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Investigation of morphology associated with biporous polymeric materials obtained by the double porogen templating approach

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Abstract

Doubly porous polymeric materials were prepared from 2-hydroxyethyl methacrylate (HEMA) through the double porogen templating approach. One such approach required the use of a macroporogenic agent, i.e., NaCl particles, and a porogenic solvent. To this purpose, sieved NaCl particles of different size ranges were used (125–200 μm, 200–250 μm, and 250–400 μm), either sintered through Spark Plasma Sintering or non-fused, in conjunction with a porogenic solvent, i.e., isopropanol. After removal of both porogens, the resulting biporous scaffolds were finely characterized in terms of porosity by scanning electron microscopy (SEM), mercury intrusion porosimetry (MIP), and nitrogen sorption porosimetry. All the obtained results indicated higher porosity ratios and specific surface areas for doubly porous materials prepared from SPS-mediated sintering of macroparticles, thus demonstrating the crucial role of macroporogen packing on the resulting porosity features. Indeed, a higher compaction of NaCl particles generated fewer interstitial voids between adjacent inorganic particles and thus afforded a higher porosity (87% porosity ratio) in the resulting porous material as compared to the corresponding analogue prepared from non-sintered NaCl particles (80% porosity ratio). A complementary 3-D imaging of the microstructure by means of laboratory X-ray computed microtomography (μCT) but also synchrotron μCT analysis qualitatively confirmed these findings. The macroporogen size was also considered to be a crucial parameter regarding the porosity features, as increasing macroporogen sizes were notably associated with increasing porosity ratios. Finally, swelling of those mono- and biporous materials was investigated. The interconnection in the higher porosity level was notably evaluated, and it was observed that the water uptake of biporous PHEMA scaffolds comprising an interconnected higher porosity level can be as high as ~ 2500%.

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References

  1. Lav TX, Carbonnier B, Guerrouache M, Grande D (2010) Porous polystyrene-based monolithic materials templated by semi-interpenetrating polymer networks for capillary electrochromatography. Polymer 51(25):5890–5894

    Article  CAS  Google Scholar 

  2. Lav TX, Grande D, Gaillet C, Guerrouache M, Carbonnier B (2012) Porous poly(styrene-co-divinylbenzene) neutral monolith: from design and characterization to reversed-phase capillary electrochromatography applications. Macromol Chem Phys 213(1):64–71

    Article  CAS  Google Scholar 

  3. Yu C, Xu MC, Svec F, Frechet JMJ (2002) Preparation of monolithic polymers with controlled porous properties for microfluidic chip applications using photoinitiated free-radical polymerization. J Polym Sci Pol Chem 40(6):755–769

    Article  CAS  Google Scholar 

  4. Langer R, Vacanti JP (1993) Tissue engineering. Science 260(5110):920–926

    Article  CAS  Google Scholar 

  5. Nair LS, Laurencin CT (2007) Biodegradable polymers as biomaterials. Prog Polym Sci 32(8-9):762–798

    Article  CAS  Google Scholar 

  6. Auriault JL, Boutin C (1992) Deformable porous-media with double porosity - quasi-statics .1. Coupling effects. Transport Porous Med 7(1):63–82

    Article  CAS  Google Scholar 

  7. Boutin C, Royer P, Auriault JL (1998) Acoustic absorption of porous surfacing with dual porosity. Int J Solids Struct 35(34-35):4709–4737

    Article  Google Scholar 

  8. Ly HB, Le Droumaguet B, Monchiet V, Grande D (2016) Tailoring doubly porous poly(2-hydroxyethyl methacrylate)-based materials via thermally induced phase separation. Polymer 86:138–146

    Article  CAS  Google Scholar 

  9. Santamaria VA, Deplaine H, Mariggio D, Villanueva-Molines AR, Garcia-Aznar JM, Ribelles JLG et al (2012) Influence of the macro and micro-porous structure on the mechanical behavior of poly(L-lactic acid) scaffolds. J Non-Cryst Solids 358(23):3141–3149

    Article  CAS  Google Scholar 

  10. Liu XH, Ma PX (2009) Phase separation, pore structure, and properties of nanofibrous gelatin scaffolds. Biomaterials 30(25):4094–4103

    Article  CAS  Google Scholar 

  11. Yang YF, Zhao J, Zhao YH, Wen L, Yuan XY, Fan YB (2008) Formation of porous PLGA scaffolds by a combining method of thermally induced phase separation and porogen leaching. J Appl Polym Sci 109(2):1232–1241

