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High-speed monitoring of the crystallinity change in poly(lactic acid) during photodegradation by using a newly developed wide area NIR imaging system (Compovision)

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Abstract

We aimed to achieve wide area rapid monitoring of the crystallinity change in poly(lactic acid) (PLA) during photodegradation caused by ultraviolet (UV) light by using a newly developed near-infrared (NIR) camera (Compovison). Several kinds of PLA samples with different crystallinities and their blends with poly[(3)-(R)-hydroxybutyrate] were prepared. Their two-dimensional NIR spectra in the 1,000–2,350-nm region were measured by Compovision at a 5-min interval during photolysis. An intensity decrease of the band in the 1,900-1,925-nm region due to the second overtone of the C = O stretching vibration of PLA was observed during photolysis. This suggests that an anhydride carbonyl is produced during photolysis. The NIR image of the crystallinity change monitored by the band at 1,917 nm in the standard normal variate spectra clearly shows the inhomogeneity of crystal evolution. A logarithmic increase was observed for all identified areas in the PLA film; however, the time to reach the maximum crystallinity was slightly different according to the initial crystallinity of the sample. It is likely that the initial crystallinity of the sample influences the degradation speed more than the degradation amount. These imaging results have provided fundamental chemical insights into the photolytic process for PLA, and at the same time they have demonstrated that the two-dimensional spectral data obtained by Compovision are useful for process monitoring of polymers.

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References

  1. Tsuji H, Ikada Y (1996) Crystallization from the melt of poly(lactide)s with different optical purities and their blends. Macromol Chem Phys 197(10):3483–3499

    Article  CAS  Google Scholar 

  2. Tsuji H, Ikada Y (1998) Blends of aliphatic polyesters. 2. Hydrolysis of solution-cast blends from poly(l-lactide) and poly(ε-caprolactone) in phosphate-buffered solution. Appl Polym Sci 67(3):405–415

    Article  CAS  Google Scholar 

  3. Zhang JM, Tsuji H, Noda I, Ozaki Y (2004) Weak intermolecular interactions during the melt crystallization of poly (L-lactide) investigated by two- dimensional infrared correlation spectroscopy. J Phys Chem B 108:11514–11520

    Article  CAS  Google Scholar 

  4. Zhang JM, Tsuji H, Noda I, Ozaki Y (2004) Structural changes and crystallization dynamics of poly(L-lactide) during the cold crystallization process investigated by infrared and two-dimensional infrared correlation spectroscopy. Macromolecules 37:6433–6439

    Article  CAS  Google Scholar 

  5. Zhang JM, Duan Y, Sato H, Tsuji H, Noda I, Yan S, Ozaki Y (2005) Crystal modifications and thermal behavior of poly(l-lactic acid) revealed by infrared spectroscopy. Macromolecules 38:8012–8021

    Article  CAS  Google Scholar 

  6. Tsuji H, Miyauchi S (2001) Enzymatic hydrolysis of poly(lactide)s: Effects of molecular weight, L-lactide content, and enantiometic and diastereoisometric polymer blending. Biomacromolecules 2:597–604

    Article  CAS  Google Scholar 

  7. Nampoothiri KM, Nair NR, John RP (2010) An overview of the recent developments in polylactide (PLA) research. Bioresour Technol 101(22):8493–8501

    Article  Google Scholar 

  8. Tujii H, Echizen Y, Saha SK, Nisimura Y (2005) Photodegradation of poly(l-lactic acid): effects of photosensitizer. Macromol Mater Eng 290:1192–1203

    Article  Google Scholar 

  9. Tujii H, Shimizu K, Sato Y (2012) Hydrolytic degradation of poly(L-lactic acid): combined effects of UV treatment and crystallization. J Appl Polym 125:2394–2406

    Article  Google Scholar 

  10. Santonja-Blasco L, Ribes-Greus A, Almo RG (2013) Comparative thermal, biological and photodegradation kinetics of polylactide and effect on crystallization rate. Polym Degrad Stab 98:771–784

    Article  CAS  Google Scholar 

  11. Araújo A, Botelho GL, Silva M, Machado AV (2013) UV stability of poly(lactic acid) nanocomposites. J Mater Sci Eng B 3(2):75–83

    Google Scholar 

  12. Tsujii H, Echizen Y, Nishikawa Y (2006) Photodegradation of biodegradable polymers: A comprehensive study on poly(L-lactide) and poly(ε-caprolactone). Polym Degrad Stab 91:1128–1137

    Article  Google Scholar 

  13. Mucha M, Bialas S, Kaczmarek H (2014) Effect of nanosilver on the photodegradation of poly(lactic acid). J Appl Polym Sci 131:40144

    Article  Google Scholar 

  14. Yasuda N, Tsukegi T, Shirai Y, Nishida H (2011) Characteristic chain-end racemization behavior during photolysis of poly(L-lactic acid). Biomacromolecules 12(9):3299–3304

    Article  CAS  Google Scholar 

  15. Tsuji H, Ikeda Y (1997) Blends of crystalline and amorphous poly(lactide). III. Hydrolysis of solution-cast blend films. J Appl Polym Sci 63:855–863

