Effect of Chitosan on the Hot-Extrusion 3D Printing Formability of Oxidized Starch Gel

doi:10.12141/j.issn.1000-565X.230433

Abstract

Abstract:

Oxidized starch gel material has become a hot material in fields such as food and biomedicine because of its advantages of hydrophilicity, chargeability, easy reaction and assembly in recent year. However, when used as a hot-extrusion 3D printing (HE-3DP) gel material, it has defects such as poor printability and low gel strength. This study investigated the influence of different chitosan addition amount on the rheological properties, printing formability and gel strength of oxidized starch-chitosan gel materials by adding different amounts of chitosan and utilizing non-covalent and chemical cross-linking between chitosan and oxidized starch. The results show that the oxidized starch-chitosan pastes exhibit typical shear-thinning characteristics. As chitosan is added in varying concentrations (0.5%~2%), non-covalent interactions such as hydrogen bonding and electrostatic attraction lead to an increase in the viscosity of the system. The thixotropic property initially increases and then decreases, while the flow stress (τ_f) first decreases, and then increases; and the yield stress (τ_y) increases first and then decreases. Compared with oxidized starch gel, oxidized starch-chitosan gel has good printing formability. Especially when the amount of chitosan added is 1%, the composite gel has the best thixotropic property, the minimum flow stress (τ_f) and the largest yield stress (τ_y), so the printing formability and printing accuracy is the best. Additionally, due to the non-covalent interaction between chitosan and oxidized starch and the schiff base chemical cross-linking, the oxidized starch-chitosan gel forms a dense network structure to improve gel stability and gel strength significantly. These effects are more significant with a higher chitosan content. The results can provide a theoretical basis and technical support for the performance improvement of oxidized starch gel material and the design and application of oxidized starch-chitosan gel materials suitable for HE-3DP.

Key words: hot-extrusion 3D printing, oxidized starch gel, chitosan, printing formability, gel strength

CLC Number:

TS236.9

CHEN Ling, LÜ Jiayu, QIU Zhipeng. Effect of Chitosan on the Hot-Extrusion 3D Printing Formability of Oxidized Starch Gel[J]. Journal of South China University of Technology(Natural Science Edition), 2024, 52(3): 1-9.

Figures/Tables 15

Fig.1

Table 1

Fig.2

Table 2

Change of G' during alternate strains sweep experiments for oxidized starch and its composite gel material with CS"

样品	G $1'$ /Pa	G $2'$ /Pa	G $3'$ /Pa	G $4'$ /Pa	G $5'$ /Pa	DSR_3-1/%	DSR_5-3/%
3DH	75 947±153^a	1 203±43^a	18 472.0±101^a	885±1^a	13 718±113^a	24.32±0.08^a	74.26±0.06^c
3DH-0.5%CS	25 638±113^d	510±23^b	6 054.3± 82^c	339±2^c	4 699±53^d	23.61±0.04^a	77.62±0.03^b
3DH-1%CS	30 119±120^c	663±12^b	6 815.5± 75^c	436±2^b	5 465±41^c	22.63±0.03^a	80.19±0.03^a
3DH-2%CS	53 472±114^b	1 196±25^a	9 871.8± 86^b	779±3^a	7 063±56^b	18.46±0.04^b	71.55±0.04^d

Table 2

Fig.3

Table 3

Fig.4

Table 4

Fig.5

Fig.6

Fig.7

Fig.8

Table 5

Fig.9

Fig.10

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样品	n	K/（Pa·s）	R²
3DH	0.024±0.011^b	736.8±16.8^d	0.999
3DH-0.5%CS	0.009±0.013^c	1 305.1±12.0^c	0.999
3DH-1%CS	0.024±0.014^b	1 397.2±25.6^b	0.996
3DH-2%CS	0.063±0.016^a	1 434.7±17.3^a	0.998

样品	流动应力τ_f/Pa	屈服应力τ_y/Pa
OMS	—	56.195
OMS-0.5%CS	996.26	133.250
OMS-1%CS	996.26	133.250
OMS-2%CS	—	99.926

样品	打印线宽/mm	打印层数
3DH	0.83±0.007^a	20±1^c
3DH-0.5%CS	0.82±0.007^b	23±1^b
3DH-1%CS	0.81±0.004^c	26±1^a
3DH-2%CS	0.83±0.003^a	22±1^b

样品	破断力/g	破断距离/cm	凝胶强度/ （g·cm^-1）
3DH（W） ^2）	32.33± 1.34^e	0.18±0.01^b	179.61± 7.27^d
3DH-0.5%CS（W） ^2）	353.82± 6.36^d	0.18±0.01^b	1 965.66± 35.33^c
3DH-0.5%CS（S） ^3）	316.57± 4.35^d	0.18±0.01^b	1 758.72± 24.16^c
3DH-1%CS（W） ^2）	471.47± 7.87^c	0.14±0.03^c	3 367.64± 56.21^b
3DH-1%CS（S） ^3）	568.45± 8.32^c	0.19±0.01^a	2 991.84± 43.79^b
3DH-2%CS（W） ^2）	1 240.61±60.48^b	0.13±0.02^c	9 543.15±465.23^a
3DH-2%CS（S） ^3）	1 642.80±40.86^a	0.19±0.02^a	8 646.21±215.05^a

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