本文選題：聚乳酸 + 3D打印��； 參考：《沈陽工業(yè)大學(xué)》2017年碩士論文

【摘要】：聚乳酸(PLA)作為熱塑性的生物可降解脂肪族聚酯材料,因其具有優(yōu)良的生物相容性、高透明性、高模量和高強(qiáng)度等特性,近年來受到人們的廣泛關(guān)注。而隨3D打印技術(shù)的發(fā)展,作為環(huán)境友好型材料的PLA在3D打印領(lǐng)域具有廣闊的應(yīng)用前景。然而,作為3D打印耗材要求材料具有良好的加工流動(dòng)性和韌性,這樣可以防止在打印過程中發(fā)生噴頭堵塞,同時(shí)避免在牽引力作用下發(fā)生斷絲現(xiàn)象。由于PLA韌性差、流動(dòng)性差和易燃等缺點(diǎn),限制了PLA在3D打印領(lǐng)域的廣泛應(yīng)用。本文首先系統(tǒng)性綜述了近年來PLA在阻燃、增韌和3D打印領(lǐng)域的研究情況。其次,采用聚乙二醇(PEG)、聚丁二酸丁二醇酯(PBS)、乙烯-醋酸乙烯共聚物(EVA)、聚磷酸銨(APP)和液晶聚合物(LCP)對PLA同時(shí)進(jìn)行阻燃和增韌改性,并通過極限氧指數(shù)測試、垂直燃燒測試、熱重分析、差示掃描量熱分析、力學(xué)性能測試、掃描電鏡分析和熔融指數(shù)分析等對PLA復(fù)合材料進(jìn)行性能表征。主要研究工作如下:(1)通過熔融共混的方法制備了PLA/PEG/APP/LCP阻燃增韌體系。極限氧指數(shù)和垂直燃燒測試表明添加15%的APP后復(fù)合材料的極限氧指數(shù)達(dá)到30.1%,達(dá)到難燃級(jí)別,通過UL-94 V-0標(biāo)準(zhǔn)。熱重分析發(fā)現(xiàn),LCP的添加降低了復(fù)合材料最大分解速率所對應(yīng)的溫度。力學(xué)性能測試發(fā)現(xiàn),PEG的添加使PLA的韌性得到明顯改善,添加15%PEG使復(fù)合材料的斷裂伸長率由4.1%提高到75.2%,隨LCP添加量的增加復(fù)合材料的斷裂伸長率逐漸降低,添加1.0%LCP時(shí),斷裂伸長率由57.1%降低到19.38%。對拉伸斷裂面進(jìn)行SEM測試發(fā)現(xiàn),PEG與PLA相容性較好,體現(xiàn)明顯的韌性斷裂,APP與PLA發(fā)生相分離現(xiàn)象。通過熔融指數(shù)分析發(fā)現(xiàn),LCP的添加可以明顯改善復(fù)合材料的加工流動(dòng)性,MFR由7.01g/10min提高到14.09g/10min。(2)通過熔融共混的方法制備了PLA/PBS/APP阻燃增韌體系。極限氧指數(shù)和垂直燃燒測試表明,APP添加量為20%時(shí)LOI達(dá)到31.5%,通過UL-94 V-0標(biāo)準(zhǔn)。熱重分析發(fā)現(xiàn),改性后復(fù)合材料初始分解溫度提高了10℃,殘?zhí)柯孰SAPP含量的增加由0.2%提高到16.8%。力學(xué)性能測試發(fā)現(xiàn),添加PBS后復(fù)合材料的沖擊強(qiáng)度和斷裂伸長率明顯提高,隨APP含量的增加復(fù)合材料的拉伸強(qiáng)度、沖擊強(qiáng)度和斷裂伸長率逐漸降低。對拉伸斷裂面進(jìn)行SEM測試發(fā)現(xiàn),PLA和PBS未完全相容,APP與PLA發(fā)生相分離現(xiàn)象。通過熔融指數(shù)分析發(fā)現(xiàn),隨APP含量的增加復(fù)合材料MFR先增大后減小,APP含量為15%時(shí)達(dá)最大值27.41g/10min。(3)通過熔融共混的方法制備了PLA/EVA/APP阻燃增韌體系。極限氧指數(shù)和垂直燃燒測試表明,當(dāng)APP添加量為20%時(shí)LOI達(dá)到28.3%,達(dá)到難燃材料級(jí)別,通過UL-94V-0標(biāo)準(zhǔn)。熱重分析發(fā)現(xiàn),改性后復(fù)合材料初始分解溫度提高了10℃左右,殘?zhí)柯孰SAPP含量的增加由1.34%提高到20.26%。力學(xué)性能測試發(fā)現(xiàn),添加EVA后復(fù)合材料的沖擊強(qiáng)度和斷裂伸長率明顯提高,隨APP含量的增加復(fù)合材料的拉伸強(qiáng)度、沖擊強(qiáng)度和斷裂伸長率逐漸降低。對拉伸斷裂面進(jìn)行SEM測試發(fā)現(xiàn),PLA和EVA相容性較差,APP與PLA發(fā)生相分離現(xiàn)象。熔融指數(shù)分析發(fā)現(xiàn),隨APP含量的增加復(fù)合材料MFR先增大后減小,APP含量為10%時(shí)達(dá)最大值22.51g/10min。
[Abstract]:Poly (lactic acid) (PLA), as a thermoplastic biodegradable aliphatic polyester material, has attracted wide attention in recent years because of its excellent biocompatibility, high transparency, high modulus and high strength. With the development of 3D printing technology, PLA as environmentally friendly material has a broad application prospect in the field of 3D printing. As the 3D printing consumables, the material has good processing fluidity and toughness, which prevents the nozzle blockage in the printing process and avoids the breaking of wire under the action of traction force. Because of the disadvantages of poor PLA toughness, poor fluidity and flammability, the wide application of PLA in the field of 3D printing is limited. The research situation of PLA in the field of flame retardancy, toughening and 3D printing in recent years is reviewed. Secondly, the flame retardancy and toughening modification of PLA with polyethylene glycol (PEG), polybutylene succinate (PBS), ethylene vinyl acetate copolymer (EVA), ammonium polyphosphate (APP) and liquid crystal polymer (LCP) are also carried out at the same time, and through the test of the limit oxygen index, the vertical combustion test and the heat. The properties of PLA composites were characterized by reanalysis, differential scanning calorimetry, mechanical properties test, scanning electron microscope