Properties and preparation progress of microfibrillated cellulose: a review

doi:10.16085/j.issn.1000-6613.2017.01.030

Abstract

Abstract: Microfibrillated Cellulose(MFC) is a renewable macromolecular material derived from lignocellulosic fiber,which possesses the characteristic of natural cellulose and nanomaterials. Recently,many studies have been carried out in the preparation,modification,and application of MFC. However,its application is hampered by the high cost,dry methods and re-dispersability,especially in large scale production of MFC. To better understand the properties and progress of microfibrillated cellulose preparation,the characteristic and definition of MFC were firstly investigated,and the different mechanical preparation methods of MFC were discussed,including high pressure homogenization treatment,microfluidization treatment,ultrafine grinding treatment,cryocrushing treatment and high intensity ultrasonication treatment. Subsequently,the problems of mechanical preparation of MFC were analyzed. The pretreatment methods for MFC preparation were also presented,including cellulase pretreatment,alkaline-acid pretreatment,carboxymethylation pretreatment,TEMPO oxidation pretreatment,and periodate oxidation pretreatment. Finally,the problems existing in the preparation and dry process of MFC in large scale were summarized.

Key words: nanomaterials, cellulose, microfibrillated cellulose, pretreatment, mechanical preparation progress

摘要： 微纤化纤维素（MFC）是一种主要由植物纤维制备而得的可再生高分子材料，兼具天然纤维和纳米材料的特点。近年来，有关MFC制备、改性及应用方面的研究越来越多，然而制备成本高、干燥以及再分散等仍然是MFC规模化生产所不可回避的问题。为了更全面地加深对MFC及其制备技术发展现状的认识，本文首先探讨了MFC物化特性及其命名，然后介绍了MFC机械制备方法，包括高压均质处理、微射流处理、超细研磨处理、冷冻破碎处理和高强超声处理等，并对MFC机械制备存在的问题进行了分析。本文还介绍了MFC制备过程中的预处理方法，包括纤维素酶预处理、酸-碱抽提预处理、羧甲基化预处理、TEMPO氧化预处理、高碘酸盐氧化预处理等。最后对MFC在规模化生产及干燥过程中存在的问题进行了总结。

关键词: 纳米材料, 纤维素, 微纤化纤维素, 预处理, 机械制备

CLC Number:

TS727⁺.1

GAO Yanhong, SHI Yu, TIAN Chao, LI Qun, LIU Weizhe. Properties and preparation progress of microfibrillated cellulose: a review[J]. Chemical Industry and Engineering Progree, 2017, 36(01): 232-246.

高艳红, 石瑜, 田超, 李群, 刘玮哲. 微纤化纤维素及其制备技术的研究进展[J]. 化工进展, 2017, 36(01): 232-246.

