The effect of crystallinity on the light scattering of regenerated cellulose tubular films

An experimental study of the effect of crystallinity on the light scattering of regenerated cellulose tubular films is reported. Several films were prepared by varying manufacturing conditions, so that thickness and surface roughness were maintained approximately constant and the degrees of crystallinity varied between 38 and 66%. The scattered radiation intensity, measured between 220 and 550 nm decreases with the increasing wavelength. It was demonstrated that for the polymeric films studied, there was excellent agreement between crystallinity and scattering radiation intensity for a given wavelength. It was found that for crystallinity values less than around 57%, scattered radiation intensity decreases with increasing crystallinity, the reverse of that for crystallinity values greater than that percentage.     

Correlation crystallinity and physical properties of heat-treated cellulose triacetate fibres

Previous measurements of crystallinity in fibres of cellulose triacetate have been qualitative or semi-quantitative; in this work quantitative measurements of relative crystallinity have been made on cellulose triacetate yarn heat treated in the range 20–300°C following the x-ray diffraction method of correlation crystallinity index. The onset of crystallization is clearly marked by a transition in the crystallinity index at 172°C, and beyond this annealing temperature tenacity and crystallinity are inversely correlated. Orientation also improves with annealing temperature with a less well defined transition around 120–180°C. Initial Young's modulus increases with temperature whilst other physical properties have optimum values in the range 180–220°C. Cutting and grinding are found to have an adverse effect on the correlation crystallinity index which is in fact a measure of lattice perfection.     

再生纤维素纤维的研究进展

概述了再生纤维素纤维的研究现状;详述了高湿模量粘胶纤维、Lyocell纤维、铜氨纤维、醋酯纤维、秸秆类可再生纤维素纤维、再生竹纤维、再生麻纤维的性能、结构特征及其适用性;探讨了我国再生纤维素纤维的发展趋势,指出超天然的功能再生纤维素纤维材料将成为未来发展的重点,我国应注重开发差别化、功能化粘胶纤维。     

Recent advances in regenerated cellulose materials

The dual threats of the depletion of nonrenewable energy and environmental pollution caused by petroleum-based polymers motivate utilization of naturally occurring polymers to create new materials. Cellulose, as the most abundant natural polymer on earth, has attracted attention due to its renewability, wide availability, low-cost, biocompatibility and biodegradability, etc. Regenerated cellulose may be constructed simply via physical dissolution and regeneration, an environmentally friendly process avoiding the consuming of chemicals since most of the reagents (solvents, coagulant, etc.) may be recycled and reused. “Green” solvents and techniques for the preparation of the environmentally friendly regenerated cellulose materials have been developed successfully, showing great potentials in the fields of polymer science and technology.In this article, the widely used non-derivatizing cellulose solvents are summarized, including their dissolution mechanisms. Regenerated cellulose materials with different functions and properties have been designed and fabricated in different forms, such as filaments, films/membranes, microspheres/beads, hydrogels/aerogels and bioplastics, etc., to meet various demands. The concept of regeneration through a physical process is illustrated, and a number of novel regenerated cellulose materials are introduced for wide applications in textiles, packaging, biomedicine, water treatment, optical/electrical devices, agriculture and food, etc. The methodology of material processing and the resultant properties and functions are also covered in this review, with emphasis on the neat regenerated cellulose materials and the composite materials. The 277 references cited concerning the direct preparation of cellulose materials via physical dissolution and regeneration are representative of the wide impact and benefits of the regenerated cellulose materials to society.     

Improvement of adhesion between polyethylene and regenerated cellulose fibers by surface fibrillation

Regenerated cellulose fibers spun from straw pulp using the N-methylmorpholine N-oxide (NMMO) process were evaluated as a reinforcement for low-density polyethylene (LDPE). Surface fibrillation was carried out by a mechanical treatment to improve interfacial adhesion. Surface fibrillation resulted in a gradual change in surface topography, as detected by SEM. Long and numerous twisted fibrils were observed on the surface of the treated fibers. The fiber perimeters, determined by the Wilhelmy plate method, increased with an extended degree of fibrillation, while the strength of the fiber was not affected by the surface treatment. Model composites were prepared by embedding untreated and surface-fibrillated single fibers into an LDPE matrix, and the single fiber fragmentation (SEF) test was carried out to determine the critical fiber length. The interfacial shear strength (τ) was then calculated by applying a modified form of the Kelly-Tyson equation. It was found that the interfacial shear strength increased significantly as a result of surface fibrillation. The proposed mechanism for the improvement of interfacial adhesion is a mechanical anchoring between the matrix and the fiber.     

