{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,25]],"date-time":"2026-04-25T02:20:20Z","timestamp":1777083620124,"version":"3.51.4"},"reference-count":57,"publisher":"MDPI AG","issue":"9","license":[{"start":{"date-parts":[[2018,9,4]],"date-time":"2018-09-04T00:00:00Z","timestamp":1536019200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100008530","name":"European Regional Development Fund","doi-asserted-by":"publisher","award":["POCI-01-0145-FEDER-006939"],"award-info":[{"award-number":["POCI-01-0145-FEDER-006939"]}],"id":[{"id":"10.13039\/501100008530","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100008530","name":"European Regional Development Fund","doi-asserted-by":"publisher","award":["LEPABE-2-ECO-INNOVATION\u201d \u2013 NORTE\u201001\u20100145\u2010FEDER\u2010000005"],"award-info":[{"award-number":["LEPABE-2-ECO-INNOVATION\u201d \u2013 NORTE\u201001\u20100145\u2010FEDER\u2010000005"]}],"id":[{"id":"10.13039\/501100008530","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["POCI-01-0145-FEDER-006939"],"award-info":[{"award-number":["POCI-01-0145-FEDER-006939"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["NORTE-01-0145-FEDER-022096"],"award-info":[{"award-number":["NORTE-01-0145-FEDER-022096"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Polymers"],"abstract":"<jats:p>Microparticles of corn starch and chitosan crosslinked with glutaraldehyde, produced by the solvent exchange technique, are studied as reinforcement fillers for thermoplastic corn starch plasticized with glycerol. The presence of 10% w\/w chitosan in the microparticles is shown to be essential to guaranteeing effective crosslinking, as demonstrated by water solubility assays. Crosslinked chitosan forms an interpenetrating polymer network with starch chains, producing microparticles with a very low solubility. The thermal stability of the microparticles is in agreement with their polysaccharide composition. An XRD analysis showed that they have crystalline fraction of 32% with Va-type structure, and have no tendency to undergo retrogradation. The tensile strength, Young\u2019s modulus, and toughness of thermoplastic starch increased by the incorporation of the crosslinked starch\/chitosan microparticles by melt-mixing. Toughness increased 360% in relation to unfilled thermoplastic starch.<\/jats:p>","DOI":"10.3390\/polym10090985","type":"journal-article","created":{"date-parts":[[2018,9,5]],"date-time":"2018-09-05T03:08:55Z","timestamp":1536116935000},"page":"985","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":41,"title":["Reinforcement of Thermoplastic Corn Starch with Crosslinked Starch\/Chitosan Microparticles"],"prefix":"10.3390","volume":"10","author":[{"given":"Diana","family":"Paiva","sequence":"first","affiliation":[{"name":"LEPABE, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal"}]},{"given":"Andr\u00e9","family":"Pereira","sequence":"additional","affiliation":[{"name":"IFIMUP and IN\u2014Institute of Nanoscience and Nanotechnology, Departamento de F\u00edsica e Astronomia, Faculdade de Ci\u00eancias, Universidade do Porto, 4169-007 Porto, Portugal"}]},{"given":"Ana","family":"Pires","sequence":"additional","affiliation":[{"name":"IFIMUP and IN\u2014Institute of Nanoscience and Nanotechnology, Departamento de F\u00edsica e Astronomia, Faculdade de Ci\u00eancias, Universidade do Porto, 4169-007 Porto, Portugal"}]},{"given":"Jorge","family":"Martins","sequence":"additional","affiliation":[{"name":"LEPABE, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal"},{"name":"DEMad\u2014Instituto Polit\u00e9cnico de Viseu, Campus Polit\u00e9cnico de Repeses 3504-510 Viseu, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4557-7113","authenticated-orcid":false,"given":"Lu\u00edsa","family":"Carvalho","sequence":"additional","affiliation":[{"name":"LEPABE, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal"},{"name":"DEMad\u2014Instituto Polit\u00e9cnico de Viseu, Campus Polit\u00e9cnico de Repeses 3504-510 Viseu, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4447-4473","authenticated-orcid":false,"given":"Fern\u00e3o","family":"Magalh\u00e3es","sequence":"additional","affiliation":[{"name":"LEPABE, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2018,9,4]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"335","DOI":"10.1002\/star.19920440905","article-title":"Extrudates of cornstarch with urea and glycols: Structure\/mechanical property relations","volume":"44","author":"Shogren","year":"1992","journal-title":"Starch-St\u00e4rke"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"311","DOI":"10.3144\/expresspolymlett.2010.39","article-title":"Starch-lignin foams","volume":"4","author":"Stevens","year":"2010","journal-title":"Express Polym. Lett."