材料挤出三维打印单材料载体配方肥的制备与控释效果

doi:10.3785/j.issn.1008-9209.2022.04.181

浙江大学学报（农业与生命科学版）

2023, Vol. 49

Issue (3): 398-412 DOI: 10.3785/j.issn.1008-9209.2022.04.181

资源利用与环境保护

材料挤出三维打印单材料载体配方肥的制备与控释效果

张鑫¹(

),伍倩²,马庆旭¹,尹俊²,何寅峰³(

),吴良欢¹(

)

^1.浙江大学环境与资源学院，污染环境修复与生态健康教育部重点实验室，浙江杭州 310058
^2.浙江大学机械工程学院，浙江杭州 310027
^3.诺丁汉大学卓越灯塔计划（宁波）创新研究院，浙江宁波 315000

Preparation of single-material carrier formulation fertilizer made by material extrusion three-dimensional printing and its controlled release effect

Xin ZHANG¹(

),Qian WU²,Qingxu MA¹,Jun YIN²,Yinfeng HE³(

),Lianghuan WU¹(

)

^1.Key Laboratory of Environment Remediation and Ecological Health, Ministry of Education, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058, Zhejiang, China
^2.School of Mechanical Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
^3.Nottingham Ningbo China Beacons of Excellence Research and Innovation Institute, Ningbo 315000, Zhejiang, China

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摘要：

三维打印（three-dimensional printing, 3D打印）作为一项可以快速小批量生产定制产品的加工技术，在园艺园林方向的应用潜力巨大。本研究借鉴3D打印缓释配方相关研究，完成单材料载体配方肥各组分的初步筛选，利用材料挤出3D打印技术成功打印出以海藻酸钠或黄原胶为黏结剂、甘露醇为填充剂、固定配比的乙醇溶液为溶剂、海泡石为增稠剂、尿素为核心肥料的单材料载体配方肥，确定尿素在海藻酸钠作为黏结剂时的最高添加比例为1∶4（尿素与溶剂质量体积比），而在黄原胶作为黏结剂时的最高添加比例为3∶4（尿素与溶剂质量体积比）；明确了用氯化钾、磷酸二氢钾、硫酸锌在最佳配方下替换尿素也可以实现打印；还通过多材料挤出3D打印技术进一步探讨了不同养分组合和元素耦合的打印可能性。通过打印参数调节试验明确了配方肥的最佳打印条件：打印速度200 mm/min、挤出速度0.02 mm/s、挤出高度1 mm、喷嘴直径1 mm。通过砂柱淋洗法进一步研究了不同配方肥的控释周期，发现不同配方及打印后处理下的单材料载体配方肥控释周期存在明显差异，经海泡石改良后的配方可以明显改变单材料载体配方肥的养分释放速率，其控释周期最长可达30 d。

关键词： 材料挤出三维打印; 新型肥料; 园艺园林; 控释效果

Abstract:

As a processing technology that can rapidly fabricate customized products in small batches, three-dimensional (3D) printing has great application potential in horticultural gardens. On the basis of existing studies on controlled releasing materials for 3D printing, the carrier materials for solo nutrition were developed after a range of formulation screening. The new formulations were suitable for material extrusion 3D printing and the single-material carrier formulation fertilizer contained sodium alginate or xanthan gum as a binder, mannitol as a filler, ethanol/water with fixed ratio as a solvent, sepiolite as a thickening agent, and urea as the core fertilizer. It was confirmed that the maximum adding ratio of urea could reach 1∶4 [m (urea)∶V (solvent)] when using sodium alginate as a binder, while the maximum adding ratio could reach 3∶4 [m (urea)∶V (solvent)] when using xanthan gum as a binder. It was confirmed that the developed formulation could also be used as the carrier of other types of nutrients including KCl, K₂HPO₄, and ZnSO₄. This work also demonstrated that it was possible to combine different nutrients and achieve element couplings by using multi-material extrusion 3D printing technology. Through the printing parameter adjustment experiment, the optimal printing was achieved when the printing speed was 200 mm/min, and the extrusion speed was 0.02 mm/s, and the extrusion height was 1 mm, and the nozzle diameter was 1 mm. The controlled release period of different formulations were further studied by the sand column leaching method. There were significant differences between the controlled release period of single-material carrier formulation fertilizers under different formulations and their post-treatments. The modified formulation with sepiolite can obviously change the release rate of single-material carrier formula fertilizer and the longest controlled release period reached 30 d.

Key words: material extrusion three-dimensional (3D) printing new fertilizer horticultural garden controlled release effect

收稿日期: 2022-04-18 出版日期: 2023-06-25

CLC:

S143

基金资助: 国家自然科学基金项目(31801936)

通讯作者: 何寅峰,吴良欢 E-mail: zhangxin1996@zju.edu.cn;Yinfeng.he@nottingham.ac.uk;finm@zju.edu.cn

作者简介: 张鑫（https://orcid.org/0000-0003-2436-395X），E-mail：zhangxin1996@zju.edu.cn

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引用本文:

张鑫,伍倩,马庆旭,尹俊,何寅峰,吴良欢. 材料挤出三维打印单材料载体配方肥的制备与控释效果[J]. 浙江大学学报（农业与生命科学版）, 2023, 49(3): 398-412.

Xin ZHANG,Qian WU,Qingxu MA,Jun YIN,Yinfeng HE,Lianghuan WU. Preparation of single-material carrier formulation fertilizer made by material extrusion three-dimensional printing and its controlled release effect. Journal of Zhejiang University (Agriculture and Life Sciences), 2023, 49(3): 398-412.

链接本文:

https://www.zjujournals.com/agr/CN/10.3785/j.issn.1008-9209.2022.04.181 或 https://www.zjujournals.com/agr/CN/Y2023/V49/I3/398

表1 配方表

图1 试验仪器及打印一维、三维结构设计图A.试验3D打印机；B.“几”字结构；C.不同孔隙度第一层打印设计图。

图2 配方F1～F16倒置前后对比图A. 配方F1～F8正置图（红框标记处代表固液分离）；B. 配方F9～F16正置图（红框标记处代表固液分离）；C. 配方F1～F8倒置图（红框标记处代表固液分离）；D. 配方F9～F16倒置图（红框标记处代表坍塌部分）。

图3 不同配方的黏度和剪切应力随剪切速率的稳态力学变化情况n=3。

图4 不同配方随角频率变化的动态损耗因子（A）及不同配方的平均动态损耗因子（B）n=3。

表2 打印参数调节

图5 配方F6和F14在不同打印速度及挤出速度下的条带表现

图6 不同打印参数下的条带宽度及填充率A～B. 配方F6和F14在不同打印参数下的条带宽度；C～D. 不同打印参数下的填充率。打印参数a～c、e～h对应的值见表2。

图7 可打印配方在不同打印参数下的成型结构建模

图8 喷嘴打印速度与打印时间之间的关系

图9 不同配方打印的“浙大校徽”展示图

图 10 配方F14打印展示图（A）以及配方F6、F14改良前后氮素累计释放率（B）

图11 不同孔隙度的配方F14氮素累计释放率P0代表孔隙度为0，P50代表孔隙度为50%，P67代表孔隙度为67%。

图12 多材料3D打印设计A. 复合结构展示图；B～C. 不同配方组合打印的复合结构展示图；D. 核壳结构展示图；E. 不同配方打印的核壳结构展示图。F17：F6+海泡石；F18：配方F14中的尿素替换成氯化钾。

图 13 配方F6、F14改良前后的SEM图

表3 不同配方的抗压强度和含水率

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