References

[1] SIMON J,M LLER H,KOCH R,et al. Thermoplastic and biodegradable polymers of cellulose[J]. Polymer Degradation and Stability,1998,59(1):107-115.
[2] DIOTALLEVI F,MULDER B. The cellulose synthase complex:a polymerization driven supramolecular motor[J]. Biophys. J.,2007,92(8):2666-2673.
[3] ZHU H,FANG Z,PRESTON C,et al. Transparent paper:fabrications,properties,and device applications[J]. Energ. Environ. Sci.,2014,7(1):269-287.
[4] BESSUEILLE L,BULONE V. A survey of cellulose biosynthesis in higher plants[J]. Plant Biotechnol.,2008,25(3):315-322.
[5] KAMEL S. Nanotechnology and its applications in lignocellulosic composites,a mini review[J]. Express Polym. Lett.,2007,1(9):546-575.
[6] LAVOINE N,DESLOGES I,DUFRESNE A,et al. Microfibrillated cellulose--its barrier properties and applications in cellulosic materials:a review[J]. Carbohydrate Polymers,2012,90(2):735-764.
[7] German Version. Nanotechnologies--terminology and definitions for nano-objects--nanoparticle,nanofibre and nanoplate (ISO/TS 27687:2008)[S]. German Version:Vornorm DIN CEN ISO/TS,2008.
[8] OSONG S H,NORGREN S,ENGSTRAND P. Processing of wood-based microfibrillated cellulose and nanofibrillated cellulose,and applications relating to papermaking:a review[J]. Cellulose,2016,23(1):93-123.
[9] ABDUL KHALIL H P,DAVOUDPOUR Y,ISLAM M N,et al. Production and modification of nanofibrillated cellulose using various mechanical processes:a review[J]. Carbohydrate Polymer,2014,99:649-665.
[10] TAPPI. Proposed new TAPPI standard:Standard terms and their definition for cellulose nanomaterial[M]. TAPPI,2011.
[11] ROMAN M,WINTER W T. Effect of sulfate groups from sulfuric acid hydrolysis on the thermal degradation behavior of bacterial cellulose[J]. Biomacromolecules,2004,5(5):1671-1677.
[12] CHEN L,WANG Q,HIRTH K,et al. Tailoring the yield and characteristics of wood cellulose nanocrystals (CNC) using concentrated acid hydrolysis[J]. Cellulose,2015,(3):1753-1762.
[13] SYVERUD K,CHINGA-CARRASCO G,TOLEDO J,et al. A comparative study of Eucalyptus and Pinus radiata pulp fibres as raw materials for production of cellulose nanofibrils[J]. Carbohydrate Polymers,2011,84(3):1033-1038.
[14] SIRÓ I,PLACKETT D. Microfibrillated cellulose and new nanocomposite materials:a review[J]. Cellulose,2010,17(3):459-494.
[15] SASSI J F,CHANZY H. Ultrastructural aspects of the acetylation of cellulose[J]. Cellulose,1995,2(2):111-127.
[16] IWAMOTO S,KAI W,ISOGAI T,et al. Comparison study of TEMPO-analogous compounds on oxidation efficiency of wood cellulose for preparation of cellulose nanofibrils[J]. Polym. Degrad. Stab.,2010,95(8):1394-1398.
[17] UETANI K,YANO H. Nanofibrillation of wood pulp using a high-speed blender[J]. Biomacromolecules,2011,12(2):348-353.
[18] AMIRALIAN N,ANNAMALAI P K,MEMMOTT P,et al. Isolation of cellulose nanofibrils from Triodia pungens via different mechanical methods[J]. Cellulose,2015,22(4):2483-2498.
[19] LEITNER J,HINTERSTOISSER B,WASTYN M,et al. Sugar beet cellulose nanofibril-reinforced composites[J]. Cellulose,2007,14(5):419-425.
[20] ZIMMERMANN T,BORDEANU N,STRUB E. Properties of nanofibrillated cellulose from different raw materials and its reinforcement potential[J]. Carbohydrate Polymers,2010,79(4):1086-1093.
[21] LIIMATAINEN H,VISANKO M,SIRVI J A,et al. Enhancement of the nanofibrillation of wood cellulose through sequential periodate-chlorite oxidation[J]. Biomacromolecules,2012,13(5):1592-1597.
[22] NAKAGAITO A N,YANO H. The effect of morphological changes from pulp fiber towards nano-scale fibrillated cellulose on the mechanical properties of high-strength plant fiber based composites[J]. Appl. Phys. A,2004,78(4):547-552.
[23] LPEZ-RUBIO A,LAGARON J M,ANKERFORS M,et al. Enhanced film forming and film properties of amylopectin using micro-fibrillated cellulose[J]. Carbohydrate Polymers,2007,47(3):249-278.
[24] HERRICK F W,CASEBIER R L,HAMILTON J K,et al. Microfibrillated cellulose:morphology and accessibility[J]. J. Appl. Polym. Sci.:Appl. Polym. Symp.(United States),1983,37:5039044.