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"121","DOI":"10.15376\/biores.5.1.121-134","article-title":"Dimensional changes of starch microcellular foam during the exchange of water with ethanol and subsequent drying","volume":"5","author":"Patel","year":"2009","journal-title":"BioResources"},{"key":"ref_4","first-page":"111","article-title":"Recent research and patents on preparation and application of starch-based plastics","volume":"10","author":"Jiankang","year":"2017","journal-title":"Recent Patents Mech. Eng."},{"key":"ref_5","unstructured":"Carvalho, A.J.F. (2016). Chapter 6: Chemical Modification of Thermoplastic Starch. RSC Green Chemistry, RSC."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"2917","DOI":"10.1002\/app.29270","article-title":"Development of cross-linked starch microcellular foam by solvent exchange and reactive supercritical fluid extrusion","volume":"111","author":"Patel","year":"2009","journal-title":"J. Appl. Polym. Sci."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"133","DOI":"10.1016\/j.carbpol.2007.11.013","article-title":"Effect of alkyl ketene dimer reacted starch on the properties of starch microcellular foam using a solvent exchange technique","volume":"73","author":"Venditti","year":"2008","journal-title":"Carbohydr. Polym."},{"key":"ref_8","doi-asserted-by":"crossref","unstructured":"Kabasci, S. (2013). Starch. Bio-Based Plastics: Materials and Applications, Wiley.","DOI":"10.1002\/9781118676646"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"246","DOI":"10.1016\/j.compositesa.2015.08.014","article-title":"A review: Starch-based composite foams","volume":"78","author":"Soykeabkaew","year":"2015","journal-title":"Compos. Part A Appl. Sci. Manuf."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"281","DOI":"10.1016\/j.carbpol.2011.02.041","article-title":"Application of small-angle X-ray and neutron scattering techniques to the characterisation of starch structure: A review","volume":"85","author":"Blazek","year":"2011","journal-title":"Carbohydr. Polym."},{"key":"ref_11","unstructured":"Gandini, A. (2008). Starch: Major Sources, Properties and Applications as Thermoplastic Materials a2\u2014Belgacem, Mohamed Naceur. Monomers, Polymers and Composites from Renewable Resources, Elsevier."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"568","DOI":"10.1111\/1541-4337.12143","article-title":"Starch retrogradation: A comprehensive review","volume":"14","author":"Wang","year":"2015","journal-title":"Compr. Rev. Food Sci. Food Saf."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"907","DOI":"10.1002\/mabi.200700080","article-title":"Extrusion foaming of semi-crystalline PLA and PLA\/thermoplastic starch blends","volume":"7","author":"Mihai","year":"2007","journal-title":"Macromol. Biosci."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"215","DOI":"10.1177\/0021955X07076532","article-title":"Foaming of polystyrene\/thermoplastic starch blends","volume":"43","author":"Mihai","year":"2007","journal-title":"J. Cell. Plast."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"2334","DOI":"10.1088\/0957-4484\/16\/10\/056","article-title":"Novel thermoplastic starch-clay nanocomposite foams","volume":"16","author":"Chen","year":"2005","journal-title":"Nanotechnology"},{"key":"ref_16","first-page":"72","article-title":"Water-assisted production of thermoplastic nanocomposites: A review","volume":"8","author":"Kmetty","year":"2015","journal-title":"Materials"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"e12447","DOI":"10.1111\/jfpe.12447","article-title":"Thermoplastic starch: A possible biodegradable food packaging material\u2014A review","volume":"40","author":"Bahram","year":"2017","journal-title":"J. Food Process Eng."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"809","DOI":"10.1002\/pi.5319","article-title":"Optimizing mechanical and physical properties of thermoplastic starch via tuning the molecular microstructure through co-plasticization by sorbitol and glycerol","volume":"66","author":"Esmaeili","year":"2017","journal-title":"Polym. Int."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"80","DOI":"10.1002\/star.200390020","article-title":"Material properties and glass transition temperatures of different thermoplastic starches after extrusion processing","volume":"55","author":"Graaf","year":"2003","journal-title":"Starch-St\u00e4rke"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"453","DOI":"10.1016\/j.jfoodeng.2005.04.031","article-title":"Effects of controlled storage on thermal, mechanical and barrier properties of plasticized films from different starch sources","volume":"75","author":"Mali","year":"2006","journal-title":"J. Food Eng."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"95","DOI":"10.7569\/JRM.2014.634104","article-title":"Thermoplastic starch: Current development and future trends","volume":"2","author":"Xie","year":"2014","journal-title":"J. Renew. Mater."