This document discusses natural nanomaterials derived from biomass, including nanocelluloses and nanocomposites. It outlines processes for separating nanofibers and nanocrystals from cellulose sources and characterizing their properties. Examples are given of using nanocelluloses to produce reinforced composite materials, films, coatings, and medical prototypes. The document concludes that there is increasing interest in renewable nanomaterials and that biobased residues can be sources for nanocellulose with applications in various industries.

1. IntroductiontoNaturalNanomaterials Kristiina Oksman Niska Wood and Bionanocomposites Composite Center Sweden Luleå University of Technology The 2nd International Musical Instruments Seminar, 14-16 September 2011, Joensuu, Finland

3. Nanomaterials from biomass

4. Separation processes

5. Properties

6. Preparation of nanocomposites

7. Examples of nanocomposites and other nanomaterials based on cellulose

9. Research on nanocellulose materials and composites: 1995-2011 ( ISI Web ofSci. Sept 2011) Yano et al, Kyoto, Japan, Zimmermann et al EMPA, Switzerland Oksman et al NTNU, Norway Simonsen et al, Oregon, USA Sain et al, UofT, Canada Glasser, Virginia Tech, USA Winter et al, Suracuse, USA Nanocrystals and composites Taniguchi and Okamora, Niigata, Japan MicrofibrillatedCellulose Cavaille et al Grenoble, France Nanocrystals & composites

11. Largescale / pilot scaleproductionmethods

12. Chemicalmodifications

13. Properties

14. Composite materials development

15. Modelling

16. Assemblingoforganizedstructures

17. Product designIncreasedindustrialinteresttouseagro or forestbasednanomaterials H Yano, Kyoto, Japan Sport goods: With over 50,000 CarrotStixrodssold during 2009, the CarrotStixwasthe best-sellingproduct in itspricecategory (Nanopatents and Innovations March 2010) Cellu Comp, Carrot Stix™ www.cellucomp.com

18. Hierarchical structure of wood Soft wood fiber, diam 20-30 mm, length 2-5 mm Nanofibers, diam <100 nm, length > mm Crystallites, width < 5 nm, length < 300 nm Mechanical properties increases with decreased size Softwood = E-modulus about 12 GPa and strength 100 MPa Wood nanocrystals = E-modulus about 140 GPa and strength 10000 MPa

20. Cellulose nanofibers originate from wood, plants, crops or bacteria width below 100 nm, length up to µm scale

23. High pressure homogenizing

24. Ultra sonication

27. Mechanicalseparationofnanofibers Wood Purification Bleaching (Chlorite ) Cellulose Isolation process Soaking in water and mixing Pretreaments (Tempo, Enzymes) Fiber suspension Repeated until gel formation Refining (grinding) Nanofiber suspension

28. Barley straw Oat straw Grass straw Carrot residue Cellulose Nanofibers from biobased resources

30. No coating

31. Solvent exchange

32. Drying

33. Coating with gold 500 nm 500 nm

34. Nanopaper preparation CNF dispersed in water Vacuum filtration Hot pressing

37. Characterizationofcrystals 100 nm Length: < 300 nm Width: < 10 nm AFM Flow birefringence between polarized filters

38. MCC Amorphous regions Crystalline regions Microcrystalline cellulose: crystalline and amorphous regions Crystals/whiskers have highcrystallinity Elementary fibrils XRD before and afterseparation

39. Dimensions measurementusing AFM Sample preparation 1 μm 1 μm Height image Amplitude image 62.2 nm 40.8 mV Tip broadening effect 1 μm

40. Cellulosenanocrystals from bioresidues Largescaleproductionofcellulose nanocrystals? Wehavefoundthat lignin residue from bioethanolproduction has a highcellulosecontent Thiscellulosecan be separatedto nanocrystals usingonlymechanicalprocessing Oksman et al, Biomass and Bioenergy35(2011)146-152

42. High thermal stability

43. Large surface area

44. Bio-compatible

45. Light weight

46. Optically transparent

48. For nanofibers and crystals

49. Polymer is dissolved in a solvent, nanocellulosesareadded and the solvent is evaporated

51. Highnanofibercontent

53. Content is low < 5%

54. Industrial process

56. Removalliquid

59. Improve mechanical properties of the laminate, paper etc

63. Self-assembling

64. Surface structureAraki J; Wada M; KugaS; Okano T. Langmuir 2000, 16, 2413

66. Biocompatible*Santis de R, et al. Comp SciTechnol 2004;64:861-871

67. Mechanical properties of cellulose-collagen nanocomposites for ligament application Effect of simulated body conditions and sterilization

68. Prototypes BraidedXColl-Cell NFPDTubules Braided NFPD Stable in PBS medium (phosphate buffered saline)

69. Possible applications High-strength spun fibers and textiles Advanced composite materials Films for barrier and other properties Additives for coatings, paints, lacquers and adhesives Optical devices Electronic applications, lightweightbatteries Pharmaceuticals and drug delivery Bone and ligament replacements Hydrogels Aerogels Improved paper, packaging applications New building products Additives for food and cosmetics Separation membranes

70. Some conclusions Increased interest for natural and renewable nanomaterials Bio based residues can be used for separation of natural nanomaterials Nanomaterials are separated to nanosize using chemical/mechanical processing Nanocomposites processing methods are casting, impregnation, compounding, spinning, freeze and supercritical CO2 drying Nanomaterials can be used in medical applications, aerogels, nanomembranescoatings, textiles, composites, packakingappl. etc.

71. Thank you for listening… Thank my research team for all results and hard work

72. Yield of the separation process of nanocelluloses Cellulosecontent and yieldwashighest for lignin residuefollowed by oatstraw > carrotresidue > barleystraw > grassstraw