    Article  CAS  Google Scholar 

  16. Shinzawa H, Nishida M, Tanaka T, Kanematsu W (2012) Accelerated weathering-induced degradation of poly(lactic acid) fiber studied by near-infrared (NIR) hyperspectral imaging. Appl Spectrosc 66(4):470–474

    Article  CAS  Google Scholar 

  17. Griffiths PR (2009) Infrared and Raman instrumentation for mapping and imaging. In: Salzer R, Siesler HW (eds) Infrared and Raman spectroscopic imaging. Wiley-VCH, Weinheim, pp pp 3–pp 64

    Google Scholar 

  18. Oellkrug D, Ostertag E, Kessler RW (2013) Quantitative Raman spectroscopy in turbid matter: reflection or transmission mode? Anal Bioanal Chem 405:3367–3379

    Article  Google Scholar 

  19. Kazarian SG, Andrew Chan KL (2010) Micro- and macro-attenuated total reflection Fourier transform infrared spectroscopic imaging. Appl Spectrosc 64(5):135A–152A

    Article  CAS  Google Scholar 

  20. Unger M, Sato H, Ozaki Y, Fischer D, Siesler HW (2013) Temperature-dependent Fourier transform infrared spectroscopy and Raman mapping spectroscopy of phase-separation in a poly(3-hydroxybutyrate)-poly(L-lactic acid) blend. Appl Spectrosc 67(2):141–148

    Article  CAS  Google Scholar 

  21. Zhang X, Espiritu M, Bilyk A, Kumiawan L (2008) Morphological behavior of poly(lactic acid) during hydrolytic degradation. Polym Degrad Stab 93:1964–1970

    Article  CAS  Google Scholar 

  22. Lee KAB, Johnson SC (1993) Comparison of mid-IR with NIR in polymer analysis. Appl Spectrosc Rev 28(3):231–284

    Article  Google Scholar 

  23. Šašić S, Ozaki Y (eds) (2009) Raman, infrared, and near-infrared chemical imaging. Wiley, New York

    Google Scholar 

  24. Kazarian SG, Brantley NH, Eckert CA (1999) Application of vibrational spectroscopy to characterize poly(ethylene terephthalate) processed with supercritical CO2. Vib Spectrosc 19:277–283

    Article  CAS  Google Scholar 

  25. Kradjel C (2001) NIR analysis of polymers. In: Burns DA, Ciurcziak EW (eds) Handbook of near-infrared analysis. Dekker, New York, pp pp 659–pp 702

    Google Scholar 

  26. Siesler HW (2002) Application to polymers and textiles. In: Siesler HW, Ozaki Y, Kawata S, Heise HM (eds) Near-infrared spectroscopy. Wiley-VCH, Weinheim, pp pp 213–pp 244

    Google Scholar 

  27. Ozaki Y (2012) Near-infrared spectroscopy - its versatility in analytical chemistry. Anal Sci 28:545–563

    Article  CAS  Google Scholar 

  28. Ishikawa D, Shinzawa H, Genkawa T, Kazarian SG, Ozaki Y (2013) Recent progress of near infrared (NIR) imaging—development of novel instruments and their applicability for practical situations—. Anal Sci 30:143–150

    Article  Google Scholar 

  29. Koenig JL (2005) FT-IR imaging of multicomponent polymers. In: Bhargava R, Levin IW (eds) Spectrochemical analysis using infrared multichemical detectors. Blackwell, Oxford, pp pp 115–pp 140

    Google Scholar 

  30. Steiner G, Koch E (2009) Trends in Fourier transform infrared spectroscopic imaging. Anal Bioanal Chem 394:671–678

    Article  CAS  Google Scholar 

  31. Kazarian SG, van der Weerd J (2008) Simultaneous FTIR spectroscopic imaging and visible photography to monitor tablet dissolution and drug release. Pham Res 25(4):853–860

    Article  CAS  Google Scholar 

  32. Gupper A, Kazarian SG (2005) Study of solvent diffusion and solvent-induced crystallization in syndiotactic polystyrene using FT-IR spectroscopy and imaging. Macromolecules 38(6):2327–2332

    Article  CAS  Google Scholar 

  33. Ishikawa D, Murayama K, Genkawa T, Awa K, Komiyama M, Ozaki Y (2012) Development of a compact near infrared imaging device with high-speed and portability for pharmaceutical process monitoring. NIR News 23(8):19–23

    Article  Google Scholar 

  34. Ishikawa D, Murayama K, Genkawa T, Awa K, Komiyama M, Kazarian SG, Ozaki Y (2013) Application of a newly developed portable NIR imaging device to monitor the dissolution process of tablets. Anal Bioanal Chem 405(29):9401–9409

    Article  CAS  Google Scholar 

  35. Ishikawa D, Nishii T, Mizuno F, Kazarian SG, Ozaki Y (2013) Development of a high-speed monitoring near infrared hyperspectral camera (Compovision) for wide area imaging and its applications. NIR News 24(5):6–11