[25] TURBAK A F,SNYDER F W,SANDBERG K R. Microfibrillated cellulose,a new cellulose product:properties,uses,and commercial potential[C]//NewYork:J. Appl. Polym. Sci.:Appl. Polym. Symp.(United States),1983-01-01.
[26] TURBAK A F,SNYDER F W,SANDBERG K R. Suspensions containing microfibrillated cellulose:US445272[P]. 1984-07-05.
[27] DUFRESNE A,DUPEYRE D,VIGNON M R. Cellulose microfibrils from potato tuber cells:processing and characterization of starch–cellulose microfibril composites[J]. J. Appl. Polym. Sci.,2000,76(14):2080-2092.
[28] HABIBI Y,MAHROUZ M,VIGNON M R. Microfibrillated cellulose from the peel of prickly pear fruits[J]. Food Chem.,2009,115(2):423-429.
[29] SPENCE K L,VENDITTI R A,ROJAS O J,et al. A comparative study of energy consumption and physical properties of microfibrillated cellulose produced by different processing methods[J]. Cellulose,2011,18(4):1097-1111.
[30] SPENCE K L,VENDITTI R A,HABIBI Y,et al. The effect of chemical composition on microfibrillar cellulose films from wood pulps:mechanical processing and physical properties[J]. Bioinformation,2010,101(101):5961-5968.
[31] WANG B,SAIN M. Dispersion of soybean stock-based nanofiber in a plastic matrix[J]. Polym. Int.,2007,56(4):538-546.
[32] IWAMOTO S,NAKAGAITO A N,YANO H,et al. Optically transparent composites reinforced with plant fiber-based nanofibers[J]. Appl. Phys. A,2005,81(6):1109-1112.
[33] STELTE W,SANADI A R. Preparation and characterization of cellulose nanofibers from two commercial hardwood and softwood pulps[J]. Indengchemres,2009,48(24):11211-11219.
[34] KARANDE V S,BHARIMALLA A K,HADGE G B,et al. Nanofibrillation of cotton fibers by disc refiner and its characterization[J]. Fibers & Polymers,2011,12(3):399-404.
[35] KUMAR A,SINGH S P,SINGH A K. Preparation and characterization of cellulose nanofibers from bleached pulp using a mechanical treatment method[J]. Tappi Journal,2014,13(5):25-31.
[36] LEE S Y,CHUN S J,KANG I A,et al. Preparation of cellulose nanofibrils by high-pressure homogenizer and cellulose-based composite films[J]. Journal of Industrial & Engineering Chemistry,2009,15(1):50-55.
[37] CHRISTIAN A,SUSANNA A,PETER J,et al. Nanoscale cellulose films with different crystallinities and mesostructures--their surface properties and interaction with water[J]. Langmuir,2009,25(13):7675-7685.
[38] FERRER A,FILPPONEN I,RODR GUEZ A,et al. Valorization of residual empty palm fruit bunch fibers (EPFBF)by microfluidization:production of nanofibrillated cellulose and EPFBF nanopaper[J]. Bioresour Technol.,2012,125C(12):249-255.
[39] TANIGUCHI T,OKAMURA K. New films produced from microfibrillated natural fibres[J]. Polym. Int.,1998,47(3):291-294.
[40] WANG Q Q,ZHU J Y,GLEISNER R,et al. Morphological development of cellulose nanofibrils (CNF) of a bleached eucalyptus pulp by mechanical fibrillation[J]. Cellulose,2012,19(5):1631-1643.
[41] HASSAN M L,MATHEW A P,HASSAN E A,et al. Nanofibers from bagasse and rice straw:process optimization and properties[J]. Wood. Sci. Technol.,2012,46(1-3):193-205.
[42] IWAMOTO S,NAKAGAITO A N,YANO H. Nano-fibrillation of pulp fibres for the processing of transparent nanocomposites[J]. Appl. Phys. A:Mater. Sci. Process,2007,89(2):461-466.
[43] NAIR S S,ZHU J Y,DENG Y,et al. Characterization of cellulose nanofibrillation by micro grinding[J]. Mol. Ecol. Notes,2006,6(1):90-92.
[44] HENRIKSSON M,ISAKSSON B P. Cellulose nanopaper structures of high toughness[J]. Biomacromolecules,2008,9(6):1579-1585.
[45] MATSUDA Y,HIROSE M,UENO K. Super microfibrillated cellulose,process for producing the same,and coated paper and tinted paper using the same:US6214163[P]. 2001-04-10.
[46] DUFRESNE A,CAVAILL J Y,HELBERT W. Thermoplastic nanocomposites filled with wheat straw cellulose whiskers. Part Ⅱ:Effect of processing and modeling[J]. Polym. Compos.,1997,18(2):198-210.
