电纺直写制备聚己内酯支架形貌及精度

作为一种新型的微纳制造技术，熔体直写电纺被广泛用于组织工程支架的可控制备,有序的纤维沉积是该领域应用的前提条件。对于支架成型精度的探究，本文使用生物可降解材料聚己内酯（PCL），采用自行设计的熔体电纺三维可控成型设备进行实验，考察了纤维间距对二维并行纤维沉积形貌及成型精度的影响，以及纺丝电压和网格大小对三维网格结构形貌及精度影响。结果表明，随着并行纤维设定距离的增大，纤维的沉积误差减小，并最终趋于平稳。对于三维网格结构，随电压的增加，最大沉积层数量先增大后减小，当纺丝电压为6kV时达到最大沉积层数15层。成型精度误差先减小后增大，当纺丝电压为7kV时，精度最高误差小于5%。随设定网格边长的增大，沉积层数不断增大。成型精度逐渐提高，当网格边长大于等于1.5mm时，沉积误差趋于稳定，并维持在5%左右。     

电纺聚己内酯纤维直径工艺参数正交设计优化

本研究采用正交设计法研究静电纺丝法工艺过程对聚己内酯纤维直径的影响因素。主要研究纺丝液浓度、纺丝电压、注射泵进料速率三个因素对于纤维直径的影响。结果表明溶液浓度是影响纤维直径最主要的因素,次要影响因素是纺丝电压、进料速率。同时成功制备了纤维直径分别为0.35±0.09μm,0.95±0.09μm,6.48±0.50μm的聚己内酯纤维支架,可作为基底模板,用于研究同种材料不同直径的纤维支架对细胞行为的影响。     

静电纺工艺参数对聚己内酯纳米纤维直径的影响

用静电纺丝法制备组织工程所需的纳米纤维及材料,在实验中主要研究了基本的工艺参数对所获纤维直径的影响。纤维或非织造膜由两种溶剂系统所制备:氯仿与N,N-二甲基甲酰胺(DMF)的混合剂及含少量(约40μg)嘧啶的乙酸溶液。为了研究聚合物浓度、DMF含量、施加电压、极距、溶剂系统等因素的影响,使用了扫描电子显微镜、溶液黏度仪、溶液电导率测试仪等。结果表明:随着聚合物浓度上升,纤维的直径先增加后减小;随着溶液中DMF含量的增加,纤维直径不断减小;电压对纤维直径无明显的影响;极距需适中,过大过小都会产生珠状纤维;含少量嘧啶(40μg的乙酸溶剂所获得的聚己内酯(PCL)纳米纤维比由氯仿和DMF的混合溶剂所获得的PCL纳米纤维更加细而均匀。     

碳酸乙烯酯对聚己内酯/冰乙酸电纺纤维的影响

在聚己内酯(PCL)/冰乙酸(GAC)溶液体系中加入低毒低挥发性溶剂碳酸乙烯酯(EC),采用静电纺丝法成功制备纳米纤维,采用扫描电子显微镜研究了不同EC浓度对制得的纤维形貌和直径的影响。结果表明,当溶液中PCL质量分数为20%,EC体积分数从0%变化到9%时,纳米纤维数量增加,平均直径逐渐变小;当EC体积分数从9%变化到15%时,微米纤维或珠串状纤维数量开始增加,平均直径逐渐变大。对比研究了EC体积分数为9%的溶液与未加EC的溶液的纺丝稳定性,同时对比研究了由这两种溶剂分别制备的纳米纤维膜和微米纤维膜的结构和性能。结果表明,PCL/GAC/EC溶液体系黏度可在24h内保持稳定,满足连续电纺要求;X射线衍射测试结果表明两种纤维膜结晶构型一致,只是结晶度和晶粒大小有所区别;傅里叶变换红外光谱分析结果表明EC对PCL的化学结构没有影响;与微米纤维膜相比,纳米纤维膜的比表面积提高了362.6%,平均孔直径有所减小,接触角有所增大;纳米纤维膜的拉伸断裂应力稍大但断裂应变明显小于微米纤维膜。     

聚己内酯的熔体流动性能和挤出胀大

应用熔体流动速率仪,在温度为90～140℃和载荷为2.16～12.50 kg的条件下,考察了温度、表观剪切速率(γα)及管壁剪切应力((Τ)R)对聚己内酯(PCL)熔体流动性能和挤出胀大比(B)的影响.结果表明:在实验条件下,PCL熔体的剪切流动基本服从幂律定律.表观剪切黏度ηa与绝对温度的关系符合Arrhenius方程,ηa随着γa或ΤR的增加而非线性减小.B随着温度的升高而非线性降低,随着γa或(Τ)R的增加而非线性增大,达到最大值后B则下降.     

