温敏型胶体对玉米淀粉3D打印固化性能的影响

张文海

doi:10.13386/j.issn1002-0306.2022060282

温敏型胶体对玉米淀粉3D打印固化性能的影响

doi: 10.13386/j.issn1002-0306.2022060282

张文海

农业农村部冷冻调理水产品加工重点实验室，福建厦门 361022

基金项目: 厦门市重大科技计划项目（3502Z20201032）。

详细信息

作者简介:
张文海（1987−），男，硕士，高级工程师，研究方向：食品科学，E-mail：814595559@qq.com

中图分类号: TS201.7
计量
- 文章访问数: 24
- HTML全文浏览量: 19
- PDF下载量: 0
- 被引次数: 0
出版历程
- 收稿日期: 2022-06-28
- 刊出日期: 2023-05-01

Effect of Temperature Sensitive Colloid on 3D Printing and Curing Properties of Corn Starch

ZHANG Wenhai

Key Laboratory of Refrigeration and Conditioning Aquatic Products Processing, Ministry of Agriculture and Rural Affairs, Xiamen 361022, China

摘要

摘要: 目的：利用温敏型胶体的相转变特性，辅助实现淀粉在打印过程中的成型固化，并揭示不同种类胶体-淀粉体系的固化性能变化规律。方法：将不同比例的温敏型胶体（低酰基结冷胶、明胶、κ-卡拉胶）与玉米淀粉进行复配并测定其流变性能，通过打印圆柱及空心球模型、测试产品力-位移曲线、温度扫描流变、全质构分析及微观结构观测评估体系可打印及固化性能。结果：结冷胶和卡拉胶在2%~4%添加量，明胶在0%~2%添加量时，体系具有适宜的流变性能及良好的可打印性能。添加4%结冷胶及4%卡拉胶的产品表现出显著的塑性，固化效果较好；添加明胶的打印产品无显著塑性，打印产品不固化。结冷胶-淀粉混合体系的固化温度在35~43 ℃之间；卡拉胶-淀粉混合体系的固化温度在30~40 ℃之间，随着胶体含量增加，固化温度上升，固化速度加快。而随着明胶含量增加，固化温度从25 ℃下降至20 ℃以下且固化速度减慢。4%低酰基结冷胶产品具有更致密的凝胶网络，硬度高于4% κ-卡拉胶产品。明胶对硬度、弹性都有削弱作用，但使粘附力大幅提高。结论：适宜含量的低酰基结冷胶和κ-卡拉胶能够实现淀粉的成型固化，且卡拉胶固化性能优于结冷胶，而明胶则无辅助固化能力。
- 温敏型胶体 /
- 玉米淀粉 /
- 3D打印 /
- 成型固化 /
- 可打印性
Abstract: Objective: To assist the molding and curing of starch in 3D printing, and to reveal the change law of curing properties of different hydrocolloid-starch systems based on the phase-change characteristics of temperature-sensitive hydrocolloids. Methods: Three hydrocolloids, low-acyl gellan gum, gelatin, and κ-carrageenan, respectively, were mixed with corn starch at different ratios for evaluating their rheological properties. The printability and curing performance were evaluated by printing cylinder and hollow sphere models, testing force-displacement curves, temperature sweep rheology, whole-texture analysis and microstructure observation. Results: When gellan gum and κ-carrageenan were added at 2%~4% and gelatin at 0%~2%, the system had suitable rheological properties and good printability. The products with 4% gellan gum and 4% κ-carrageenan showed remarkable plasticity and better curing effect. Whereas the products with gelatin was not significantly plastic and cured. The curing temperature of gellan gum-starch system and κ-carrageenan-starch system were between 35~43 ℃ and 30~40 ℃ respectively, meanwhile, the curing temperature and speed increased with the increase of hydrocolloids content. However, as the gelatin content increased, the curing temperature decreased from 25 °C to 20 °C and the curing speed slowed down as well. The products with 4% low-acyl gellan gum had a denser gel network, which was harder than that with 4% κ-carrageenan. Gelatin weakened the hardness and elasticity, but greatly increased the adhesion. Conclusion: Appropriate low-acyl gellan gum and κ-carrageenan contributed to the molding and curing of starch, and the curing performance of κ-carrageenan was better than that of gellan gum, while gelatin had no auxiliary curing ability.
- temperature-sensitive hydrocolloids /
- corn starch /
- 3D printing /
- molding and curing /
- printability

