3D打印用PA6/PA12复合粉末的制备与性能
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摘要
采用溶剂沉淀法制备了用于3D打印的尼龙(PA)6/PA12复合粉末,使用扫描电子显微镜和X射线衍射对复合粉末微观形貌与结构进行分析,使用差示扫描量热测试了复合粉末的熔融和结晶温度,同时测试了不同PA12含量下复合粉末的表观密度、粒径分布、熔体流动速率(MFR)和注射成型件的力学性能。结果表明,复合粉末颗粒近球形,其结晶度明显低于纯PA6粉末的结晶度,当PA12的质量分数增加至20%时,复合粉末的结晶度由纯PA6的66.48%降至42.66%;随着PA12含量的增加,复合粉末的表观密度减小,粒径大于150μm的粉末含量增加,当PA12质量分数为20%时,复合粉末的表观密度仍大于0.35g/cm~3,粒径在75～100μm的粉末含量虽有所减少,但仍在70%以上,且加入成核剂可明显减少大粒径粉末的含量;MFR及注射成型件的韧性随PA12含量增加而提高,但成型件强度和模量下降;PA12使复合粉末的烧结温度有明显的降低,烧结温度窗口增大,有利于选择性激光烧结。
The composite powder of polyamide(PA) 6 and PA12 used for 3D printing was prepared by solvent deposition method. The morphology and structure of the composite powder were analyzed by SEM and XRD,the melting and crystallization temperature of the composite powder were measured by DSC,the apparent density,particle size distribution,melt ?ow rate(MFR)of the composite powder and mechanical properties of injection parts molded with the powder under different PA12 content were tested. The results show that,the powder particles were nearly spherical,and the crystallinity of composite powder was lower than that of pure PA6 powder. When the mass fraction of PA12 increases to 20%,the crystallinity of composite powder decreases from66.48% to 42.66%. With the increase of PA12 content,the apparent density of the composite powder decreases,the proportion of powder with particle size larger than 150 μm increases,when the mass fraction of PA12 is 20%,the apparent density is still higher than 0.35 g/cm~3,although the proportion of powder with particle size 75–100 μm reduces,it is still above 70%,and adding nucleating agent can reduce the proportion of powder with larger particle size obviously. The MFR of the powder and the toughness of the molding parts increase signi?cantly with the increase of PA12 content,but the strength and modulus decrease. The sintering temperature of the composite powder decreases obviously and the sintering temperature window range increases with the addition of PA12,which is conducive to selective laser sintering.
The composite powder of polyamide(PA) 6 and PA12 used for 3D printing was prepared by solvent deposition method. The morphology and structure of the composite powder were analyzed by SEM and XRD,the melting and crystallization temperature of the composite powder were measured by DSC,the apparent density,particle size distribution,melt ?ow rate(MFR)of the composite powder and mechanical properties of injection parts molded with the powder under different PA12 content were tested. The results show that,the powder particles were nearly spherical,and the crystallinity of composite powder was lower than that of pure PA6 powder. When the mass fraction of PA12 increases to 20%,the crystallinity of composite powder decreases from66.48% to 42.66%. With the increase of PA12 content,the apparent density of the composite powder decreases,the proportion of powder with particle size larger than 150 μm increases,when the mass fraction of PA12 is 20%,the apparent density is still higher than 0.35 g/cm~3,although the proportion of powder with particle size 75–100 μm reduces,it is still above 70%,and adding nucleating agent can reduce the proportion of powder with larger particle size obviously. The MFR of the powder and the toughness of the molding parts increase signi?cantly with the increase of PA12 content,but the strength and modulus decrease. The sintering temperature of the composite powder decreases obviously and the sintering temperature window range increases with the addition of PA12,which is conducive to selective laser sintering.
引文
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[2]Kumar S.Selective laser sintering:A qualitative and objective approach[J].The Journal of The Minerals,2003,55(10):43-47.
