PLA基生物复材丝材熔融沉积成型中增强相在层间界面的分布状态

周政; 谢明慧; 王延庆

doi:10.13801/j.cnki.fhclxb.20220414.003

PLA基生物复材丝材熔融沉积成型中增强相在层间界面的分布状态

doi: 10.13801/j.cnki.fhclxb.20220414.003

中国矿业大学　材料与物理学院，徐州 221116

基金项目: 中国矿业大学中央高校基本科研业务费专项资金(2020ZDPYMS36)

详细信息

通讯作者:
王延庆，博士，副教授，硕士生导师，研究方向为3D打印及树脂复合材料　E-mail:cumtwyq@163.com

中图分类号: TB332
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出版历程
- 收稿日期: 2022-02-11
- 修回日期: 2022-03-19
- 录用日期: 2022-04-05
- 网络出版日期: 2022-04-15
- 刊出日期: 2023-01-15

Distribution state of reinforcement phase at the interface between layers in the fused deposition modeling of PLA based biocomposite filaments

School of Materials and Physics, China University of Mining and Technology, Xuzhou 221116, China

Funds: Fundamental Research Funds for the Central Universities of China University of Mining and Technology (2020ZDPYMS36)

摘要

摘要: 通过熔融沉积成型3D打印的三维模型，不可避免存有层间界面，针对层间界面增强，本文采用超声浸渍法制备了纳米羟基磷灰石(n-HA)与微米短切碳纤维(CF)两相增强材料在聚乳酸(PLA)基体上牢固结合、均匀分布的PLA基生物复材丝材，该方法避免混炼的同时，也为层间界面储备了增强相。然而，经过熔融沉积成型3D打印之后，n-HA与微米短切CF两相增强材料在层间界面区域的分布状态尤为关键。运用Ansys进行流体数值计算，借助Minitab进行正交参数设计和信噪比数据分析，研究喷嘴直径、送丝速度、微米短切CF含量3个关键因素对于喷嘴出口流体速度的影响规律，并进一步通过熔融沉积成型3D打印机，在相同的打印参数设置下，制备标准拉伸试样，进行拉伸性能表征和SEM观察，研究PLA基生物复材丝材中，两相增强材料n-HA与微米短切CF在层间界面区域的分布状态。结果表明：借助Minitab信噪比优化实验参数，比正交试验参数设计手段更加有效；选取熔融温度为210℃、喷嘴直径为0.5 mm、送丝速度为14 mm·s⁻¹、微米短切CF含量为7wt%，上述参数组合进行数值计算获得的喷嘴出口流体速度方差最大，为两相增强材料n-HA与微米短切CF在层间界面区域最均匀分布创造了积极有利条件，且试样拉伸性能最强。
- 熔融沉积成型 /
- n-HA /
- 微米短切CF /
- PLA基生物复材丝材 /
- 信噪比
Abstract: The interlayer interface was unavoidable in 3D parts additive manufactured by fused deposition modeling. Aiming at the enhancement of the interlayer interface, the poly (lactic acid) (PLA) based biocomposite filaments were formerly prepared by the ultrasonic impregnating. In the PLA based biocomposite filament, nano-hydroxyapatite (n-HA) and micron chopped carbon fiber (CF) were firmly bonded and uniformly distributed on the surface of the PLA filament, and they were reserved as reinforcement phases for interlayer interface after being fused. However, after fused deposition modeling, the distribution state of above two reinforcement phases was particularly critical, and it was closely decided by the melting fluid velocity of the nozzle outlet. The influence of three key factors of nozzle diameter, filament feeding speed and micron chopped CF content on the melting fluid velocity of the nozzle outlet was studied, with Ansys being used for fluid numerical calculations, Minitab being applied for orthogonal parameter design and signal-to-noise ratio data analysis, standard tensile samples being 3D printed for tensile performance characterization and distribution state observation of above two reinforcement phases. The results show that the optimization of experimental parameters with Minitab signal-to-noise ratio is more effective than orthogonal experimental parameter design along. Since then, when the melting temperature is 210℃, the nozzle diameter is 0.5 mm, the filament feeding speed is 14 mm·s⁻¹, and the micron chopped CF content is 7wt%, the melting fluid velocity of the nozzle outlet numerically owns the largest variance, which means the most uniform distribution of the above two reinforcement phases in the interlayer interface, and the sample experimentally obtains the strongest tensile properties.
- fused deposition modeling /
- n-HA /
- micron chopped CF /
- PLA based biocomposite filament /
- signal-to-noise ratio

