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。     

热塑性聚氨酯/石墨烯改性聚氨酯注浆材料的制备与性能研究

采用石墨烯、热塑性聚氨酯（TPU）复合改性聚氨酯注浆材料,并添加少量的粉煤灰、炉底渣及碱性激发剂制备一种低密度、高强度、快硬性的TPU/石墨烯改性聚氨酯注浆材料。借助聚氨酯弹性体材料密度测试仪、万能材料试验机、渗透系数测试仪、荧光显微镜对TPU/石墨烯改性聚氨酯注浆材料的密度、膨胀倍数、抗压强度、阻燃性能、渗透系数及微观形貌进行表征,深入分析了石墨烯和TPU的种类和含量对聚氨酯注浆材料基本物理性能、力学性能及微观结构的影响。结果表明,TPU/石墨烯改性聚氨酯注浆材料的密度为0.24~1.25 g/cm³,膨胀倍数最高可达38倍,抗压强度为15.0~43.8 MPa,相比普通聚氨酯注浆材料,改性聚氨酯注浆材料抗压强度提升1倍以上。酒精灯燃烧试验显示注浆材料无焰燃烧时间均小于20 s。石墨烯和TPU均可提高聚氨酯的强度和耐久性,改善TPU的微观形貌。TPU/石墨烯改性聚氨酯注浆材料表现出良好的强度、耐久性及弹性,是一种性能优异的注浆材料。     

A comparison of thermoplastic polyurethane incorporated with graphene oxide and thermally reduced graphene oxide: Reduction is not always necessary

Despite wide applications of reduced graphene-oxide (GO)-reinforced polymer-based composites, the necessity of the reduction procedure toward GO is still controversial. In this article, thermoplastic polyurethane (TPU) composites incorporated with GO and thermally reduced graphene oxide (TGO) were fabricated. GO and TGO exhibited different effects on crystallization behaviors, and mechanical and thermal properties of the TPU matrix. With 2.0 wt % filler loading, TPU composite reinforced by GO (TPU-GO-2 wt %) exhibited better thermal stability than that reinforced by TGO (TPU-TGO-2 wt %). The interfacial interaction between the nanofillers and the TPU matrix as well as their influence on the mobility of TPU chains were investigated, which proved that GO is superior to TGO in improving interface adhesion and maintaining crystallization of the TPU matrix. Compared with TPU-TGO-2 wt %, improved mechanical properties of TPU-GO-2 wt % were also evidenced owing to more oxygen-containing groups. This work demonstrates that the reduction of GO is not always necessary in fabricating polymer composites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47745.     

Preparation and characterization of plla composite scaffolds by ScCO2‐induced phase separation

Composite Scaffolds have received much attention in the tissue engineering, and how to choose the materials has become the research focus in this field. Supercritical CO₂ (ScCO₂)‐induced phase separation process was employed to prepare porous poly‐L ‐lactide (PLLA) composite scaffolds. An experiment system was set up for the purpose of investigating the effects of such parameters as the mass ratios of PLLA to polyethylene glycol (PEG) and PLLA to β‐TCP on porosity and compressive strength of composite scaffolds. The obtained composite scaffolds were characterized in many ways. Scanning electron microscopy was used to examine the morphology and pore size; porosity was analyzed by pycnometer; and the compressive strength was recorded by texture analyzer. The results indicated that the porosity was increased with the addition of PEG, and the highest porosity of PLLA/PEG composite scaffolds was 92% with the mass ratio of PLLA to PEG of 1:0.05; the compressive strength was increased with the addition of β‐TCP, and the highest compressive strength of PLLA/β‐TCP composite scaffolds was 1.76 MPa with the mass ratio of PLLA to β‐TCP of 1:0.1. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Preparation of PVDF/CaCO3 composite hollow fiber membrane via a thermally induced phase separation method

The spinnabiliy of polyvinylidene fluoride (PVDF)/CaCO₃ microparticle dope solution were explored via a thermally induced phase separation process, and composite hollow fiber (CHF) membranes were prepared successfully. The experiment results showed that the self‐supporting property of CHF got improved after adding CaCO₃ at low concentration of PVDF, so the control of spinning process became easy. The effects of CaCO₃ on the structure and properties of hollow fiber membrane were investigated in terms of morphology, water flux, porosity, breakage strength, and crystallization. The results indicated that CHF presented a uniform bicontinuous structure. The permeability and porosity of CHF increased obviously when CaCO₃ was removed by acid, while the breakage strength decreased slightly. CHF presented a good drying stability. POLYM. COMPOS., 34:1204–1210, 2013. © 2013 Society of Plastics Engineers     

