Skip to main content
Log in

Cellulose scaffolds with an aligned and open porosity fabricated via ice-templating

  • Original Paper
  • Published:
Cellulose Aims and scope Submit manuscript

Abstract

Regenerated cellulose scaffolds with an aligned, columnar and open porosity were fabricated by an ice-templating process. For this purpose, cellulose dissolved in the non-derivatizing aqueous solvent NaOH/urea was used. This cellulose solution was frozen from the bottom side of the mold leading to a directional heat flow in only one direction. Consequently, the directional solidification leads to a directional ice crystal growth. The ice crystals grow as aligned columns repelling and enriching the cellulose molecules between them. After a complete solidification and sublimation of the ice crystals, which act as a sacrificial phase, a structured porous cellulose network is achieved. The scaffold was analysed by light microscopy and X-ray diffraction. The pore sizes in the scaffold can be adjusted by the processing conditions. However, an approach for structural control which is only based on the solution of the heat conduction equation and which was found to be appropriate for ceramic suspensions has only limited suitability for cellulose solutions. In the case of cellulose solutions the diffusion and redistribution of solutes seem to be of significant impact and have to be considered in an adapted model.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  • Bareggi A, Maire E, Lasalle A, Deville S (2011) Dynamics of the freezing front during the solidification of a colloidal alumina suspension. In situ X-ray radiography, tomography and modeling. J Am Ceram Soc 94:3570–3578

    Article  CAS  Google Scholar 

  • Cai J, Zhang L (2005) Rapid dissolution of cellulose in LiOH/urea and NaOH/urea aqueous solutions. Macromol Biosci 5:539–548

    Article  CAS  Google Scholar 

  • Cai J, Zhang L (2006) Unique gelation behavior of cellulose in NaOH/urea aqueous solution. Biomacromolecules 7:183–189

    Article  CAS  Google Scholar 

  • Cai J, Zhang L, Zhou J, Li H, Chen H, Jin H (2004) Novel fibers prepared from cellulose in NaOH/urea aqueous solution. Macromol Rapid Commun 25:1558–1562

    Article  CAS  Google Scholar 

  • Cai J, Zhang L, Liu S, Liu Y, Xu X, Chen X, Chu B, Guo X, Xu J, Cheng H, Han CC, Kuga S (2008a) Dynamic self-assembly induced rapid dissolution of cellulose at low temperatures. Macromolecules 41:9345–9351

    Article  CAS  Google Scholar 

  • Cai J, Kimura S, Wada M, Kuga S, Zhang L (2008b) Cellulose aerogels from aqueous alkali hydroxide–urea solution. ChemSusChem 1:149–154

    Article  CAS  Google Scholar 

  • Deville S (2008) Freeze-casting of porous ceramics: a review of current achievements and issues. Adv Eng Mater 10:155–169

    Article  CAS  Google Scholar 

  • Deville S, Saiz E, Nalla RK, Tomsia AP (2006) Freezing as a path to build complex composites. Science 311:515–518

    Article  CAS  Google Scholar 

  • Deville S, Maire E, Lasalle A, Bogner A, Gauthier C, Leloup J, Guizard C (2009) In situ X-Ray radiography and tomography observations of the solidification of aqueous alumina particle suspensions—part I: initial instants. J Am Ceram Soc 92:2489–2496

    Article  CAS  Google Scholar 

  • Flauder S, Gbureck U, Müller FA (2013) β-TCP scaffolds with an interconnected and aligned porosity fabricated via ice-templating. Key Eng Mater 529–530:129–132

    Google Scholar 

  • Flemings MC (1974) Cellular solidification. In: Clark BJ, Gardner M (eds) Solidification processing. McGraw-Hill, New York, pp 58–64

    Google Scholar 

  • Fukasawa T, Ando M, Ohji T, Kanzaki S (2001) Synthesis of porous ceramics with complex pore structure by freeze-dry processing. J Am Ceram Soc 84:230–232

    Article  CAS  Google Scholar 

  • Isogai A, Atalla RH (1998) Dissolution of cellulose in aqueous NaOH solutions. Cellulose 5:309–319

    Article  CAS  Google Scholar 

  • Kamide K, Okajima K, Kowsaka K (1992) Dissolution of natural cellulose into aqueous alkali solution: role of super-molecular structure of cellulose. Polym J 24:71–86