HTML全文

图 1 低酰基结冷胶（A）、κ-卡拉胶（B）和明胶（C）复配体系的粘度随剪切速率的变化

Figure 1. The viscosity of low acyl gellan gum (A), κ-carrageenan (B) and gelatin (C) varied with shear rate

下载: 全尺寸图片幻灯片

图 2 低酰基结冷胶（A）、κ-卡拉胶（B）和明胶（C）复配体系的储能模量（G′）随角频度的变化

Figure 2. The storage modulus (G') of low acyl gellan gum (A), κ-carrageenan (B) and gelatin (C) varied with angular frequency

下载: 全尺寸图片幻灯片

图 3 低酰基结冷胶（A）、κ-卡拉胶（B）和明胶（C）复配体系的损耗角正切（tan δ）随角频度的变化

Figure 3. The loss tangent (tan δ) of low acyl gellan gum (A), κ-carrageenan (B) and gelatin (C) varied with angular frequency

下载: 全尺寸图片幻灯片

图 4 不同浓度温敏型胶体与淀粉复配体系的3D打印圆柱产品

Figure 4. 3D printing of cylinder products with different concentrations of temperature sensitive colloid and starch

下载: 全尺寸图片幻灯片

图 5 不同温敏型胶体添加量复配体系3D打印圆柱产品的高度

注：不同字母代表有显著性差异（P<0.05）。

Figure 5. Height of 3D printing cylinder products with different temperature sensitive colloid addition system

下载: 全尺寸图片幻灯片

图 6 低酰基结冷胶、κ-卡拉胶（A）和明胶（B）复配体系3D打印圆柱模型的力-位移曲线

Figure 6. Force-displacement curve of 3D printed cylindrical model of low acyl gellan gum, κ-carrageenan (A) and gelatin (B) compound system

下载: 全尺寸图片幻灯片

图 7 不同低酰基结冷胶添加量复配体系（0%~4%）3D打印空心球整体图、剖面图及局部图

Figure 7. 3D printed hollow ball, section and local drawing of compound system with different low acyl gellan gum addition (0%~4%)

下载: 全尺寸图片幻灯片

图 8 不同κ-卡拉胶添加量复配体系（0%~4%）3D打印空心球整体图、剖面图及局部图

Figure 8. 3D printed hollow ball, section and local drawing of compound system with different κ-carrageenan addition (0%~4%)

下载: 全尺寸图片幻灯片

图 9 不同明胶添加量复配体系（0%~10%）3D打印空心球整体图、剖面图及局部图

Figure 9. 3D printing of hollow spheres, sections and local drawing with different gelatin addition (0%~10%)

下载: 全尺寸图片幻灯片

图 10 低酰基结冷胶（A）、κ-卡拉胶（B）和明胶（C）复配体系的储能模量（G′）随温度变化图

Figure 10. The storage modulus (G') of low acyl gellan gum (A), κ-carrageenan (B) and gelatin (C) varied with temperature

下载: 全尺寸图片幻灯片

图 11 不同温敏型胶体添加量复配体系的微观结构

Figure 11. Microstructure of composite system with different temperature sensitive colloid addition system

下载: 全尺寸图片幻灯片

表 1 3D打印模型打印参数

Table 1. The print parameter for 3D printing models

模型	尺寸（mm）	打印速度（mm/s）	每层厚度（mm）	填充密度（%）	外壳厚度（mm）
圆柱	高度，25 半径，15	40	1	80	1
空心圆柱	高度，25 外径，15 内径，10	40	1	0	6
空心球	高度，28 外径，15 内径，10	40	1	0	6