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图 1 纳米羟基磷灰石(n-HA)的改性处理过程

Figure 1. Nano-hydroxyapatite (n-HA) modification process

PLA—Poly(lactic acid); KH550—3-aminopropyltriethoxysilane

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图 2 微米短切碳纤维(CF)的改性处理过程

Figure 2. Micron chopped carbon fiber (CF) modification process

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图 3 聚乳酸(PLA)基生物复材丝材制备示意图

Figure 3. Schematic diagram of preparation of poly(lactic acid) (PLA) based biocomposite filament

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图 4 纯PLA丝材和PLA基生物复材丝材的SEM表面形貌图像

Figure 4. SEM surface morphology images of pure PLA filament and PLA based biocomposite filament

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图 5 PLA基生物复材丝材黏度随温度及剪切速率的变化曲线：(a) 丝材1 (5wt%n-HA、5wt%CF)；(b) 丝材2 (5wt%n-HA、6wt%CF)；(c) 丝材3 (5wt%n-HA、7wt%CF)；(d) 丝材样品颗粒

Figure 5. Curves of viscosity of each PLA based biocomposite filament with temperature and shear rate: (a) Filament 1 (5wt%n-HA, 5wt%CF); (b) Filament 2 (5wt%n-HA, 6wt%CF); (c) Filament 3 (5wt%n-HA, 7wt%CF); (d) Filament sample particles

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图 6 熔融沉积成型原理图和丝材在熔腔内状态转化示意图

Figure 6. Schematic diagram of fused deposition modeling and the state transformation of filament in the melting chamber

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图 7 计算模型(a)和模型网格(b)划分

Figure 7. Calculation model (a) and model meshing (b)

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图 8 用PLA基生物复材丝材制备的13组标准试样的拉伸实验

Figure 8. Tensile test of thirteen groups of standard samples prepared with PLA based biocomposite filament

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图 9 PLA基生物复材的SEM试样的制备过程

Figure 9. Preparation process of SEM samples of PLA based biocomposite

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图 10 190℃下各参数试样的喷嘴出口流体速度采样点导出曲线

Figure 10. Derive curves of sampling point of nozzle outlet fluid velocity of samples with various parameters at 190℃

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图 11 190℃下各参数条件的1~9号试样增强相层间界面分布状态SEM图像

Figure 11. SEM images of the distribution state of the interlayer interface of the reinforced phase of the samples No. 1-9 under the conditions of various parameters at 190℃

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图 12 190℃下各参数条件的1~9号试样及0号对比试样的应力-应变曲线(a)和屈服强度值(b)

Figure 12. Stress-strain curves (a) and yield strength value (b) of No. 1-9 samples and No. 0 comparative samples under various parameter conditions at 190℃

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图 13 各温度下喷嘴出口流体速度信噪比数据均值：(a) 190℃；(b) 200℃；(c) 210℃；(d) 220℃

Figure 13. Mean value of the signal-to-noise ratio data of the nozzle outlet fluid velocity at various temperatures: (a) 190°C; (b) 200°C; (c) 210°C; (d) 220°C

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图 14 O1~O4号试样的喷嘴出口流体速度采样点导出曲线

Figure 14. Derived curves of the sampling point of the nozzle outlet fluid velocity of the O1-O4 samples

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图 15 O1~O4号试样增强相层间界面分布状态SEM图像

Figure 15. SEM images of the distribution state of the interlayer interface of the O1-O4 samples

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图 16 O1~O4号试样的应力-应变曲线(a)和屈服强度值(b)

Figure 16. Stress-strain curves (a) and yield strength value (b) of O1-O4 samples

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表 1 PLA基生物复材丝材流体的非牛顿指数n、黏度系数K及黏流活化能E_η

Table 1. Non-Newtonian index n, viscosity coefficient K and viscous activation energy E_η of PLA based biocomposite filament fluid