Comparison of cellulose and chitin nanocrystals for reinforcing regenerated cellulose fibers

In this study, regenerated cellulose fibers reinforced by cellulose nanocrystals (CENC) and chitin nanocrystals (CHNC) were prepared by blending the nanocrystals suspensions with the cellulose solution in NaOH/urea/water solvent at room temperature. The effect of nanocrystals' addition on the properties of spinning dopes and regenerated fibers were investigated and compared. Results showed that the obtained CENC and CHNC had different dimensions, and both of them increased the viscosity and decreased the transparency of the spinning dopes. However, the dissolution state of cellulose was not changed. CHNC had a greater influence on the properties of spinning dopes, while CENC had more obvious effect on the performance of regenerated fibers. The CENC reinforced fibers showed a higher crystallinity index as compared to the CHNC reinforced fibers. The tensile strength of the regenerated fibers was evidently improved when 3 wt % CENC or 2 wt % CHNC were added, while the elongation at break of the fibers was slightly decreased with the increase of nanocrystals content. The morphology and thermal stability of the regenerated fibers was not affected by the addition of nanocrystals. This study suggested that the dimension, group and content of nanocrystals were important factors for the reinforcement of regenerated cellulose fibers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44880.     

Correlation between structural and dynamic mechanical transitions of regenerated silk fibroin

Dynamic mechanical analysis (DMA) was applied to investigate the correlation between dynamic mechanical behaviors of regenerated silk fibroin (RSF) and its structural transition which was characterized by near-infrared (NIR) spectroscopy. The tan δ peak split of DMA demonstrated that the apparent glass transition of amorphous RSF film (at around 177 °C) was the contribution of both uncrystallizable and crystallizable segments through homogeneous amide-amide hydrogen bonds, which were gradually separated from each other and produced disordered and β-sheet domains during ethanol treatment. Furthermore, DMA was also applied as “thermal fingerprint” to investigate water effect on the disordered domains of silk fibroin. The results showed that glass transition temperature of permanently disordered domains in crystallized RSF films was increased from 155 °C to 190 °C after thermal dehydration, and even approached 205 °C for stretched RSF films.     

Tensile deformation of regenerated and native cellulose fibres

The tensile deformation of well-oriented cellulose fibres has been reexamined. It is demonstrated that not only the fibre structure but also the deformation mechanism is similar to that found in high performance aramid fibres. An explanation is proposed for the difference between the elastic moduli of cellulose I and II. In view of these results it is possible to assess the prospect for improving the mechanical properties of cellulose fibres.     

Enhanced bondability between inorganic particles and a polysaccharide substrate by encapsulation with regenerated cellulose

Inorganic fillers are widely used in coatings, paints, printing inks, and papermaking. A general problem in such applications is the poor compatibility and weak bondability of the filler with polymeric substrates. Surface modification and encapsulation are common methods adapted to enhance interactions between the filler surface and the substrate. This article presents a bondability improvement between inorganic particles and a polysaccharide substrate by the use of cellulose‐coated, inorganic core–shell nanoparticles. The crystallinity of the coated carbohydrate layer is shown to significantly affect the bondability of the core–shell particles. The impact of the coating layer on the light scattering efficiency has also been studied with theoretical Mie scattering calculations. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and properties of chemical cellulose from ascidian tunic and their regenerated cellulose fibers

Chemical cellulose (dissolving pulp) was prepared from ascidian tunic by modified paper‐pulp process (prehydrolysis with acidic aqueous solution of H₂SO₄, digestion with alkali aqueous solution of NaOH/Na₂S, bleaching with aqueous NaOCl solution, and washing with acetone/water). The α‐ cellulose content and the degree of polymerization (DPw) of the chemical cellulose was about 98 wt % and 918, respectively. The Japanese Industrial Standard (JIS) whiteness of the chemical cellulose was about 98%. From the X‐ray diffraction patterns and ¹³C‐NMR spectrum, it was found that the chemical cellulose obtained here has cellulose Iβ crystal structure. A new regenerated cellulose fiber was prepared from the chemical cellulose by dry–wet spinning using N‐methylmorpholine‐ N‐oxide (NMMO)/water (87/13 wt %) as solvent. The new regenerated cellulose fiber prepared in this study has a higher ratio of wet‐to‐dry strength (<0.97) than commercially regenerated cellulose fibers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1634–1643, 2002.     