    Article  Google Scholar 

  36. Ishikawa D, Nishii T, Mizuno F, Sato H, Kazarian SG, Ozaki Y (2013) Potential of a newly developed high-speed near infrared (NIR) camera (Compovision) in polymer industrial analyses: monitoring crystallinity and crystal evolution of polylactic acid (PLA) and concentration of PLA in PLA/poly-(R)-3hydroxybutyrate (PHB) blends. Appl Spectrosc 67(12):1441–1446

    Article  CAS  Google Scholar 

  37. Sato H, Nakamura M, Padermshoke A, Yamaguchi H, Terauchi H, Ekgasit S, Noda I, Ozaki Y (2004) Thermal behavior and molecular interaction of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) studied by wide-angle x-ray diffraction. Macromolecules 37:3763–3769

    Article  CAS  Google Scholar 

  38. Park JW, Doi Y, Iwata T (2005) Unique crystalline orientation of poly[(R)-3-hydroxybutyrate]/cellulose propionate blends under uniaxial drawing. Macromolecules 38:2345–2354

    Article  CAS  Google Scholar 

  39. Sudesh K, Doi Y (2005) Polyhydroxyalkanoates. In: Bastioli C (ed) Handbook of biodegradable polymers. Rapra Technology, Shawbury, pp pp 219–pp 256

    Google Scholar 

  40. Savitzky A, Golay MJE (1964) Smoothing and differentiation of data by simplified least squares procedures. Anal Chem 36(8):1627–1639

    Article  CAS  Google Scholar 

  41. Griffiths PR, Olinger JM (2002) Continuum theories of diffuse reflection. In: Chalmers JM, Griffiths PR (eds) Handbook of vibrational spectroscopy 2. Wiley, Chichester, pp pp 1125–pp 1139

    Google Scholar 

  42. Dhanoa MS, Lister SJ, Sanderson R, Barnes RJ (1994) The link between multiplicative scatter correction (MSC) and standard normal variate (SNV) transformations of NIR spectra. J Near Infrared Spectrosc 2:43–47

    Article  CAS  Google Scholar 

  43. Fearn T, Riccioli C, Varo AG, Ginel JEG (2009) On the geometry of SNV and MSC. Chemom Intell Lab Syst 96:22–26

    Article  CAS  Google Scholar 

  44. Furukawa T, Sato H, Shinzawa H, Noda I, Ochiai S (2007) Evaluation of homogeneity of binary blends of poly(3-hydroxybutyrate) and poly(L-lactic acid) studied by near infrared chemical imaging (NIRCI). Anal Sci 23:871–876

    Article  CAS  Google Scholar 

  45. Furukawa T, Sato H, Murakami R, Zhang J, Noda I, Ochiai S, Ozaki Y (2006) Raman microspectroscopy study of structure, dispersibility, and crystallinity of poly(hydroxybutyrate)-poly(l-lactic acid) blends. Polymer 47:3132–3140

    Article  CAS  Google Scholar 

  46. Furukawa T, Sato H, Murakami R, Zhang J, Duan Y, Noda I, Ochiai S, Ozaki Y (2005) Structure, dispersibility, and crystallinity of poly(hydroxybutyrate)/poly(l-lactic acid) blends studied by FT-IR microspectroscopy and differential scanning calorimetry. Macromolecules 38:6445–6454

    Article  CAS  Google Scholar 

  47. Hu Y, Zhang J, Sato H, Futami Y, Noda I, Ozaki Y (2006) C-H…O = C Hydrogen bonding and isothermal crystallization kinetics of poly(3-hydroxybutyrate) investigated by near-infrared spectroscopy. Macromolecules 39:3841–3847

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Graduate School of Agriculture, Tohoku University, 1-1, Amamiya, Tsutumidori, Aoba-ku, Sendai, 981-8555, Japan

    Daitaro Ishikawa

  2. Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, 669-1337, Japan

    Daitaro Ishikawa, Daiki Furukawa, Tseng Tsai Wei, Kummetha Raghunatha Reddy & Yukihiro Ozaki

  3. Sumitomo Electric Industries Ltd, 1, Taya, Sakae-ku, Yokohama, 244-8588, Japan

    Asako Motomura & Yoko Igarashi

  4. Graduate School of Human Development and Environmental Science, Kobe University, 3-11, Tsurukabuto, Nada-ku, Kobe, 657-8501, Japan

    Harumi Sato

  5. Department of Chemical Engineering, Imperial College London, London, SW7 2AZ, UK

    Sergei G. Kazarian

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  1. Daitaro Ishikawa
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  2. Daiki Furukawa
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  9. Yukihiro Ozaki
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Correspondence to Daitaro Ishikawa.

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Ishikawa, D., Furukawa, D., Wei, T.T. et al. High-speed monitoring of the crystallinity change in poly(lactic acid) during photodegradation by using a newly developed wide area NIR imaging system (Compovision). Anal Bioanal Chem 407, 397–403 (2015). https://doi.org/10.1007/s00216-014-8211-z

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  • DOI: https://doi.org/10.1007/s00216-014-8211-z

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