相分离制备聚己内酯纳米纤维支架的工艺探讨

以二氧六环/水为溶剂体系采用相分离方法首次成功制备了高孔隙率、具有纳米纤维状结构的聚己内酯（PCL）支架,并且支架是以球体为结构单元的基体。文中主要探讨了陈化温度和溶剂比例对于球状纳米纤维结构支架形成的影响,太低（-40 ℃）或太高的陈化温度（≥8 ℃）均不利于PCL纳米纤维结构的出现,只有适宜的实验温度才可以得到纳米纤维球状基体。同样,非溶剂比例越大越不利于纳米纤维球状基体的形成。     

静电纺丝法制备聚己内酯纳米纤维的工艺研究

以可生物降解的两亲性聚合物-聚己内酯(PCL)为原料,三氯甲烷和N,N-二甲基酰胺(DMF)为混合溶剂,采用静电纺丝技术制备了不同尺寸的PCL纳米纤维,研究了不同的PCL溶液浓度和针头尺寸相关工艺参数对纳米纤维微观形貌结构和尺寸分布的影响,同时对有序PCL纳米纤维的制备工艺进行了初步研究。     

静电纺丝制备聚己内酯载药纤维工艺参数研究

选用聚己内酯作为载体材料、5-氟尿嘧啶作为承载药物,研究了静电纺丝过程中纺丝液浓度、纺丝电压及收集距离对纤维直径的影响,对制备的聚己内酯载药纤维膜进行元素检测分析及力学性能测试,通过体外药物释放实验,验证了聚己内酯载药纤维膜药物控释的效果.结果表明,随着纺丝液的浓度和收集距离增加,纤维的平均直径增大;随着纺丝电压增加,...     

丝素-聚己内酯纳米纤维膜的制备工艺

以六氟异丙醇(HFIP)为溶剂,采用静电纺丝技术制备丝素(SF)-聚己内酯(PCL)复合纳米纤维膜。采用热场发射扫描电镜、Image-Pro Plus图像分析和力学拉伸的方法表征了纳米纤维膜的结构与力学性能。通过设计的三因素四水平正交试验对复合纳米纤维膜的多个指标进行了分析,采取归一化数据处理及平均权重分配的方式量化了复合纳米纤维膜的品质,确定了共混复合纳米纤维膜制备的最优工艺参数,并且采用最佳工艺参数制备了SF-PCL复合纳米纤维膜,分析了其力学性能。结果表明:在溶质质量分数为6%、溶质SF与PCL质量比为3∶2、纺丝流速1.2 mL/h时,SF-PCL复合纳米纤维膜具有较好的品质;双轴拉伸时的破坏机制与单轴不同,其断裂应力和应变只是单轴时的一半左右,膜的力学性能表现为各向同性。     

聚己内酯电纺直写支架纤维黏结性能研究

作为一种新型的微纳制造技术,电纺直写对于生物组织工程而言意义重大,而纤维间的黏结力直接影响最终组织支架的稳定性。本研究采用生物可降解材料聚己内酯(PCL),通过自行设计的熔体电纺三维可控成型设备进行直写电纺,探究了喷头温度、冷热纤维的搭接间隔时间以及环境温度对纤维黏结效果的影响,并用热重分析仪(TGA)进行表征。研究表明:随着喷头温度的升高,纤维间的黏结力先逐渐增大,在出现轻微波动后又呈减小趋势,其中在190~210℃区间内黏结效果最佳;随冷热纤维搭接时间间隔的延长,纤维间的黏结效果不断下降;此外,环境温度对纤维黏结效果的影响较大。     

Melt electrospinning writing of three‐dimensional star poly(ϵ‐caprolactone) scaffolds

In the last decade, the melt‐electrospinning technique has gained attention for the production of highly porous microfibrous tissue engineering scaffolds. The possibility of processing polymers without the use of organic solvents is one of the main advantages over solution electrospinning. In this study, computer‐controlled melt‐electrospinning of a commercial poly(?‐caprolactone) and of two batches with different molecular weights of a three‐arm star poly(?‐caprolactone) by means of a screw‐extruder‐based additive manufacturing system is reported. Experimental parameters such as processing temperature, extrusion flow rate and applied voltage were studied and optimized in order to obtain non‐woven meshes with uniform fibre morphology. Applying the optimized parameters, three‐dimensional scaffolds were produced using a layer‐by‐layer approach (0 ? 90° lay‐down pattern). © 2013 Society of Chemical Industry     

