be considered and further evaluated for their potential to treat pulp fibres to improve paper properties.

aCentro de Investigaciones Biológicas, CSIC, Ramiro de Maeztu 9, E-28040 Madrid, Spain bInstituto de Recursos Naturales y Agrobiología, CSIC, PO Box 1042, E-41080 Sevilla, Spain cENCE, CIT, Carretera de Campañó s/n, E-36157 Pontevedra, Spain, In the context of environmentally-friendly bleaching in paper pulp manufacturing, an enzymatic procedure was developed for the isolation of residual lignins from eucalypt pulp. The method was based on the hydrolysis and complete solubilization of pulp cellulose using a combination of Trichoderma cellulase and Aspergillus beta-glucosidase, followed by lignin purification using Bacillus protease (for hydrolysis of contaminating cellulase) and extraction of lignin with dimethylacetamide and NaOH. This method was applied to both unbleached and totally chlorine free bleached eucalypt kraft pulps. The different fractions obtained were analyzed by Fourier-transform infrared spectroscopy and pyrolysis-gas chromatography/mass spectrometry to evaluate the effect of the different isolation steps, and optimize the lignin isolation procedure. Depending of the type of pulp and its delignification degree most of the lignin was recovered from the cellulase hydrolyzate or the non-hydrolyzable residue. High-purity lignins were obtained from pulps by a new isolation procedure that included double solvent purification after combining the two fractions from protease treatment. This method is being used to analyze the effect of chlorine-free reagents (including enzymes) in clean bleaching sequences., This study has been supported by ENCE, the EU-Contract QLK5-99-1357, and the Spanish project AGL2002-00393.

The development of mathematical models that describe industrial processes is playing an increasing role in industrial context, because such models can replace, in some cases, experimental simulation, in a more inexpensive and flexible way. In this paper is presented a preliminary study of a transient model of a continuous moving bed reactor - the digester - used in the pulp and paper industry. In this complex and heterogeneous digester a moving bed of wood chips, containing cellulose, hemicellulose and lignin, reacts with sodium hydroxide and sodium sulfide - dissolved in a liquid phase - to remove the lignin from the cellulose fibers. The mathematical model studied here has been developed by Fernandes in a forthcoming Ph.D Thesis. The model is derived from the fundamental principles of mass and energy balance and is represented by a system of 15 partial differential equations (PDE) of convection-reaction type. The numerical methods used in the discretization of this PDE system are based on operator splitting which essentially consists in considering separately convection and reaction phenomena. This approach allows the use of methods with different properties - explicitness, implicitness and order - for each subprocess. The final global class of methods represents in some sense a “patching of tailored methods” well adapted to the feature of individual phenomena. Numerical simulations of the concentrations of organics and inorganics are presented.

A semi-batch cultivation of a Prasinophyceae, Tetraselmis sp.Tt-1, was examined using a 50L scale tubular bioreactor under lamps with a view to estimating its performance. The mean productivity of more than 20g/m 2 /day could be obtained by fixing the flow rate of the culture medium at 0.5m/s, which was the maximum in this apparatus, by drawing a partial medium once in two days, and by adjusting an initial cell concentration to 0.5-1.0g/L. A long-term and stable cultivation for more than two months could be carried out by this system. Our previous study, on the other hand, has shown that cell bodies of this microalga are of use as the partial substitute of a wood pulp paper [1]. In the present study, whole kenaf pulp paper including algae obtained by the above cultivation was made and its properties were examined. It was indicated that they also could be used as an agent for surface improvement of kenaf pulp paper in addition to a partial substitute for the pulp as in the case of a paper made from wood pulp.

1)Instituto de Recursos Naturales y Agrobiología de Sevilla, P.O. Box 1052, 41080-Seville, Spain; 2)ENCE-CIT, Ctra. Campañó, Ribeiro-Vao, 36157 Pontevedra, Spain; 3)Centro de Investigaciones Biológicas, Ramiro de Maeztu 9, E-28040 Madrid, Spain. E-mail address: delrio@irnase.csic.es (J.C. del Río), A set of Eucalyptus globulus woods from different origins and growth conditions, giving a wide range of pulp yields (from 40% to 60%) upon kraft cooking, was analyzed using Py-GC/MS. The carbohydrate-derived compounds and the compounds derived from syringyl (S) and guaiacyl (G) lignin units were analyzed and the lignin/carbohydrate and S/G ratios determined. Eucalypt woods giving higher pulp yield released higher amounts of S-type compounds upon Py-GC/MS. A significant correlation was observed between pulp yield and the lignin composition in terms of the S/G ratio. By contrast, the lignin/carbohydrate ratio obtained by Py-GC/MS, did not show a significant correlation with the pulp yield. This indicates that the lignin composition is a more important parameter influencing pulp yield than the lignin content., This study has been supported by Grupo Empresarial ENCE S.A. and the Spanish Ministerio de Ciencia y Tecnología (MCyT) (project AGL2002-00393). A.G. acknowledges a "Ramón y Cajal" contract of the Spanish MCyT.

