Preparation of Flexible Calcium Carbonate by In Situ Carbonation of the Chitin Fibrils and Its Use for Producing High Loaded Paper.

Flexible calcium carbonate (FCC) was developed as a functional papermaking filler for high loaded paper, which was a fiber-like shaped calcium carbonate produced from the in situ carbonation process on the cellulose micro-or nanofibril surface. Chitin is the second most abundant renewable material after cellulose. In this study, a chitin microfibril was utilized as the fibril core for making the FCC. Cellulose fibrils for the preparation of FCC were obtained by fibrillation of the TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical) treated wood fibers. The chitin fibril was obtained from the ß-chitin from the born of squid fibrillated in water by grinding. Both fibrils were mixed with calcium oxide and underwent a carbonation process by the addition of carbon dioxide, thus the calcium carbonate attached on the fibrils to make FCC. When used in papermaking, both the FCC from chitin and cellulose gave a much higher bulk and tensile strength simultaneously than the conventional papermaking filler of ground calcium carbonate, while maintaining the other essential properties of paper. The FCC from chitin caused an even higher bulk and higher tensile strength than those of the FCC from cellulose in paper materials. Furthermore, the simple preparation method of the chitin FCC in comparison with the cellulose FCC may enable a reduction in the use of wood fibers, process energy, and the production cost of paper materials.

Effect of Calendering on the Properties of Paper Containing Flexible Calcium Carbonate with a Cellulose Nanofibril Core.

Flexible calcium carbonate (FCC) was prepared by attaching a large amount of calcium carbonate to cellulose nanofibrils (CNFs) by an in situ calcium carbonate formation method. FCC normally consists of CNFs and calcium carbonate at a 1:40 ratio by weight. FCC-containing papers resulted in a higher bulk, higher stiffness, and higher tensile strength than a commercialized ground calcium carbonate (GCC)-containing papers at the same ash content. However, there were speculations that calendering on FCC-containing paper might cause a large drop in bulk and no increase in smoothness due to the larger size of the FCC (avg. dia. 20-30 µm) than the GCC (dia. 2 µm). FCC-containing paper was shown to respond to the calendering process very effectively to increase the Bekk smoothness and to maintain high bulk. Furthermore, FCC-containing paper was so effective in increasing smoothness that it might need less calendering pressure to match the smoothness of GCC-containing paper. If so, there could be potential to increase the bulk and stiffness further in FCC-containing papers at the same smoothness as GCC-containing paper by applying reduced calendering pressure.

Disk-shaped cellulose fibers from red algae, Eucheuma cottonii and its use for high oxygen barrier.

We could prepare disk-shaped fibers without particular mechanical treatments from Eucheuma cottonii, the commonly used red algae for obtaining carrageenan. After carrageenan extraction from cottonii, the residues were bleached using chlorine dioxide and hydrogen peroxide. The morphology of the bleached fiber was disk-shaped one with a very thin fiber wall thickness of less than 100 nm and a diameter of approximately 100 µm. The sugar analysis and X-ray diffraction of the bleached fibers showed that they consisted of mostly glucose and had the same pattern as cellulose I with more than 50% crystalline structure, respectively. Compared to one-dimensional cellulose micro- or nanofibrils, which exhibits slow drainage and possess intolerably high drying energy, these two-dimensional disk-shaped fibers, when formed a layer in water medium, exhibit fast drainage and low drying energy. The formed sheet resulted in excellent transparency and high oxygen barrier property. Therefore, by using these disk-shaped, thin fibers from cottonii, we expect that the biodegradable and transparent oxygen barrier layer can be produced at a paper machine, which is, if possible, extremely difficult in the case of cellulose micro- or nanofibrils due to their slow drainage and high drying energy.

Application of In Situ Calcium Carbonate Process for Producing Papermaking Fillers from Lime Mud.

A portion of the lime mud formed during the causticizing process in the recovery process of kraft pulping should be purged from the calcium cycle as waste before it is fed to the lime kiln; this ensures that the quality of the pulp and pulping chemicals is maintained. The discharged greenish-gray lime mud, which is often disposed as an industrial waste, has been transformed herein into a high-quality papermaking filler via the hybrid calcium carbonate (HCC) and post-HCC (pHCC) technology. Initially, the lime mud was heat-treated and then ground to small-size particles. The ground lime mud was preflocculated with calcium oxide by ionic polymers, and carbon dioxide was injected to the flocs to produce lime mud HCC (LHCC). To produce lime mud pHCC (pLHCC), only the ground lime mud was preflocculated first, calcium oxide was added next, and finally, carbon dioxide was injected to the flocs. The resultant products, LHCC and pLHCC, gave brightness as high as that of the ground calcium carbonate (GCC) in paper while a little higher brightness for pLHCC than for LHCC. They also enabled to increase bulk, stiffness, and tensile strength. Application of the LHCC and pLHCC technology to the lime mud could save waste disposal expenses and produce better-quality paper.

Development of Deformable Calcium Carbonate for High Filler Paper.

Controlling the size and rigidity of calcium carbonate became possible. HCCs were developed and manufactured by the in situ reaction of carbon dioxide and calcium oxide, which were already preflocculated together with GCC using ionic polymers before the reaction. HCC is deformable under pressure during the papermaking process, and its degree of rigidity can be controlled by adjusting the fraction of calcium oxide. The size of HCC can be further controlled by adjusting shearing force. The more the fraction of calcium oxide, the more rigid the HCC and the smaller the diameter of the HCC. When used in papermaking, HCC increased the tensile strength and bulk of paper simultaneously without lowering other essential paper properties, and its deformable nature under pressure improved paper smoothness. Saving chemical pulp by 10% by replacing it with HCC, which is 3-4 times less expensive than the chemical pulp, was demonstrated successfully without lowering the essential properties of paper. Implementation of HCC in the paper mill may result in saving chemical pulp, drying energy, and production cost. The paper mill may utilize the carbon dioxide from the mill stack after purification for HCC preparation.

Simultaneous production of bio-ethanol and bleached pulp from red algae.

The red algae, Gelidium corneum, was used to produce bleached pulp for papermaking and ethanol. Aqueous extracts obtained at 100-140 °C were subjected to saccharification, purification, fermentation, and distillation to produce ethanol. The solid remnants were bleached with chlorine dioxide and peroxide to make pulp. In the extraction process, sulfuric acid and sodium thiosulfate were added to increase the extract yield and to improve de-polymerization of the extracts, as well as to generate high-quality pulp. An extraction process incorporating 5% sodium thiosulfate by dry weight of the algae provided optimal production conditions for the production of both strong pulp and a high ethanol yield. These results suggest that it might be possible to utilize algae instead of trees and starch for pulp and ethanol production, respectively.

Red algae and their use in papermaking.

Gelidialian red algae, that contain rhizoidal filaments, except the family Gelidiellaceae were processed to make bleached pulps, which can be used as raw materials for papermaking. Red algae consist of rhizoidal filaments, cortical cells usually reddish in color, and medullary cells filled with mucilaginous carbohydrates. Red algae pulp consists of mostly rhizoidal filaments. Red algae pulp of high brightness can be produced by extracting mucilaginous carbohydrates after heating the algae in an aqueous medium and subsequently treating the extracted with bleaching chemicals. In this study, we prepared paper samples from bleached pulps obtained from two red algae species (Gelidium amansii and Gelidium corneum) and compared their properties to those of bleached wood chemical pulps.