熔体静电纺丝直写技术在组织工程中的应用进展

熔体静电纺丝直写技术以其纤维直径、沉积形貌可控性高及无溶剂残留等优势,为高强度复杂形貌可控仿生组织工程（TE）支架的制备提供了巨大的空间,成为近年来的研究热点。本文首先简述了熔体静电纺丝直写技术相对于各类其他TE支架制备方法的优势;其次从工艺调控方面综述了熔体静电纺丝直写技术的工艺研究进展,并总结了实现复杂可控形貌TE支架的调控方法;随后从支架材料、形貌表征和细胞培养效果等方面综述了熔体静电纺丝直写技术的TE应用进展,并概括了该技术制备的TE拓扑结构支架的种类及特点;最后指出熔体静电纺丝直写技术具有广阔的研究前景,且该技术应以制备仿生、材料多样化以及复合支架为研究重点。     

High definition fibrous poly(2-ethyl-2-oxazoline) scaffolds through melt electrospinning writing

Melt electrospinning writing (MEW), a computer-aided fiber deposition process based on an electrohydrodynamic working principle, enables the rational design and fabrication of fibrous scaffolds with micrometer thin fibers. So far, MEW has mainly been applied for poly(ε-caprolactone). Here we manufactured scaffolds of poly(2-ethyl-2-oxazoline), a hydrophilic polymer with high melting temperature, by MEW for the first time. We systematically varied and investigated the crucial instrument parameters: heating temperature (200–220 °C), feeding pressure (1.0–3.0 bar), accelerating voltage (3.0–7.0 kV) and collector distance (3.0–7.0 mm) in dependence of differently sized spinnerets (23 G, 25 G, 27 G, 30 G). As criteria for homogeneous deposition, we studied the resulting fiber diameters which could be adjusted from 8 μm to 138 μm and the corresponding variances. Furthermore this letter clarifies the need of a dynamic balance between involved mass flows in order to reduce pulsing failures of the jet and thereby structural defects of the deposited structures.     

Melt‐electrospinning of poly(ethylene terephthalate) and polyalirate

Rodlike polymer samples were made from three kinds of poly(ethylene terephthalate) (PET) pellets with different intrinsic viscosities (IV), and from polyalirate (Vectra) pellets. PET and Vectra fibers were produced using a melt‐electrospinning system equipped with a CO₂‐laser melting device from these rodlike samples. The effects of IV value and laser output power on the fiber diameter of PET were investigated. Furthermore, the effect of the laser output power on the fiber diameter of Vectra was investigated. The crystal orientation of these produced fibers was also investigated by X‐ray photographs. The following conclusions were reached: (i) the diameter of PET fiber decreases with increasing laser output power; (ii) the minimum average diameter of PET fibers is scarcely influenced by the value of IV; (iii) the electrospun PET fibers show isotropic crystal orientation; (iv) fibers having an average fiber diameter smaller than 1 μm cannot be obtained from PET and Vectra using the system developed; and (v) preferred liquid crystal orientation can be seen in electrospun Vectra fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effects of ethylene content of poly(ethylene‐co‐vinyl alcohol) on diameter of fibers produced by melt‐electrospinning

Rodlike samples were made from four kinds of poly(ethylene‐co‐vinyl alcohol) (EVAL) pellets with different ethylene contents. From these rodlike samples, fibers were produced using a melt‐electrospinning system equipped with a CO₂‐laser melting device. The effects on the fiber diameter of the ethylene content and the moisture regain of the rodlike samples were investigated. Furthermore, the physical properties of the fibers were investigated. The following conclusions were reached: (i) EVAL fibers having an average fiber diameter smaller than 1 μm can be obtained using the system developed; (ii) the diameter of EVAL fiber is influenced by the ethylene content and the moisture regain of the starting rods; (iii) the laser heating does not greatly decrease the melting point and the molecular weight of EVAL; and (iv) preferred crystal orientation can be seen in electrospun EVAL fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1368–1375, 2007     

Characterization of nano-structured poly(ε-caprolactone) nonwoven mats via electrospinning