Instituto de Recursos Naturales y Agrobiología, CSIC, P.O. Box 1052, E-41080, Seville, Spain E-mail address: delrio@irnase.csic.es, The composition of pitch deposits occurring in pulp sheets and mill circuits during soda/anthraquinone pulping and elemental chlorine-free pulp bleaching of bast fibers of industrial hemp (Cannabis sativa) has been studied. Pitch deposits were extracted with acetone, and the extracts analyzed by gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS). Acetone extracts (15-25% of pitch deposits) were constituted by the defoamers used at the mill and by lipophilic extractives from hemp fibers. Acetone-insoluble residues (75-85% of pitch deposits) were analyzed by pyrolysis-GC/MS in the presence and absence of tetramethylammonium hydroxide. These residues were constituted by salts of fatty acids (arising from hemp fibers) with calcium, magnesium, aluminum and other cations that were identified in the deposits. It was concluded that inappropriate use of defoamer together with the presence of multivalent ions seemed to be among the causes of hemp extractives deposition in the pitch problems reported here., This study has been supported by the Spanish Ministerio de Ciencia y Tecnología (MCYT) and FEDER funds (projects 2FD97-0896-C02-02 and AGL2002-00393). A.G. acknowledges a "Ramón y Cajal" contract of the Spanish MCYT. We also thank CELESA (Tortosa, Spain) for providing the samples.

The electrochemically coated conducting paper based point-of-care diagnostics using amperometric sensing principles for troponin detection has been demonstrated in the present report. The cost-effective and stable conducting polymer coating was achieved on papers using screen printing followed by electrochemical deposition techniques for the first time. The cyclic voltammetric analysis has revealed the stable and uniform conducting polyaniline (PANI) coating onto filter papers fabricated using the simple and novel approach. These strips were found to be very sensitive for the futuristic diagnostics and the concept was proved by utilizing these strips for the troponin detection in a wide physiological range (1–100 ng/mL) with sensitivity of 5.5 μA/ng mL−1 cm−2. Association constant of the electrode has been found to be 1.2×1013 Lmol−1. Keywords: Conducting paper, Screen-printed electrode, Polyaniline, Biosensor, Troponin

The enzymatic modification of cellulose, the major carbohydrate in different pulp fibres, offers unique opportunities for new applications, due to the different modes of action of individual cellulases. Although they all act on the same glycosidic β-1,4-linkage, different structural and functional modifications can be obtained depending on the type of fiber, enzyme and process phase used. Thus, cellulase based applications have been developed aiming at energy saving in refining, improvement of beatability, drainage and runnability of the paper machine, or enhancing de-inking processes. In these applications, the enzymatic treatment has been carried out on coarse or refined mechanical pulps, chemical pulps or recycled fibers at different phases of the processing. When applying cellulases, it is important to minimize the detrimental effects of these enzymes on the yield and strength properties of fibers. In this paper, the mode of action and effects of different types of cellulases; cellobiohydrolases and endoglucanases, are reviewed in the light of present applications.

In this study, commercially available softwood lignin was esterified with tall oil fatty acid (TOFA) and studied as barrier material in fibre-based packaging material. The lignin was esterified to different degrees of substitution and the chemical analyses of the resulting samples were carried out by FTIR, TMAH thermochemolysis GC–MS, 31P NMR and SEC. After functionalization, the thermoplastic properties of the lignin were enhanced as shown by DSC. The novel thermoplastic lignin samples were applied with a bar coater forming an even coating on the paperboard substrate. The WVTR of the paperboard (840 g/m2 × 24 h) could be reduced to 260 g/m2 × 24 h with a TOFA lignin ester double coating of 3.9 g/m2. Furthermore, a decrease in OTR value was observed for the TOFA lignin ester as well as the TOFA coated paperboard samples. In contrast to the TOFA coating, the modified lignin coatings exhibited a high and stable contact angle (80° for 2 min). The coating material did not affect the tensile strength of the paperboard. According to the results, the demonstration of the conversion of lignin into a value added product has been shown. Furthermore, the novel coating material shows promising properties for the development as sustainable barrier material in fibre-based packaging material to replace oil-based barriers.