下载: 导出CSV

表 2 不同温敏型胶体添加量复配体系产品质构特性的变化

Table 2. Changes of texture characteristics of products with different amount of temperature sensitive colloid

胶添加量	硬度（g）	粘附力（g/s）	弹性	内聚性	回复性
0%	128.99±10.85^d	0.66±0.70^f	1.70±0.07^a	0.99±0.01^a	0.84±0.03^a
2%低酰基结冷胶	844.10±145.27^c	12.47±0.56^e	1.32±0.28^bc	0.90±0.04^ab	0.73±0.05^b
4%低酰基结冷胶	4588.72±969.17^a	0.44±0.26^f	0.92±0.04^d	0.85±0.04^b	0.61±0.05^c
2% κ-卡拉胶	981.43±224.75^c	3.98±2.84^ef	1.58±0.24^ab	0.97±0.01^a	0.79±0.03^ab
4% κ-卡拉胶	2058.69±418.73^b	0.16±0.06^f	1.44±0.43^ab	0.95±0.03^ab	0.78±0.05^ab
2%明胶	148.69±16.94^d	25.05±3.87^d	1.05±0.15^cd	0.96±0.02^ab	0.81±0.04^a
4%明胶	74.27±3.65^e	54.94±9.91^c	0.88±0.03^d	0.72±0.06^c	0.41±0.04^d
6%明胶	15.65±0.29^f	87.03±2.59^b	0.75±0.00^d	0.51±0.07^d	0.24±0.02^e
8%明胶	15.76±0.49^f	99.01±5.15^a	0.71±0.03^d	0.48±0.10^d	0.18±0.03^e
10%明胶	12.41±0.19^g	86.89±20.23^b	0.72±0.04^d	0.57±0.13^d	0.18±0.06^e
注：同列不同小写字母表示存在显著差异（P<0.05）。

下载: 导出CSV

参考文献(37)