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"1453","DOI":"10.1021\/bm1000235","article-title":"Synthesis and characterization of starch citrate\u2212chitosan foam with superior water and saline absorbance properties","volume":"11","author":"Salam","year":"2010","journal-title":"Biomacromolecules"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"2401","DOI":"10.1007\/s00289-016-1814-0","article-title":"Cellulosic materials as natural fillers in starch-containing matrix-based films: A review","volume":"74","author":"Alvarez","year":"2017","journal-title":"Polym. Bull."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"858","DOI":"10.1016\/j.compscitech.2012.02.019","article-title":"Natural fiber-reinforced thermoplastic starch composites obtained by melt processing","volume":"72","author":"Carvalho","year":"2012","journal-title":"Compos. Sci. Technol."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"576","DOI":"10.1016\/j.carbpol.2013.11.020","article-title":"Bio-composites of cassava starch-green coconut fiber: Part ii\u2014Structure and properties","volume":"102","author":"Kestur","year":"2014","journal-title":"Carbohydr. Polym."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"2428","DOI":"10.1002\/app.33447","article-title":"Thermoplastic corn starch reinforced with cotton cellulose nanofibers","volume":"120","author":"Teixeira","year":"2011","journal-title":"J. Appl. Polym. Sci."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"801","DOI":"10.1007\/s10924-012-0494-6","article-title":"Preparation and properties of green composites based on tapioca starch and differently recycled paper cellulose fibers","volume":"20","author":"Wattanakornsiri","year":"2012","journal-title":"J. Polym. Environ."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1002\/app.41827","article-title":"Effect of graphene loading on thermomechanical properties of poly(vinyl alcohol)\/starch blend","volume":"132","author":"Jose","year":"2015","journal-title":"J. Appl. Polym. Sci."},{"key":"ref_29","doi-asserted-by":"crossref","unstructured":"Kellermayer, M.S., Sun, Q., Xi, T., Li, Y., and Xiong, L. (2014). Characterization of corn starch films reinforced with caco3 nanoparticles. PLoS ONE, 9.","DOI":"10.1371\/journal.pone.0106727"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"455","DOI":"10.1016\/j.carbpol.2005.06.020","article-title":"Thermoplastic starch\u2013clay nanocomposites and their characteristics","volume":"61","author":"Chen","year":"2005","journal-title":"Carbohydr. Polym."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"18","DOI":"10.1016\/j.foodhyd.2014.04.021","article-title":"Food packaging bags based on thermoplastic corn starch reinforced with talc nanoparticles","volume":"43","author":"Castillo","year":"2015","journal-title":"Food Hydrocoll."},{"key":"ref_32","first-page":"48","article-title":"Controlled release of metformin hydrochloride through crosslinked blends of chitosan-starch","volume":"2","author":"Kumari","year":"2011","journal-title":"Adv. Appl. Sci. Res."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"319","DOI":"10.1016\/j.carbpol.2006.05.029","article-title":"Aspects of the preparation of starch microcellular foam particles crosslinked with glutaraldehyde using a solvent exchange technique","volume":"67","author":"Venditti","year":"2007","journal-title":"Carbohydr. Polym."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"189","DOI":"10.1016\/S0144-8617(00)00315-5","article-title":"A first insight on composites of thermoplastic starch and kaolin","volume":"45","author":"Carvalho","year":"2001","journal-title":"Carbohydr. Polym."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"534","DOI":"10.1038\/nnano.2011.145","article-title":"The scherrer equation versus the \u2018debye-scherrer equation\u2019","volume":"6","author":"Holzwarth","year":"2011","journal-title":"Nat. Nanotechnol."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"2052","DOI":"10.1039\/b915758a","article-title":"Non-catalyzed and pt\/\u03b3-Al2O3-catalyzed hydrothermal cellulose dissolution\u2013conversion: Influence of the reaction parameters and analysis of the unreacted cellulose","volume":"11","author":"Jollet","year":"2009","journal-title":"Green Chem."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"1126","DOI":"10.1107\/S0021889810030499","article-title":"Fityk: A general-purpose peak fitting program","volume":"43","author":"Wojdyr","year":"2010","journal-title":"J. Appl. Crystallogr."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"1600113","DOI":"10.1002\/star.201600113","article-title":"Effect of neem wood sawdust content on properties of biodegradable thermoplastic acetylated cassava starch\/neem wood sawdust composites","volume":"69","author":"Prachayawarakorn","year":"2017","journal-title":"Starch-St\u00e4rke"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"482810","DOI":"10.1155\/2012\/482810","article-title":"Films from glyoxal-crosslinked spruce galactoglucomannans plasticized with sorbitol","volume":"2012","author":"Mikkonen","year":"2012","journal-title":"Int. J. Polym. Sci."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"3869","DOI":"10.1002\/app.37685","article-title":"Preparation of chitosan-based adhesives and assessment of their mechanical properties","volume":"127","author":"Patel","year":"2013","journal-title":"J. Appl. Polym. Sci."