analysis and melt index analysis. The main research work is as follows: (1) the PLA/PEG/APP/LCP flame retardant toughening system was prepared by melt blending. The limit oxygen index and vertical combustion test showed that the composite after adding 15% of APP The limit oxygen index of the material reaches 30.1%, reaching the refractory grade. Through the UL-94 V-0 standard, the thermogravimetric analysis shows that the addition of LCP reduces the temperature corresponding to the maximum decomposition rate of the composite. The mechanical properties test shows that the addition of PEG makes the toughness of PLA obviously improved, and the elongation at break of the composite material is increased from 4.1% to 7 by adding 15%PEG. 5.2%, with the addition of LCP, the elongation at break of the composite gradually decreased. When 1.0%LCP was added, the elongation at break decreased from 57.1% to 19.38%. to the tensile fracture surface, and SEM test found that the compatibility of PEG and PLA was better, it showed obvious ductile fracture, and APP was separated from PLA. The addition of LCP can be found by the melt index analysis. In order to improve the processing fluidity of the composite obviously, MFR was raised from 7.01g/10min to 14.09g/10min. (2) to prepare the PLA/PBS/APP flame-retardant toughening system by melt blending. The limit oxygen index and vertical combustion test showed that LOI reached 31.5% when the APP addition amount was 20%, through the UL-94 V-0 standard. The initial decomposition temperature increased by 10 degrees C, the residual carbon rate increased from 0.2% to the APP content from 0.2% to the mechanical properties test. After adding PBS, the impact strength and elongation at break increased obviously. With the increase of APP content, the tensile strength of the composite material, the impact strength and the elongation at break gradually decreased. The tensile fracture surface was measured by SEM. It is found that PLA and PBS are not completely compatible, APP and PLA are separated. Through the melting index analysis, it is found that the composite MFR first increases and then decreases with the increase of APP content, and the maximum value 27.41g/10min. (3) when the APP content is 15%. The PLA/EVA/ APP flame retardant toughening system is prepared by the melt blending method. The test shows that when the addition of APP is 20%, LOI reaches 28.3%, reaching the grade of refractory material. Through the UL-94V-0 standard, it is found that the initial decomposition temperature of the modified composite is raised about 10 degrees C, the residual carbon rate increases from 1.34% to the 20.26%. mechanical properties by the increase of APP content, and the impact strength and fracture of the composites after adding EVA are found. With the increase of APP content, the impact strength and elongation at break gradually decreased with the increase of the tensile strength of the composite. The SEM test of the tensile fracture surface showed that the compatibility of PLA and EVA was poor and the APP and PLA were separated. The melting index analysis found that with the increase of APP content, the composite MFR increased first and then decreased, APP content contained. When the amount is 10%, the maximum value is 22.51g/10min.

【學(xué)位授予單位】：沈陽工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TQ323.41

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