[1]	赵子龙. 微波3D打印固化单元设计及打印鱼糜制品品质研究[D]. 无锡: 江南大学, 2021 ZHAO Z L. Design of microwave 3D printing curing unit and study on the quality of printed surimi products[D]. Wuxi: Jiangnan University, 2021.
[2]	DANKAR I, HADDARAH A, OMAR F E L, et al. 3D Printing technology: The new era for food customization and elaboration[J]. Trends in Food Science & Technology,2018,75:231−242.
[3]	CHEN Y Y, ZHANG M, SUN Y N, et al. Improving 3D/4D printing characteristics of natural food gels by novel additives: A review[J]. Food Hydrocolloids,2022,123:107160. doi: 10.1016/j.foodhyd.2021.107160
[4]	ZHAO Z L, WANG Q, YAN B W, et al. Synergistic effect of microwave 3D print and transglutaminase on the self-gelation of surimi during printing[J]. Innovative Food Science and Emerging Technologies,2021,67:102546. doi: 10.1016/j.ifset.2020.102546
[5]	MANTIHAL S, PRAKASH S, BHANDARI B. Textural modification of 3D printed dark chocolate by varying internal infill structure[J]. Food Research International,2019,121:648−657. doi: 10.1016/j.foodres.2018.12.034
[6]	HYUNJUNG K, YAXIN W, JIHO C, et al. Meat analog production through artificial muscle fiber insertion using coaxial nozzle-assisted three-dimensional food printing[J]. Food Hydrocolloids,2021,120:106898. doi: 10.1016/j.foodhyd.2021.106898
[7]	CHEN H, XIE F W, CHEN L, et al. Effect of rheological properties of potato, rice and corn starches on their hot-extrusion 3D printing behaviors[J]. Journal of Food Engineering,2019,244:150−158. doi: 10.1016/j.jfoodeng.2018.09.011
[8]	ZHENG L Y, LIU J B, LIU R, et al. 3D Printing performance of gels from wheat starch, flour and whole meal[J]. Food Chemistry,2021,365:15.
[9]	CUI Y, LI C Y, GUO Y, et al. Rheological & 3D printing properties of potato starch composite gels[J]. Journal of Food Engineering,2022,313:110756. doi: 10.1016/j.jfoodeng.2021.110756
[10]	ZENG X X, CHEN H, CHEN L, et al. Insights into the relationship between structure and rheological properties of starch gels in hot-extrusion 3D printing[J]. Food Chemistry,2021,342:128362. doi: 10.1016/j.foodchem.2020.128362
[11]	ZHU S C, WANG W W, STIEGER M, et al. Shear-induced structuring of phase-separated sodium caseinate-sodium alginate blends using extrusion-based 3D printing: Creation of anisotropic aligned micron-size fibrous structures and macroscale filament bundles[J]. Innovative Food Science & Emerging Technologies,2022,81:103146.
[12]	YAN B W, ZHAO Z L, ZHANG N N, et al. 3D Food printing curing technology based on gellan gum[J]. Journal of Food Engineering,2022,327:111036. doi: 10.1016/j.jfoodeng.2022.111036
[13]	LIU Z P, CHEN H, ZHENG B, et al. Understanding the structure and rheological properties of potato starch induced by hot-extrusion 3D printing[J]. Food Hydrocolloids,2020,105:8.
[14]	SHIN S, KWAK H, SHIN D, et al. Solid matrix-assisted printing for three-dimensional structuring of a viscoelastic medium surface[J]. Nature Communications,2019,10:12. doi: 10.1038/s41467-018-07943-y
[15]	MIN H, KENNEDY J F, LI B, et al. Characters of rice starch gel modified by gellan, carrageenan, and glucomannan: A texture profile analysis study[J]. Carbohydrate Polymers,2007,69(3):411−418. doi: 10.1016/j.carbpol.2006.12.025
[16]	KIM N P, EO J S, CHO D. Optimization of piston type extrusion (pte) techniques for 3D printed food[J]. Journal of Food Engineering,2018,235:41−49. doi: 10.1016/j.jfoodeng.2018.04.019
[17]	彭凯, 吴薇, 龙蕾, 等. 非淀粉成分对淀粉糊化特性的影响[J]. 粮食与饲料工业,2015(5):41−44. [PENG K, WU W, LONG L, et al. Effect of non starch components on pasting properties of starch[J]. Cereal & Feed Industry,2015(5):41−44. doi: 10.7633/j.issn.1003-6202.2015.05.011
[18]	XU L L, GU L P, SU Y J, et al. Impact of thermal treatment on the rheological, microstructural, protein structures and extrusion 3D printing characteristics of egg yolk[J]. Food Hydrocolloids,2020,100:105399. doi: 10.1016/j.foodhyd.2019.105399
[19]	SCHWARTZ J J, BOYDSTON A J. Multimaterial actinic spatial control 3D and 4D printing[J]. Nature Communications,2019,10:10. doi: 10.1038/s41467-018-07709-6