    Article  CAS  Google Scholar 

  12. Kovacic S, Stefanec D, Krajnc P (2007) Highly porous open-cellular monoliths from 2-hydroxyethyl methacrylate based high internal phase emulsions (HIPEs): preparation and void size tuning. Macromolecules 40(22):8056–8060

    Article  CAS  Google Scholar 

  13. Kulygin O, Silverstein MS (2007) Porous poly(2-hydroxyethyl methacrylate) hydrogels synthesized within high internal phase emulsions. Soft Matter 3(12):1525–1529

    Article  CAS  Google Scholar 

  14. Cameron NR (2005) High internal phase emulsion templating as a route to well-defined porous polymers. Polymer 46(5):1439–1449

    Article  CAS  Google Scholar 

  15. Silverstein MS (2014) Emulsion-templated porous polymers: a retrospective perspective. Polymer 55(1):304–320

    Article  CAS  Google Scholar 

  16. Ghosh S, Viana JC, Reis RL, Mano JF (2007) The double porogen approach as a new technique for the fabrication of interconnected poly(L-lactic acid) and starch based biodegradable scaffolds. J Mater Sci-Mater Med 18(2):185–193

    Article  CAS  Google Scholar 

  17. Le Droumaguet B, Lacombe R, Ly H-B, Carbonnier B, Grande D (2014) Novel polymeric materials with double porosity: synthesis and characterization. Macromol Symp 340(1):18–27

    Article  CAS  Google Scholar 

  18. Le Droumaguet B, Lacombe R, Ly H-B, Guerrouache M, Carbonnier B, Grande D (2014) Engineering functional doubly porous PHEMA-based materials. Polymer 55(1):373–379

    Article  Google Scholar 

  19. Ly HB, Le Droumaguet B, Monchiet V, Grande D (2015) Facile fabrication of doubly porous polymeric materials with controlled nano- and macro-porosity. Polymer 78:13–21

    Article  CAS  Google Scholar 

  20. Ly H-B, Le Droumaguet B, Monchiet V, Grande D (2015) Designing and modeling doubly porous polymeric materials. Eur Phys J Spec Top 224(9):1689–1706

    Article  CAS  Google Scholar 

  21. Kim UJ, Park J, Kim HJ, Wada M, Kaplan DL (2005) Three-dimensional aqueous-derived biomaterial scaffolds from silk fibroin. Biomaterials 26(15):2775–2785

    Article  CAS  Google Scholar 

  22. Gross KA, Rodriguez-Lorenzo LM (2004) Thermally sprayed scaffolds for tissue engineering applications. Key Eng Mater 254:961–964

    Google Scholar 

  23. Gross KA, Rodriguez-Lorenzo LM (2004) Biodegradable composite scaffolds with an interconnected spherical network for bone tissue engineering. Biomaterials 25(20):4955–4962

    Article  CAS  Google Scholar 

  24. Audouin F, Heise A (2014) Synthesis of polymer–silica hybrid polyHIPEs by double in situ polymerization of concentrated water in oil emulsion. Polymer 55(1):403–409

    Article  CAS  Google Scholar 

  25. Aligizaki KK (2005) Pore structure of cement-based materials: testing, interpretation and requirements. Taylor & Francis, New-York

    Book  Google Scholar 

  26. Cartmell S, Huynh K, Lin A, Nagaraja S, Guldberg R (2004) Quantitative microcomputed tomography analysis of mineralization within three-dimensional scaffolds in vitro. J Biomed Mater Res Part A 69A(1):97–104

    Article  CAS  Google Scholar 

  27. Darling AL, Sun W (2004) 3D microtomographic characterization of precision extruded poly-epsilon-caprolactone scaffolds. J Biomed Mater Res Part B Appl Biomater 70B(2):311–317

    Article  CAS  Google Scholar 

  28. Lin ASP, Barrows TH, Cartmell SH, Guldberg RE (2003) Microarchitectural and mechanical characterization of oriented porous polymer scaffolds. Biomaterials 24(3):481–489

    Article  CAS  Google Scholar 

  29. van Lenthe GH, Hagenmuller H, Bohner M, Hollister SJ, Meinel L, Muller R (2007) Nondestructive micro-computed tomography for biological imaging and quantification of scaffold-bone interaction in vivo. Biomaterials 28(15):2479–2490

    Article  Google Scholar 

  30. Jones AC, Milthorpe B, Averdunk H, Limaye A, Senden TJ, Sakellariou A, Sheppard AP, Sok RM, Knackstedt MA, Brandwood A, Rohner D, Hutmacher DW (2004) Analysis of 3D bone ingrowth into polymer scaffolds via micro-computed tomography imaging. Biomaterials 25(20):4947–4954