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"393","DOI":"10.1016\/j.carbpol.2005.04.017","article-title":"Investigations of the effects of glyoxal cross-linking on the structure and properties of chitosan fiber","volume":"61","author":"Yang","year":"2005","journal-title":"Carbohydr. Polym."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"119","DOI":"10.1016\/S0141-8130(99)00068-9","article-title":"Some studies of crosslinking chitosan\u2013glutaraldehyde interaction in a homogeneous system","volume":"26","author":"Monteiro","year":"1999","journal-title":"Int. J. Biol. Macromol."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"126","DOI":"10.1016\/j.memsci.2007.06.015","article-title":"Crosslinking of chitosan membranes using glutaraldehyde: Effect on ion permeability and water absorption","volume":"301","author":"Beppu","year":"2007","journal-title":"J. Membr. Sci."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"48","DOI":"10.1002\/star.201200198","article-title":"Thermal degradation and stability of starch under different processing conditions","volume":"65","author":"Liu","year":"2013","journal-title":"Starch-St\u00e4rke"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"383","DOI":"10.1094\/CCHEM-86-4-0383","article-title":"Thermal decomposition of corn starch with different amylose\/amylopectin ratios in open and sealed systems","volume":"86","author":"Liu","year":"2009","journal-title":"Cereal Chem."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"267","DOI":"10.1016\/j.carbpol.2005.11.042","article-title":"Urea and ethanolamine as a mixed plasticizer for thermoplastic starch","volume":"64","author":"Ma","year":"2006","journal-title":"Carbohydr. Polym."},{"key":"ref_47","unstructured":"BeMiller, J., and Whistler, R. (2009). Chapter IX\u2014Gelatinization of Starch and Mechanical Properties of Starch Pastes. Starch: Chemistry and Technology, Academic Press. [3rd ed.]."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"954","DOI":"10.1080\/10942910903506202","article-title":"Modeling of retrogradation of waxy and normal corn starches","volume":"14","author":"Us","year":"2011","journal-title":"Int. J. Food Prop."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"277","DOI":"10.1016\/S0144-8617(98)00007-1","article-title":"Variation in crystalline type with amylose content in maize starch granules: An X-ray powder diffraction study","volume":"36","author":"Cheetham","year":"1998","journal-title":"Carbohydr. Polym."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"222","DOI":"10.1016\/j.matdes.2017.02.027","article-title":"A new biodegradable composite with open cell by combining modified starch and plant fibers","volume":"120","author":"Zhang","year":"2017","journal-title":"Mater. Des."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"11","DOI":"10.1016\/0926-6690(95)00048-8","article-title":"Crystallinity in starch bioplastics","volume":"5","author":"Hulleman","year":"1996","journal-title":"Ind. Crop Prod."},{"key":"ref_52","doi-asserted-by":"crossref","unstructured":"El-Sonbati, P.A. (2012). Thermoplastic starch. Thermoplastic Elastomers, InTech.","DOI":"10.5772\/2038"},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"61","DOI":"10.1002\/star.201200201","article-title":"Thermoplastic starches: Properties, challenges, and prospects","volume":"65","author":"Nafchi","year":"2013","journal-title":"Starch-Staerke"},{"key":"ref_54","unstructured":"Roylance, D. (1996). Mechanics of Materials, Wiley."},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"8163","DOI":"10.1007\/s10853-007-1699-2","article-title":"Characterization of starch based nanocomposites","volume":"42","author":"Kvien","year":"2007","journal-title":"J. Mater. Sci."},{"key":"ref_56","doi-asserted-by":"crossref","first-page":"647","DOI":"10.1080\/714975803","article-title":"Wood pulp reinforced thermoplastic starch composites","volume":"51","author":"Carvalho","year":"2002","journal-title":"Int. J. Polym. Mater. Polym. Biomater."},{"key":"ref_57","doi-asserted-by":"crossref","first-page":"2693","DOI":"10.1021\/ma971532b","article-title":"Improvement of starch film performances using cellulose microfibrils","volume":"31","author":"Dufresne","year":"1998","journal-title":"Macromolecules"}],"container-title":["Polymers"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-4360\/10\/9\/985\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T15:18:40Z","timestamp":1760195920000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-4360\/10\/9\/985"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2018,9,4]]},"references-count":57,"journal-issue":{"issue":"9","published-online":{"date-parts":[[2018,9]]}},"alternative-id":["polym10090985"],"URL":"https:\/\/doi.org\/10.3390\/polym10090985","relation":{},"ISSN":["2073-4360"],"issn-type":[{"value":"2073-4360","type":"electronic"}],"subject":[],"published":{"date-parts":[[2018,9,4]]}}}