The effects of retained wood resin and polysaccharides on paper strength, optical properties and fiction were studied. Wood resin, glucomannans and pectic acids were extracted from thermomechanical pulp (TMP). The wood resin was added in colloidal form to the fibre suspension and aggregated by the addition of cationic polymers or electrolytes. In part of the tests, polysaccharides were also added. Hand sheets were made and tested. The amounts of resin and polysaccharides in the sheets were determined by gas chromatography. The strength properties of the hand sheets deteriorated when the amount of wood resin was increased up to 2 mg/g. When the amount of wood resin was increased from 2 mg/g to 10 mg/g, only a slight decrease in strength properties was obtained. The static friction was lowered when the amount of wood resin was increased in the sheets. However, the optical properties were not significantly affected, even at high wood resin levels. When polysaccharides were added to fibre suspensions, together with wood resin, the strength properties were higher compared, at the same resin content, to sheets without added polysaccharides. Deacetylated glucomannans and pectic acids especially diminished the negative effect on paper strength caused by high wood resin content. Some of the polysaccharides were probably adsorbed onto the surface of the TMP fibres or wood resin droplets, which will increase the hydrophilicity of the surfaces, thereby promoting hydrogen bonds in the sheet. Aggregates of polymer and polysaccharides could also be retained in the fibre network.

The transport of nuclear materials is strictly regulated and has an impressive safety record spanning six decades. Radioactive materials are designated “Class 7” and their safety in transit is achieved mainly by appropriate packaging, which must allow for accidents. Radiation exposure to those handling shipments and to the public need to be well within permitted levels. The security of radioactive materials in transport has received more attention since 2001.

This chapter provides background information on the use of nonwood fiber in pulp and paper. Nonwood fiber is increasingly being used worldwide as a fiber source for papermaking. Annual plants have been used since the early 1800s, except for cotton. Straw has traditionally been pulped by boiling solutions of lime for board grades of paper; this led to a bright yellow pulp. Sodium hydroxide was used to make bleachable grades of pulp as well as board grades. The soda anthraquinone (AQ) method is replacing the soda method and the results of the soda/AQ for straw are said to be similar to those for kraft pulping of straw. Other methods of pulping include neutral sulfite and chlorine systems. Ash and silica both interfere with the pulping of many nonwood fibers. The cellulose, hemicellulose, lignin, and extractive contents are fundamental to pulping.

This chapter provides an overview of the pumps that are used in pulp and paper industry. In pulp and paper industry, high temperatures, very high suction pressures, low NPSHR requirements, poor lubricity, air entrainment, corrosive and acidic mixture of sodium or calcium bisulfite and sulfurous acid, and reliability are major considerations. The standard small process pump in pump and paper industry is the end suction, ANSI B73 or ISO 2858 chemical pump with centreline discharge open impeller and today more often than not mechanical seals. The larger pulp and low concentration transfer pumps are end suction, open impeller and adjustable wear plate, packing or mechanical seal type pumps with centerline discharge. Centrifugal stock pumps are used for consistencies up to approximately 5.5%, above this there are pumps with special internal features such as an inlet fluidizer that will allow consistencies up to as high as 18% consistency to be pumped. The pumps in the paper machine area are the screen, refiner, washer, cleaner and head box units as well as the refiner reject pump.

A study on toxicity discharges from three pulp and paper mills, two in Vietnam and one in Thailand, was conducted using the Microtox method, a rapid toxicity test with the marine bioluminescent bacterium, Photobacterium phosphoreum, as the test organism. Based on the EC50 values after 5 and 15 min of exposure, i.e. 5 min EC50 and 15 min EC50, respectively, the hypochlorite bleaching stage (H-H) effluent in the Thai mill was most toxic (EC50 were about 0.1% of the undiluted effluent) but still comparable with corresponding data obtained for COGIDO (0.4–0.5%). In BAPACO, toxicity of the effluent from the hypochlorite stages (H1 and H2) was much lower with the EC50 in the range of 38–83%. The chlorination (C) stage effluent in COGIDO with the 15 min EC50 of 18% was less toxic while the 15 min EC50 of this stage effluent was almost the same for both BAPACO and the Thai mill. The EC50 of the alkali-extraction (E) stage effluent were almost in the same range in all three mills. The combined effluent from the bleaching process was the most toxic in the Thai mill (EC50=0.4%), second toxic in COGIDO (8–10%) and the least toxic in BAPACO (14–24%). TEF (toxicity emission factors) values of this effluent show the same ranking: highest for the Thai mill (15000) followed by COGIDO with much lower TEF (1200) and the least was BAPACO (800). A less-than-additive, i.e. antagonistic, mode of toxicity was found for the combined effluent from bleaching plants and for various other combined effluents in the three mills. The bleaching plant is the largest toxicity source in terms of TEF in BAPACO, but not in COGIDO where the discharge of black liquor is the largest contribution of toxicity. For this reason, the total toxicity discharged from COGIDO with TEF>6000 was much higher than BAPACO with TEF of 750. For the Thai mill, the TEF of the pond system effluent alone was already much higher than TEF of the other two mills. Good house-keeping and process control improvement may greatly reduce acute toxicity from the mills.