    Article  CAS  Google Scholar 

  31. Moore MJ, Jabbari E, Ritman EL, Lu LC, Currier BL, Windebank AJ, Yaszemski MJ (2004) Quantitative analysis of interconnectivity of porous biodegradable scaffolds with micro-computed tomography. J Biomed Mater Res Part A 71A(2):258–267

    Article  CAS  Google Scholar 

  32. Bruchon JF, Pereira JM, Vandamme M, Lenoir N, Delage P, Bornert M (2013) Full 3D investigation and characterisation of capillary collapse of a loose unsaturated sand using X-ray CT. Granul Matter 15(6):783–800

    Article  Google Scholar 

  33. Flannery BP, Deckman HW, Roberge WG, Amico KL (1987) Three-Dimensional X-ray Microtomography. Science 237(4821):1439

    Article  CAS  Google Scholar 

  34. Kinney JH, Nichols MC (1992) X-Ray tomographic microscopy (XTM) using synchrotron radiation. Annu Rev Mater Sci 22(1):121–152

    Article  CAS  Google Scholar 

  35. Lerouge T, Maillet B, Coutier-Murias D, Grande D, Le Droumaguet B, Pitois O et al (2020) Drying of a compressible biporous material. Phys Rev Appl 13(4)

  36. Lerouge T, Pitois O, Grande D, Le Droumaguet B, Coussot P (2018) Synergistic actions of mixed small and large pores for capillary absorption through biporous polymeric materials. Soft Matter 14(40):8137–8146

    Article  CAS  Google Scholar 

  37. Mabilleau G, Stancu IC, Honoré T, Legeay G, Cincu C, Baslé MF, Chappard D (2006) Effects of the length of crosslink chain on poly(2-hydroxyethyl methacrylate) (pHEMA) swelling and biomechanical properties. J Biomed Mater Res Part A 77A(1):35–42

    Article  CAS  Google Scholar 

  38. Refojo MF (1967) Hydrophobic interaction in poly(2-hydroxyethyl methacrylate) homogeneous hydrogel. J Polym Sci Pol Chem 5(12):3103–3113

    Article  CAS  Google Scholar 

  39. Uzun L, Say R, Denizli A (2005) Porous poly(hydroxyethyl methacrylate) based monolith as a new adsorbent for affinity chromatography. React Funct Polym 64(2):93–102

    Article  CAS  Google Scholar 

  40. Gomes ME, Ribeiro AS, Malafaya PB, Reis RL, Cunha AM (2001) A new approach based on injection moulding to produce biodegradable starch-based polymeric scaffolds: morphology, mechanical and degradation behaviour. Biomaterials 22(9):883–889

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors are indebted to B. Villeroy (ICMPE, CNRS) for his kind technical assistance in the SPS technique. Synchrotron µCT imaging was run on the Anatomix beamline of Synchrotron Soleil in the context of the 20171213 standard proposal. The authors wish to deeply thank the scientific staff of the beamline, Mario Scheel, Jonathan Perrin and Timm Weitkamp, for their assistance during the experiment.

Funding

This work was supported by a French government grant from ANR within the frame of the national program Investments for the Future ANR-11-LABX-022-01 (LabEx MMCD project).

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Authors and Affiliations

  1. Univ Paris Est Creteil, CNRS, Institut de Chimie et des Matériaux Paris-Est (ICMPE), UMR 7182, 2 rue Henri Dunant, 94320, Thiais, France

    Sarra Mezhoud, Benjamin Le Droumaguet & Daniel Grande

  2. Laboratoire Navier, Ecole des Ponts ParisTech, UMR 8205 CNRS, Univ. Gustave Eiffel, 6/8 avenue Blaise Pascal, 77455, Marne-la-Vallée Cedex 2, France

    Sarra Mezhoud, Patrick Aimedieu & Michel Bornert

  3. Univ Gustave Eiffel, Laboratoire de Modélisation et de Simulation Multi Echelle, CNRS UMR 8208, Univ Paris Est-Créteil, 5 boulevard Descartes, 77454, Marne-la-Vallée Cedex, France

    Sarra Mezhoud & Vincent Monchiet

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  1. Sarra Mezhoud
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  2. Benjamin Le Droumaguet
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  4. Vincent Monchiet
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  6. Daniel Grande
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Correspondence to Benjamin Le Droumaguet or Daniel Grande.

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Mezhoud, S., Le Droumaguet, B., Aimedieu, P. et al. Investigation of morphology associated with biporous polymeric materials obtained by the double porogen templating approach. Colloid Polym Sci 299, 537–550 (2021). https://doi.org/10.1007/s00396-020-04747-9

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  • DOI: https://doi.org/10.1007/s00396-020-04747-9

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