Effect of glass fibers and coupling agents on the degradation properties of polylactic acid
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摘要: 聚乳酸因其优异的性能广泛应用在骨折内固定领域，但其存在降解速度过快导致的弯曲和剪切性能下降问题，因此复合改性是提高其性能的途经之一。本文采用三维编织技术制备了玻璃纤维(GF)和聚乳酸(PLA)混编预制体，并采用偶联剂KH550对预制体进行改性处理。采取热压成型工艺制备复合材料。在37℃条件下将复合材料浸泡在磷酸盐缓冲溶液(PBS)中进行体外降解实验。结果显示：GF质量分数增加会降低复合材料的质量损失率及吸水率。降解28天后，GF质量分数为40wt%的结晶度较GF质量分数为30wt%的试样增加了12.3%，GF质量分数为30wt%、35wt%和40wt%时，弯曲强度分别下降了32.3%、28.13%和16.16%，剪切强度分别下降了53.74%、51.1%和47.18%。说明提高GF质量分数有助于维持复合材料的力学性能，缓解因降解引起的界面损伤。KH550的引入使降解介质(PBS缓冲液) pH值下降幅度小。降解28天后，改性复合材料弯曲强度下降了22.85%，剪切强度下降了56.11%。结合SEM图像，发现降解第7天时GF质量分数为30wt%的试样出现细小沟壑，第28天时表面损伤明显。而GF质量分数为40wt%的试样降解损伤较小。可见，GF对PLA复合材料的力学性能和结晶度起到促进作用，同时抑制了PLA的降解。KH550改善了GF和PLA的界面，对降解介质pH值变化影响较小。Abstract: Polylactic acid (PLA) is widely used in the field of fracture internal fixation because of its excellent performance, but it has the problem of degradation of flexural and shear properties due to rapid degradation rate, so compound modification is one of the ways to improve its performance. In this study, glass fiber (GF) and PLA blended preforms were prepared by the three-dimensional braiding technique, followed by modification of the preforms using coupling agent KH550. The composite materials were prepared using a hot-press molding technique. The composite materials were subjected to in vitro degradation experiments by immersing them in phosphate buffered saline (PBS) solution at 37℃. The results reveal that an increase in GF content leads to a decrease in the quality loss rate and water absorption of the composite. After 28 days of degradation, the crystallinity of samples with 40wt%GF content increases by 12.3% compared to samples with 30wt%GF content. Additionally, the flexural strength decreases by 32.3%, 28.13%, and 16.16% for samples with GF contents of 30wt%, 35wt%, and 40wt%. Similarly, the shear strength decrease by 53.74%, 51.1%, and 47.18% for samples with GF contents of 30wt%, 35wt%, and 40wt%, respectively. This finding indicates that increasing the GF content helps to preserve the mechanical properties of the composite material and alleviate interface damage caused by degradation. The introduction of KH550 resulted in a minimal decrease in the pH value of the degradation medium (PBS buffer solution). After 28 days of degradation, the modified composite material exhibits a decrease in flexural strength of 22.85% and a decrease in shear strength of 56.11%. While combined with SEM images, it is observed that the sample with 30wt%GF content exhibits small fissures on the surface after 7 days of degradation, while significant surface damage is observed after 28 days. In contrast, the sample with 40wt%GF content exhibits less degradation damage, which corroborates the testing results of flexural strength and shear strength. It can be observed that GF promoted the mechanical properties and crystallinity of PLA composites while inhibiting the degradation of PLA. KH550 improved the interface between GF and PLA and had less effect on the pH change of the degradation medium.
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Key words:
- polylactic acid /
- glass fiber /
- coupling agent /
- three-dimensional braiding /
- degradability
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图 1 (a) 聚乳酸(PLA)纤维DSC曲线；(b) 玻璃纤维(GF)/PLA复合材料热压成型工艺曲线
Figure 1. (a) DSC curve of polylactic acid (PLA) fiber; (b) Hot press molding process curves of glass fiber (GF)/PLA composite
图 2 GF/PLA复合材料降解过程中质量损失率(a)及吸水率(b)
5 mod sample is the modified sample of KH550 with 40wt%GF
Figure 2. Quality retention rate (a) and water absorption rate (b) during the degradation of GF/PLA composite materials
图 3 GF/PLA复合材料降解过程中pH值变化
Figure 3. pH value change during degradation of GF/PLA composite materials
图 4 GF/PLA复合材料降解过程中结晶度变化
Figure 4. Changes in crystallinity during the degradation of GF/PLA composite materials
图 5 GF/PLA复合材料降解过程中弯曲强度变化
Figure 5. Flexural strength change during degradation of GF/PLA composite materials
图 6 GF/PLA复合材料降解过程中剪切强度变化
Figure 6. Shear strength change during degradation of GF/PLA composite materials
图 7 GF/PLA复合材料的SEM图像：(a) 40wt%GF；(b) 5 mod
Figure 7. SEM images of GF/PLA composite materials: (a) 40wt%GF; (b) 5 mod
图 8 GF/PLA复合材料降解第7天的SEM图像：(a) 30wt%GF；(b) 35wt%GF；(c) 40wt%GF；(d) 5 mod
Figure 8. SEM images of GF/PLA composite degradation at 7 days: (a) 30wt%GF; (b) 35wt%GF; (c) 40wt%GF; (d) 5 mod
图 9 GF/PLA复合材料降解第14天的SEM图像：(a) 30wt%GF；(b) 35wt%GF；(c) 40wt%GF；(d) 5 mod
Figure 9. SEM images of GF/PLA composite degradation at 14 days: (a) 30wt%GF; (b) 35wt%GF; (c) 40wt%GF; (d) 5 mod
图 10 GF/PLA复合材料降解第21天的SEM图像：(a) 30wt%GF；(b) 35wt%GF；(c) 40wt%GF；(d) 5 mod
Figure 10. SEM images of GF/PLA composite degradation at 21 days: (a) 30wt%GF; (b) 35wt%GF; (c) 40wt%GF; (d) 5 mod
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