[20]	LAI J C, LI L, WANG D P, et al. A rigid and healable polymer cross-linked by weak but abundant Zn (II)-carboxylate interactions[J]. Nature Communications,2018,9:9. doi: 10.1038/s41467-017-01881-x
[21]	VISSER J, MELCHELS F P W, JEON J E, et al. Reinforcement of hydrogels using three-dimensionally printed microfibres[J]. Nature Communications,2015,6:10.
[22]	THOMPSON Y, GONZALEZ-GUTIERREZ J, KUKLA C, et al. Fused filament fabrication, debinding and sintering as a low cost additive manufacturing method of 316l stainless steel[J]. Additive Manufacturing,2019,30:8.
[23]	WEN K J, LI Y, HUANG W, et al. Mechanical behaviors of hydrogel-impregnated sand[J]. Construction and Building Materials,2019,207:174−180. doi: 10.1016/j.conbuildmat.2019.02.141
[24]	ZALDIVAR R J, MCLOUTH T D, FERRELLI G L, et al. Effect of initial filament moisture content on the microstructure and mechanical performance of ultem (r) 9085 3D printed parts[J]. Additive Manufacturing,2018,24:457−466. doi: 10.1016/j.addma.2018.10.022
[25]	ZHANG J X, MIAO Y G, QIN Q H, et al. Static and dynamic experiments on hydrogels: Effects of the chemical composition of the fluid[J]. Mechanics of Materials,2021,154:8.
[26]	PATTARAPON P, MIN Z AND, SAKAMON D. Investigation on 3D printing ability of soybean protein isolate gels and correlations with their rheological and textural properties via LF-NMR spectroscopic characteristics[J]. LWT-Food Science and Technology,2020,122:109019. doi: 10.1016/j.lwt.2020.109019
[27]	CHEN J W, MU T H, GOFFIN D, et al. Application of soy protein isolate and hydrocolloids based mixtures as promising food material in 3D food printing[J]. Journal of Food Engineering,2019,261:76−86. doi: 10.1016/j.jfoodeng.2019.03.016
[28]	KANG D H, LOUIS F, LIU H, et al. Engineered whole cut meat-like tissue by the assembly of cell fibers using tendon-gel integrated bioprinting[J]. Nature Communications,2021,12(1):12. doi: 10.1038/s41467-020-20168-2
[29]	WU L F, LIU Z C, GUAN Y P, et al. Visual presentation for monitoring layer-wise curing quality in dlp 3D printing[J]. Rapid Prototyping Journal,2021,27(10):1776−1790. doi: 10.1108/RPJ-03-2020-0056
[30]	BABAEI J, KHODAIYAN F, MOHAMMADIAN M. Effects of enriching with gellan gum on the structural, functional, and degradation properties of egg white heat-induced hydrogels[J]. International Journal of Biological Macromolecules,2019,128:94−100. doi: 10.1016/j.ijbiomac.2019.01.116
[31]	MIYOSHI E, TAKAYA T, NISHINARI K. Rheological and thermal studies of gel-sol transition in gellan gum aqueous solutions[J]. Carbohydrate Polymers,1996,30(2-3):109−119. doi: 10.1016/S0144-8617(96)00093-8
[32]	XU X J, FANG S, LI Y H, et al. Effects of low acyl and high acyl gellan gum on the thermal stability of purple sweet potato anthocyanins in the presence of ascorbic acid[J]. Food Hydrocolloids,2019,86:116−123. doi: 10.1016/j.foodhyd.2018.03.007
[33]	SHINSHO A, BRENNER T, DESCALLAR F B, et al. The thickening properties of native gellan gum are due to freeze drying-induced aggregation[J]. Food Hydrocolloids,2020,109:4.
[34]	JIMENEZ A, FABRA M J, TALENS P, et al. Effect of sodium caseinate on properties and ageing behaviour of corn starch based films[J]. Food Hydrocolloids,2012,29(2):265−271. doi: 10.1016/j.foodhyd.2012.03.014
[35]	WANG K, WANG W H, YE R, et al. Mechanical properties and solubility in water of corn starch-collagen composite films: Effect of starch type and concentrations[J]. Food Chemistry,2017,216:209−216. doi: 10.1016/j.foodchem.2016.08.048
[36]	THUAN-CHEW T, WAN-TECK F, MIN-TZE L, et al. Comparative assessment of textural properties and microstructure of composite gels prepared from gelatine or gellan with maize starch and/or egg white[J]. International Journal of Food Science & Technology,2015,50(3):592−604.
[37]	MAHMOOD K, KAMILAH H, SHANG P L, et al. A review: Interaction of starch/non-starch hydrocolloid blending and the recent food applications[J]. Food Bioscience,2017,19:110−120. doi: 10.1016/j.fbio.2017.05.006