[47] ALEMDAR A,SAIN M. Biocomposites from wheat straw nanofibers:morphology,thermal and mechanical properties[J]. Composites Science & Technology,2008,68(2):557-565.
[48] CHENG Q,WANG S,RIALS T G. Poly(vinyl alcohol) nanocomposites reinforced with cellulose fibrils isolated by high intensity ultrasonication[J]. Composites Part A:Applied Science & Manufacturing,2009,40(2):218-224.
[49] 冯若. 声化学基础研究中的声学问题[J]. 物理学进展,1996,16(3):402-412. FENG Ruo. the Acoustic problems in in fundamental study on sonochemistry[J]. Progress in Physics,1996,16(3):402-412.
[50] IWASAKI T,LINDBERG B,MEIER H. The effect of ultrasonic treatment on individual wood fibers[J]. Svensk Papperstidning,1962,65(20):795-816.
[51] WANG S,CHENG Q. A novel process to isolate fibrils from cellulose fibers by high-intensity ultrasonication,part 1:process optimization[J]. J. Appl. Polym. Sci.,2009,113(2):1270-1275.
[52] CHEN W,YU H,LIU Y,et al. Isolation and characterization of cellulose nanofibers from four plant cellulose fibers using a chemical-ultrasonic process[J]. Cellulose,2011,18(2):433-442.
[53] HUANG Z M,ZHANG Y Z,KOTAKI M,et al. A review on polymer nanofibers by electrospinning and their applications in nanocomposites[J]. Composites Science & Technology,2003,63(15):2223-2253.
[54] AULIN C,GÄLLSTEDT M,LINDSTRÖM T. Oxygen and oil barrier properties of microfibrillated cellulose films and coatings[J]. Cellulose,2010,17(3):559-574.
[55] ANKERFORS M. Microfibrillated cellulose:energy-efficient preparation techniques and key properties[R]. Stockholm:KTH Royal Institute of Technology,2012.
[56] ISOGAI A,TSUGUYUKI S,HAYAKA F. TEMPO-oxidized cellulose nanofibers[J]. Nanoscale,2010,3(1):71-85.
[57] ERIKSEN. The use of microfibrillated cellulose produced from kraft pulp as strength enhancer in TMP paper[J]. Nord. Pulp. Pap. Res. J.,2008,23(3):299-304.
[58] SZCZĘSNA-ANTCZAK M,KAZIMIERCZAK J,ANTCZAK T. Nanotechnology--methods of manufacturing cellulose nanofibres[J]. Fibres and Texitiles in Eastern Europe,2012,20(2):8-12.
[59] FUKUZUMI H,SAITO T,OKITA Y,et al. Thermal stabilization of TEMPO-oxidized cellulose[J]. Polym. Degrad. Stab.,2010,95(9):1502-1508.
[60] MILLER Jack. Nanocellulose:technology applications,and markets[C]//Vancouver,BC:TAPPI International Conference on Nanotechnology for Renewable Materials. 2014.
[61] HENRIKSSON M,HENRIKSSON G,BERGLUND L A,et al. An environmentally friendly method for enzyme-assisted preparation of microfibrillated cellulose (MFC) nanofibers[J]. Eur. Polym. J.,2007,43(8):3434-3441.
[62] MISSOUM K,BELGACEM M N,BRAS J. Nanofibrillated cellulose surface modification:a review[J]. Materials,2013,6(5):1745-1766.
[63] PÄÄKKÖ M,VAPAAVUORI J,SILVENNOINEN R,et al. Long and entangled native cellulose I nanofibers allow flexible aerogels and hierarchically porous templates for functionalities[J]. Soft Matter,2008,4(12):2492-2499.
[64] HOEGER I C,NAIR S S,RAGAUSKAS A J,et al. Mechanical deconstruction of lignocellulose cell walls and their enzymatic saccharification[J]. Cellulose,2013,20(2):807-818.
[65] Innventia. Nanocellulose for the first time on a large scale[R]. Sweden:Innventia. 2011.
[66] QVINTUS Pia. Cellulose nanofibrils:overcoming challenges on the development of nanocellulose-based products[C]//Proceedings of the TAPPI International Conference on Nanotechnology for Renewable Materials,Atlanta,GA,2015.
[67] SAIN M M,BHATNAGAR A. Manufacturing process of cellulose nanofibers from renewable feed stocks:US20080146701A1[P]. 2008-06-19.
[68] SAIN M M,BHATNAGAR A. Manufacturing of nano-fibrils from natural fibres,agro based fibres and root fibres:CA2437616A1[P]. 2005-02-04.
[69] HAN J Q,ZHOU C J,WU Y Q,et al. Self-assembling behavior of cellulose nanoparticles during freeze-drying:effect of suspension concentration,particle size,crystal structure,and surface charge[J]. Biomacromolecules,2013,14(5):1529-1540.
[70] WALECKA J A. An investigation of low degree of substitution carboxymethylcelluloses[J]. Georgia Institute of Technology,1956,