    Article  CAS  Google Scholar 

  • Kawando Y, Ohashi T (2009) A mesoscopic numerical study of sea ice crystal growth and texture development. Cold Reg Sci Technol 57:39–48

    Article  Google Scholar 

  • Kolpak FJ, Blackwell J (1976) Determination of the structure of cellulose II. Macromolecules 9:273–278

    Article  CAS  Google Scholar 

  • Lasalle A, Guizard C, Leloup J, Deville S, Maire E, Bogner A, Gauthier C, Adrien J, Courtois L (2007) Ice-templating of alumina suspensions: effect of supercooling and crystal growth during the initial freezing regime. J Am Ceram Soc 95:799–804

    Article  Google Scholar 

  • Meghri NW, Donius AE, Riblett BW, Martin EJ, Clyne AM, Wegst UGK (2010) Directionally solidified biopolymer scaffolds: mechanical properties and endothelial cell responses. Biol Biomed Mater 92:71–75

    Google Scholar 

  • Miyamoto T, Takahashi S, Ito H, Inagaki H, Nooishiki Y (1989) Tissue biocompatibility of cellulose and its derivatives. J Biomed Mater Res 23:125–133

    Article  CAS  Google Scholar 

  • Müller FA, Müller L, Hofmann I, Greil P, Wenzel MM, Staudemaier R (2006) Cellulose-based scaffold materials for cartilage tissue engineering. Biomaterials 27:3955–3963

    Article  Google Scholar 

  • Nada H, Furukawa Y (1996) Anisotropic growth kinetics of ice crystals from water studied by molecular dynamics simulation. J Cryst Growth 169:587–597

    Article  CAS  Google Scholar 

  • Stefan J (1891) Über die Theorie der Eisbildung, insbesondere über die Eisbildung im Polarmeere. Ann Phys Chem 42:269–286

    Article  Google Scholar 

  • Tong HM, Noda I, Gryte CC (1984) Formation of anisotropic ice–agar composites by directional freezing. Colloid Polym Sci 262:589–595

    Article  CAS  Google Scholar 

  • Waschkies T, Oberacker R, Hoffmann MJ (2009) Control of lamellae spacing during freeze casting of ceramic using double-side cooling as a novel processing route. J Am Ceram Soc 92:79–84

    Article  Google Scholar 

  • Waschkies T, Oberacker R, Hoffmann MJ (2011) Investigation of structure formation during freeze-casting from very slow to very fast solidification velocities. Acta Mater 59:5135–5145

    Article  CAS  Google Scholar 

  • Wesarg F, Schlott F, Grabow J, Kurland HD, Heßler N, Kralisch D, Müller FA (2012) In situ synthesis of photocatalytically active hybrids consisting of bacterial nanocellulose and anatase nanoparticles. Langmuir 28:13518–13525

    Article  CAS  Google Scholar 

  • Zhang L, Ruan D, Zhou J (2001) Structure and properties of regenerated cellulose films prepared from cotton linters in NaOH/urea aqueous solution. Ind Eng Chem Res 40:5923–5928

    Article  CAS  Google Scholar 

  • Zhang L, Mao Y, Zhou J, Cai J (2005a) Effects of coagulation conditions on the properties of regenerated cellulose films prepared in NaOH/urea aqueous solution. Ind Eng Chem Res 44:522–529

    Article  CAS  Google Scholar 

  • Zhang H, Hussain I, Brust M, Butler MF, Rannard SP, Cooper AI (2005b) Aligned two- and three-dimensional structures by directional freezing of polymers and nanoparticles. Nat Mater 4:787–793

    Article  CAS  Google Scholar 

  • Zmora S, Glicklis R, Cohen S (2002) Tailoring the pore architecture in 3-D alginate scaffolds by controlling the freezing regime during fabrication. Biomaterials 23:4087–4094

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The European Commision is thankfully acknowledged for financial support of the OPHIS project under contract FP7-NMP-2009-SMALL-3-246373. Prof. Paul Seidel and Matthias Thürk from the Low Temperature Physics group of the Friedrich-Schiller-University of Jena are thankfully acknowledged for the support during the design and fabrication of the freezing device.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Stefan Flauder.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Flauder, S., Heinze, T. & Müller, F.A. Cellulose scaffolds with an aligned and open porosity fabricated via ice-templating. Cellulose 21, 97–103 (2014). https://doi.org/10.1007/s10570-013-0119-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10570-013-0119-9

Keywords

Navigation