Parameter	Special composite filament fluid	Temperature
Parameter	Special composite filament fluid	190℃	200℃	210℃	220℃
n	Filament 1	0.5851	0.8112	0.8301	0.7941
	Filament 2	0.8270	0.9738	0.7269	0.8014
	Filament 3	0.7311	0.9076	0.9410	0.8374

K	Filament 1	6177.7537	886.2242	518.6348	556.9971
	Filament 2	1141.5702	257.8248	1250.9768	529.5619
	Filament 3	2032.3946	394.0824	219.7433	348.3055

E_η/(kJ·mol⁻¹)	Filament 1	69458.0590
	Filament 2	73876.8404
	Filament 3	68175.0905

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表 2 喷嘴出口速度影响因素的正交参数方案

Table 2. Orthogonal parameter scheme for influencing factors of nozzle outlet velocity

Test number	Nozzle diameter/mm	Filament feding speed/(mm·s⁻¹)	Micron chopped CF content/wt%
1	0.4	2	5
2	0.4	8	6
3	0.4	14	7
4	0.5	2	6
5	0.5	8	7
6	0.5	14	5
7	0.6	2	7
8	0.6	8	5
9	0.6	14	6

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表 3 计算模型各部分材料的主要物理属性

Table 3. Calculate the main physical properties of the materials in each part of the model

Materials	Thermal conductivity/ (W·m⁻¹·℃⁻¹)	Thermal expansivity/ (10⁻⁵ K⁻¹)	Density/ (kg·m⁻³)	Specific heat capacity/ (kJ·kg⁻¹·℃⁻¹)	Size
PLA	0.23	0.20	1250	2.040	60 nm
n-HA	1.20	0.80	3160	0.840	60 nm
Micron chopped CF	500.00	0.00	1750	7.120	100 μm
Brass	387.60	2.00	8978	0.381	—
Aluminum alloy	202.40	2.32	2719	0.871	—

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表 4 190℃下的喷嘴出口流体速度均值、速度方差、Delta值汇总表

Table 4. Summary of the mean value, velocity variance, and Delta value of the nozzle outlet fluid velocity at 190℃

Test number	Factors			Mean value of fluid velocity at nozzle outlet/ (10⁻² m·s⁻¹)	Variance of fluid velocity at nozzle outlet/(10⁻³ m·s⁻¹)
Test number	Nozzle diameter/mm	Filament feeding speed/(mm·s⁻¹)	Micron chopped CF content/wt%	Mean value of fluid velocity at nozzle outlet/ (10⁻² m·s⁻¹)	Variance of fluid velocity at nozzle outlet/(10⁻³ m·s⁻¹)
1	0.4	2	5	5.89	0.413
2	0.4	8	6	23.81	6.139
3	0.4	14	7	41.11	16.565
4	0.5	2	6	5.81	0.479
5	0.5	8	7	22.83	6.616
6	0.5	14	5	38.82	15.979
7	0.6	2	7	2.84	0.086
8	0.6	8	5	10.82	1.041
9	0.6	14	6	19.23	3.554
Delta	4.33	7.70	0.49	—	—
Rank	2	1	3	—	—

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表 5 喷嘴出口流体速度信噪比数据均值优化结果表

Table 5. Optimization results of the mean value of the signal-to-noise ratio data of the fluid velocity at the nozzle outlet

Test number	Tempera- ture/℃	Factors
Test number	Tempera- ture/℃	Nozzle diameter/ mm	Filament feeding speed/ (mm·s⁻¹)	Micron chopped CF content/wt%
O1	190	0.5	14	6
O2	200	0.5	14	7
O3	210	0.5	14	7
O4	220	0.5	14	7

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表 6 O1~O4号试样喷嘴出口流体速度均值和方差表

Table 6. Mean value and variance of the fluid velocity at the nozzle exit of the O1-O4 samples

Velocity	Test number
Velocity	O1	O2	O3	O4
Mean value of fluid velocity at nozzle outlet/ (10⁻² m·s⁻¹)	41.63	42.57	42.82	41.81
Variance of fluid velocity at nozzle outlet/(10⁻³ m·s⁻¹)	22.086	24.836	25.222	23.171

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