A microscopic study of fracture in regenerated cellulose film

The fracture edge of a strip of regenerated cellulose film broken under tension can usually be divided into three regions: (A) the site of the initial failure, (B) the slow-tear region, and (C) the fast-tear region. Photomicrographs showing these regions are presented and discussed. Three different types of initial failure are described and some data presented relating the breaking strain to the type of initial failure.     

Interfacial properties of regenerated cellulose fiber and thermoplastic systems

In dry-formed polymer-bonded networks of cellulose fibers and in other types of nonwovens, the fiber-polymer joint is considered to be the primary factor determining the ultimate properties of the network structure. In an attempt to develop a model describing the joint failure, the well-known fiber pullout test has been applied to a system consisting of regenerated cellulose fibers and three different polymer matrices: a styrene–acrylate copolymer, poly(vinyl alcohol), and high density polyethylene. For each system, the interfacial bond strength was evaluated. The results are, to some extent, discussed in relation to the mechanical behavior of dry-formed networks bonded with similar polymeric materials. It is suggested that both the interfacial properties and the cohesive strength of the polymer binder are of importance for the mechanical strength of the bonded network.     

Inner surface and void system of regenerated cellulose fibers

Both the inner surface and the void system of different cellulose regenerate fibers are investigated with X-ray small angle scattering. Thereby it turns out that all fibers have a void system of 0.01 to 0.1% (volume fraction 10^?4–10^?3). However, the amount of the void system has little influence on the mechanical properties. Rather, it is the shape of the voids and their orientation which proves essential. It is found that elongated voids, probably well oriented, are responsible for superior mechanical properties. This explains also improved textile properties of lyocell fibers of the NMMO type.     

Correlation between crystallinity and thermal expansion in LiAlSiO4 ceramics prepared by spark plasma sintering

LiAlSiO₄ (LAS) ceramics are prepared by using the sol-gel method followed by spark plasma sintering. XRD patterns and SEM images verify that the ceramics contain amorphous and LAS phases and that microcracks appear in the sample prepared at 900 °C due to its larger grain size. Compared with applied pressure and soaking time, sintering temperature has a greater impact on the crystallinity and density of the ceramics during sintering. High-temperature XRD results reveal that the LAS phase exhibits its intrinsic negative thermal expansion independently in all samples regardless of crystallinity. The coefficients of thermal expansion (CTE) measured by the dilatometric method change from positive values in samples prepared at 600 and 650 °C to near zero in samples prepared at 700 and 800 °C and then to a negative value in the sample prepared at 900 °C. The combined effects of an amorphous phase with a positive CTE and the LAS phase with a negative CTE are responsible for the observed transformation of thermal expansion in the samples. The calculated total CTEs of the glass-ceramic bulks are in agreement with the results measured through the dilatometric method in samples prepared at 650–800 °C. Microcracks in the sample prepared at 900 °C cause a more negative bulk CTE than the calculated CTE.     

过氧化氢氧化再生纤维素及其阻燃、吸附性能

以过氧化氢氧化再生纤维素(GC)制备羧基再生纤维素(OGC),表征OGC结构变化及其对阻燃和吸附性能影响机理。通过碱泡预处理能有效提高GC比表面积,增加反应效率,获得羧基含量达15.6%的OGC。FT-IR和¹³C NMR表征结果说明OGC葡萄糖基环上的C₆位伯羟基能被选择性氧化成羧基。随着羧基含量的提高,OGC无定形部分溶解而提高其结晶度,晶型则无显著变化,OGC的热分解温度下降,但是成炭率显著提高。当添加6.25%OGC为成炭剂用于环氧树脂膨胀型阻燃时,氧指数达到27.2,阻燃等级为V0。以火焰原子吸收分光光度法测定结果表明,当羧基含量为15.6%,OGC对铅和铜离子吸附量分别提高14倍和3.5倍,其原因在于氧化改性能显著提高OGC的比表面积和容积率,增加吸附容量。研究结果说明以过氧化氢氧化制备的OGC在阻燃成炭剂以及金属离子吸附领域中具有良好的应用前景。