Nano-structured poly(ε-caprolactone) (PCL) nonwoven mats were prepared by electrospinning process. In this study, three types of solution were used. One dissolved in only methylene chloride (MC), the second dissolved in mixture of MC and N,N-dimethylformamide (DMF), the third dissolved in mixture of MC and toluene. MC, toluene and DMF are a good, poor, and nonsolvent for PCL, respectively. For the MC only, electrospun fibers had very regular diameter of about 5500 nm, but electrospinng is not facilitated. For the mixture of MC and DMF, electrospinning is certainly enhanced as well as fiber diameter decreased dramatically as increasing DMF volume fraction. It was due to high electric properties of solution such as dielectric constant and conductivity. Whereas, as increasing toluene volume fraction, electrospinning is strictly restricted due to very high viscosity and low conductivity. As the results, it has regarded that solution properties is one of the important parameter in electrospinning. Properties such as conductivity, surface tension, viscosity and dielectric constant of the PCL solutions prepared from three types of solvent system were studied. The morphology, crystallinity and mechanical properties of electrospun PCL nonwoven mats were characterized by scanning electron microscopy (SEM), wide angle X-ray diffraction (WAXD) and universal testing method (UTM), respectively.     

化学物理联合微孔发泡成型制备聚己内酯多孔材料

将超临界气体发泡技术与化学发泡技术联合用于制备多孔材料。采用碳酸氢钠作为化学发泡剂,将聚己内酯与碳酸氢钠挤出共混之后,使用传统注射成型和微注射成型,进行了发泡实验对比。结果表明,物理化学联合发泡用于制备多孔材料具有可行性,化学发泡剂的加入不仅改善了整体发泡效果,还能够作为气泡成核剂促进物理发泡的质量。对于所得结构在一定程度上表现的泡孔相互连通性进行了讨论,同时对泡孔壁面上出现的“网”状结构进行了分析。气泡在成核生长过程中,对于泡孔壁产生多方向拉伸的作用,相邻气泡共同作用于公共壁面,最终导致壁面部分形成“网”状结构。     

Synthesis of ultrafine poly(styrene‐maleic anhydride) and polystyrene fibers by electrospinning

Fiber formation from atactic polystyrene (aPS) and alternating poly(styrene‐maleic anhydride) (PSMA) synthesized by free radical polymerization (AIBN, 90°C, 4 h) were investigated by electrospinning from various solutions. aPS was soluble in dimethylformamide (DMF), tetrahydrofuran (THF), toluene, styrene, and benzene, whereas PSMA was soluble in acetone, DMF, THF, dimethylsulfoxide (DMSO), ethyl acetate, and methanol. aPS fibers could be electrospun from 15 to 20% DMF and 20% THF solutions, but not from styrene nor toluene. PSMA, on the other hand, could be efficiently electrospun into fibers from DMF and DMSO at 20 and 25%, respectively. Few PSMA fibers were, however, produced from acetone, THF, or ethyl acetate solutions. Results showed that solvent properties and polymer–solvent miscibility strongly influenced the fiber formation from electrospinning. The addition of solvents, such as THF, generally improved the fiber uniformity and reduced fiber sizes for both polymers. The nonsolvents, however, had opposing effects on the two polymers, i.e., significantly reducing PSMA fiber diameters to 200 to 300 nm, creating larger and irregularly shaped aPS fibers. The ability to incorporate the styrene monomer and divinylbenzene crosslinker in aPS fibers as well as to hydrolyze PSMA fibers with diluted NaOH solutions demonstrated potential for post‐electrospinning reactions and modification of these ultrafine fibers for reactive support materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Poly(lactide) nanofibers produced by a melt‐electrospinning system with a laser melting device

A new melt‐electrospinning system equipped with a CO₂‐laser melting device was developed. Rod‐like samples were prepared from poly(lactide) pellets, and then fibers were produced from the samples using the new system. The effects of producing conditions on the fiber diameter were investigated. Furthermore, the physical properties of the fibers were investigated. The following conclusions were obtained: (i) in a special case, fibers having an average fiber diameter smaller than 1 μm could be obtained using the system developed; (ii) the fiber diameter could be decreased with increased laser output power, but the physical properties of the fibers such as the melting point and the molecular weight were decreased; and (iii) the electrospun fibers exhibited an amorphous state, and the annealed fibers exhibited an isotropic crystal orientation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1640–1645, 2007