Waste papers are recycled by deinking. All over the world, the flotation method is the mainstream as the deinking method because of the advantages such as higher pulp yield, less use of water, less area for installation and less total reagent cost. The flotation method is mainly consisted of pulping and flotation processes, the former for ink separation from cellulose, the latter for ink rejecting out from the system. Function to assist the mechanical separation of printing ink from cellulose is required for the deinking agent in the pulping process. In the flotation process, there are three particles, namely, ink, cellulose and bubble, and main four interaction between them in the flotation cell. The following relationship must be held to reject out the ink particles effectively. Vr0

International audience; Wheat gluten coated papers containing carvacrol (15wt%) as anti-microbial agent and montmorillonite (0-7wt%) as filler were investigated as anti-microbial controlled delivery systems. The carvacrol losses were followed during the coating process and storage time at 30 infinity C under controlled RH from 40 to 100% RH. Increasing MMT content limited carvacrol losses during the coating process. A mathematical model based on Fick's second law was used to determine the apparent diffusivities of carvacrol from experimental data of kinetic release at 30 infinity C and controlled RH. Diffusivity values varied from 0.143 x 10(-14) m(2)/s (0wt% MMT, 40% RH) to 6.010 x 10(-14) m(2)/s (5wt% MMT, 100%RH) depending on both MMT% and RH. The carvacrol diffusivities increased with increasing RH, and the presence of a high amount of MMT(>= 5wt%) accentuated the RH-induced effect. Specific aggregated structure was evidenced by SEM and TEM in the presence of carvacrol and 5wt% MMT creating a preferential pathway for carvacrol diffusion. The anti-microbial efficiency of the MMT-WG-coated papers toward Escherichia Coil was assessed and showed that the antimicrobial effect was related to the carvacrol diffusivity. The diffusivity coefficients were utilized to optimize the packaging characteristics required to develop an efficient anti-microbial system and were finally validated against Botrytis cinerea.

This paper reports work carried out at three laboratories, aimed at assessing the repeatability of various test methods used in the study of tribological coatings. The test methods were the ball crater technique for coating thickness, the Vickers microhardness test, the scratch test for adhesion and the pin on disc test for friction and wear. Three different coatings were studied, based on various compounds of titanium, boron, nitrogen and aluminium. Also different novel ionisation assisted PVD methods were used to produce the coatings The paper demonstrates the spread of results obtained by each of the tests on each of the coatings, both within each laboratory and also between laboratories. The results show that assessment of properties such as thickness and hardness can be made with reasonable repeatablity; greater care must be taken however in ascribing quantitive measures to adhesion levels. In particular it is necessary to define the criteria to be used for failure. In the case of friction and wear assessment the laboratories involved demonstrated that considerable variability can be seen, both in friction coefficients and wear rates. Nevertheless we demonstrate that the tests described provide a good basis for the assessment of coating properties and for the investigation of tribological behaviour, permitting further coating development.

It is well known that the microstructure of physical vapour deposited (PVD) coatings controls many of the properties (hardness, adhesion, residual stress) which are important in tribological applications. However, it is not generally recognised that the coating microstructure dictates the operating wear mechanism, both indirectly through determining the range of properties of a particular coating, and directly through its promotion of wear mechanisms that depend purely on the morphology of the coating. In this paper the effects of microstructure on hardness, internal stress and adhesion are briefly reviewed and the relevance of these properties to wear applications is discussed for titanium nitride coatings.

This paper measured the P-V diagram of 52100 steel/1045 steel rubbing pair under lubrication with and without oxide coating on the “ball-on-disc” testing machine. The oxide coating was pretreated on the steel surface by heating in the atmosphere of CO 2 gas. The effect of coating thickness and hardness of substrate on the P-V diagram was examined, and an optimum condition had been obtained, by which the load bearing capacity can vbe increased significantly. The microanalyses of oxide film were conducted by AES and XPS as well, and a model of three-sublayer structure of oxide coating had been proposed

The morphologies of particles generated during the grinding of metals are analyzed. The ground materials include several steels, titanium, and copper while aluminum oxide, cubic boron nitride, and diamond abrasive grinding wheels are used. Interest is focused on spherical particles of which three distinct morphologies have been typically observed. The occurrence of these particles is related to the different grinding induced temperatures and arguments are advanced to suggest that the spherical particles are formed by frictionally induced melting and subsequent solidification. Finally, it is suggested that analysis of chip morphology may afford a simple means of determining whether the grinding process is thermally “out of control.”