[3]王延庆,沈竞兴,吴海全.3D打印材料应用和研究现状[J].航空材料学报,2016,36(4):89-98.Wang Yanqing,Shen Jingxing,Wu Haiquan.Application and research status of alternative materials for 3D-printing technology[J].Journal of Aeronautical Materials,2016,36(4):89-98.
[4]Shi Y,Wang Y,Chen J,et al.Experimental investigation into the selective laser sintering of high-impact polystyrene[J].Journal of Applied Polymer Science,2008,108(1):535-540.
[5]Franco A,Lanzetta M,Romoli L.Experimental analysis of selective laser sintering of polyamide powders:an energy perspective[J].Journal of Cleaner Production,2010,18(16):1 722-1 730.
[6]Zhao M,Wudy K,Drummer D.Crystallization Kinetics of Polyamide 12 during selective laser sintering[J/OL].Polymers,2018,10(2):[2018-12-09].https://doi.org/10.3390/polym10020168.
[7]Zarringhalam H,Hopkinson N,Kamperman N F,et al.Effects of processing on microstructure and properties of SLS nylon 12[J].Materials Science&Engineering A,2006,435(4):172-180.
[8]Neugebauer F,Ploshikhin V,Ambrosy J,et al.Isothermal and nonisothermal crystallization kinetics of polyamide 12 used in laser sintering[J].Journal of Thermal Analysis&Calorimetry,2016,124(2):925-933.
[9]郑立.选择性激光烧结尼龙12复合粉末的制备及中试化[D].武汉:武汉工程大学,2016.Zheng Li.Synthesis of nylon 12 composite powder for selective laser sintering and pilot scale production[D].Wuhan:Wuhan Institute of Technology,2016.
[10]彭梦飞,汪艳.尼龙12/OMMT纳米复合粉末的制备及性能[J].工程塑料应用,2017,45(3):50-53.Peng Mengfei,Wang Yan.Preparation and performance of PA12/OMMT nanocomposites[J].Engineering Plastics Application,2017,45(3):50-53.
[11]袁绍彦,刘奇祥,叶南飙,等.耐高温聚酰胺的性能及应用[J].中国塑料,2009,23(10):6-9.Yuan Shaoyan,Liu Qixiang,Ye Nanbiao,et al.Properties and application of high-temperature resistant polyamides[J].China Plastics,2009,23(10):6-9.
[12]汤教佳,葸舒婷,张佩瑶,等.深冷粉碎制备尼龙粉末流动性的改善及选择性激光烧结性能[J].塑料工业,2018,46(7):26-31.Tang Jiaojia,Xi Shuting,Zhang Peiyao,et al.Improvement of fluidity and selective laser sintering of nylon powder prepared by cryogenic crushing[J].China Plastics Industry,2018,46(7):26-31.
[13]杨旭生,汪艳,陈亚武.选择性激光烧结用尼龙6粉末的性能研究[J].塑料工业,2018,46(3):135-138.Yang Xusheng,Wang Yan,Chen Yawu.Study on properties of nylon 6 powder for selective laser sintering[J].China Plastics Industry,2018,46(3):135-138.
[14]陈震,汪艳.抗氧剂对选择性激光烧结PA6粉末热氧稳定性影响[J].工程塑料应用,2018,46(6):126-130.Chen Zhen,Wang Yan.Effect of antioxidants on thermal oxygen stability of pa6 powder for selective laser sintering[J].Engineering Plastics Application,2018,46(6):126-130.
[15]Drummer D,Drexler M,Wudy K.Impact of heating rate during exposure of laser molten parts on the processing window of PA12powder[J].Physics Procedia,2014,56:184-192.
[16]蔡琤,易国斌,陈旭东.尼龙老化机理研究进展[J].合成材料老化与应用,2013,42(4):42-47.Cai Zheng,Yi Guobin,Chen Xudong.The development of study on nylon ageing mechanism[J].Synthetic Materials Aging and Application,2013,42(4):42-47.
[17]Wudy K,Drummer D.Aging effects of polyamide 12 in selective laser sintering:Molecular weight distribution and thermal properties[J].Additive Manufacturing,2019,25:1-9.