[71] WÅGBERG L,DECHER G,NORGREN M,et al. The build-up of polyelectrolyte multilayers of microfibrillated cellulose and cationic polyelectrolytes[J]. Langmuir the Acs Journal of Surfaces & Colloids,2008,24(3):784-795.
[72] EYHOLZER C,BORDEANU N,LOPEZ-SUEVOS F,et al. Preparation and characterization of water-redispersible nanofibrillated cellulose in powder form[J]. Cellulose,2010,17(1):19-30.
[73] TAIPALE T,ÖSTERBERG M,NYK NEN A,et al. Effect of microfibrillated cellulose and fines on the drainage of kraft pulp suspension and paper strength[J]. Cellulose,2010,17(17):1005-1020.
[74] SIRÓ I,PLACKETT D,HEDENQVIST M,et al. Highly transparent films from carboxymethylated microfibrillated cellulose:the effect of multiple homogenization steps on key properties[J]. J. Appl. Polym. Sci.,2011,119(5):2652-2660.
[75] SEMMELHACK M F,CHOU C S,CORTES D A. Nitroxyl-mediated electrooxidation of alcohols to aldehydes and ketones[J]. Jamchemsoc,1983,105(13):4492-4494.
[76] SEMMELHACK M F,SCHMID C R,CORTES D A,et al. Oxidation of alcohols to aldehydes with oxygen and cupric ion,mediated by nitrosonium ion[J]. Jamchemsoc,1984,106(11):3374-3376.
[77] ANELLI P L,BIFFI C,MONTANARI F,et al. Fast and selective oxidation of primary alcohols to aldehydes or to carboxylic acids and of secondary alcohols to ketones mediated by oxoammonium salts under two-phase conditions[J]. J. Org. Chem.,1987,52(12):2559-2562
[78] DE NOOY A E J,BESEMER A C,BEKKUM H V. Selective oxidation of primary alcohols mediated by nitroxyl radical in aqueous solution. Kinetics and mechanism[J]. Tetrahedron,1995,51(29):8023-8032.
[79] ISOGAI A,KATO Y. Preparation of polyuronic acid from cellulose by TEMPO-mediated oxidation[J]. Cellulose,1998,5(3):153-164.
[80] PÄÄKKÖNEN T,DIMIC-MISIC K,ORELMA H,et al. Effect of xylan in hardwood pulp on the reaction rate of TEMPO-mediated oxidation and the rheology of the final nanofibrillated cellulose gel[J]. Cellulose,2015,23(1):1-17.
[81] MAO L,LAW K,CLAUDE D,et al. Effects of carboxyl content on the characteristics of TMP long fibers[J]. Indengchemres,2008,47(11):3809-3812.
[82] TSUGUYUKI S,SATOSHI K,YOSHIHARU N,et al. Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose[J]. Biomacromolecules,2007,8(8):2485-2491.
[83] YOSHIDA Y,YANAGISAWA M,ISOGAI A,et al. Preparation of polymer brush-type cellulose β-ketoesters using LiCl/1,3-dimethyl-2-imidazolidinone as a solvent[J]. Polymer,2005,46(8):2548-2557.
[84] TSUGUYUKI S,MASAYUKI H,NAOYUKI T,et al. Individualization of nano-sized plant cellulose fibrils by direct surface carboxylation using TEMPO catalyst under neutral conditions[J]. Biomacromolecules,2009,10(7):1992-1996.
[85] TSUGUYUKI S,YOSHIHARU N,JEAN-LUC P,et al. Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose[J]. Biomacromolecules,2006,7(6):1687-1691.
[86] HIROTA M,TAMURA N,SAITO T,et al. Oxidation of regenerated cellulose with NaClO2 catalyzed by TEMPO and NaClO under acid-neutral conditions[J]. Carbohydrate Polymers,2009,78(2):330-335.
[87] RINAUDO M. Periodate Oxidation of methylcellulose:characterization and properties of oxidized derivatives[J]. Polymers:Basel,2010,2(4):505-521.
[88] KIM U J,KUGA S,WADA M,et al. Periodate oxidation of crystalline cellulose[J]. Biomacromolecules,2000,1(3):488-492.
[89] LIIMATAINEN H,VISANKO M,SIRVI J,et al. Sulfonated cellulose nanofibrils obtained from wood pulp through regioselective oxidative bisulfite pre-treatment[J]. Cellulose,2013,20(2):741-749.
[90] ZIMMERMANN M V,BORSOI C,LAVORATTI A,et al. Drying techniques applied to cellulose nanofibers[J]. J. Reinf. Plast. Compos.,2016,
[91] BECK S,BOUCHARD J,BERRY R. Dispersibility in water of dried nanocrystalline cellulose[J]. Biomacromolecules,2012,13(5):1486-1494.
[92] PENG Y,GARDNER D J,HAN Y,et al. Influence of drying method on the material properties of nanocellulose Ⅰ:thermostability and crystallinity[J]. Cellulose,2013,20(5):2379-2392.
[93] PENG Y,GARDNER D J,HAN Y. Drying cellulose nanofibrils:in search of a suitable method[J]. Cellulose,2012,19(19):91-102.