热致相分离法制备聚乙烯/纳米二氧化钛共混膜

采用相对分子质量为130 000的聚乙烯(PE)为膜材、DIDP为稀释剂、平均直径为180 nm的TiO2粉末作添加剂,用热致相分离(TIPS)法制备了PE膜和PE/TiO2共混膜。研究了共混组成和冷却速率对膜结构的影响。所有制备的膜均是海绵状孔,冷却速率越大,膜孔越小。对PE质量分数为15%,当PE与TiO2的质量比大于1时,TiO2在膜内的分布不均匀,当PE与TiO2的质量比为0.5时,TiO2能比较均匀的分布于膜内。共混膜浸于水中经过紫外照射后,其亲水性显著增加。     

聚氨酯/石墨烯复合纤维的制备及其发泡性能研究

以热塑性聚氨酯(TPU)、单层纳米石墨烯(GR)通过溶液与熔融共混并用的方法制备TPU/GR共混物,利用不同牵引速度纺丝制得不同直径的TPU/GR复合纤维,对其进行超临界二氧化碳微孔发泡,制得发泡TPU/GR复合纤维,探究了GR在TPU中的分散性,纤维尺寸和GR含量对发泡TPU/GR复合纤维泡孔结构及力学性能的影响。结果表明:GR在TPU体系中具有良好的分散形态及较高的二氧化碳气体阻隔性能;当发泡TPU/GR复合纤维直径为200μm时,随着GR含量的增加,纤维的发泡面积逐渐变大,泡孔直径呈现先减少后增加的趋势;对于直径为500μm的发泡TPU/GR复合纤维,随着GR含量的增加,纤维的泡孔直径逐渐变小,泡孔密度逐渐增加,即当加入质量分数为5%的GR,纤维泡孔直径由原来未加GR时的3. 78μm降低至1. 97μm,泡孔密度由原来的未加GR时4. 93×10~9cells/cm~3增加至2. 42×10~(10)cells/cm~3。     

Preparation and characterization of thermally conductive thermoplastic polyurethane/h‐BN nanocomposites

Polyurethane nanocomposites are versatile engineering polymers with unique properties. In this study, nano hexagonal boron nitride containing thermoplastic polyurethane elastomers were prepared via melt blending and hot‐pressing techniques. The nanocomposites were characterized using Fourier transform infrared, differential scanning calorimetry, thermal gravimetric analysis, tensile tests, and thermal conductivity measurements. The surface morphology of the TPU/h‐BN composites was characterized by scanning electron microscopy. The optical properties of the composites were determined by UV transmittance measurements and as the amount of h‐BN increased, optical transparencies decreased dramatically. Nanocomposites displayed higher E‐modulus values and lower elongation at break values than the pure TPU elastomer. Char yields of TPUs increased with increasing h‐BN percentage. Moreover, thermal conductivity of the composite materials improved with the incorporation of h‐BN. POLYM. COMPOS., 35:530–538, 2014. © 2013 Society of Plastics Engineers     

Formation of porous PLGA scaffolds by a combining method of thermally induced phase separation and porogen leaching

A novel method for the fabrication of porous poly(L -lactide-co-glycolide) (PLGA) scaffolds by combining thermally induced phase separation and porogen leaching is presented in this article. Big pores with about 75–400 μm diameters in the obtained scaffolds were generated by the porogen, sucrose particles, while small pores with diameters less than 20 μm induced via phase separation. Extraction of the solvent, chloroform by ethanol at cool temperatures could reduce the scaffold toxicity. Effects of PLGA concentration, freezing temperature, volume fraction of porogen, and introduction of β-tricalcium phosphate (β-TCP) on morphology, porosity, and compressive properties of the scaffolds were systematically discussed. Results showed that the size of small pores decreased by decreasing the polymer concentration and reducing the freezing temperature, whereas the interconnectivity of the scaffolds was improved by increasing the porogen fraction. The compressive modulus and strength were significantly lowered by increasing the scaffold porosity, that is, by increasing porogen fraction, or decreasing the polymer concentration, or reducing the freezing temperature. Addition of β-TCP into the scaffolds did not influence the compressive modulus significantly but tended to decrease the compressive strength. The obtained scaffolds with diverse pore sizes would be potentially used in bone tissue engineering. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of graphene oxide/polyamide composite nanofiltration membranes for enhancing stability and separation efficiency

Polyamide (PA) NF membranes are synthesized on a hollow fiber support by the interfacial polymerization (IP) of piperazine (PIP) and trimesoyl chloride (TMC). Then, GO is coated on the PA layer to decorate the NF membrane surface (denoted GO/PA-NF). This strategy aims to improve the hydrophilicity, chlorine resistance and separation stability of the membrane. The optimization, chemical composition, morphology, and hydrophilicity of the synthesized GO/PA-NF membrane are characterized. Results indicate that the optimized GO/PA-NF in terms of rejection rate and flux are with 0.05 wt% GO. The rejection of GO/PA-NF for Na2SO₄ and MgSO₄ is 99.4% and 96.9%, respectively. Even if the GO/PA-NF is immersed in 1000 ppm NaClO solution for 48 h, the NF membrane still maintains stable salt rejection. The developed NF membranes exhibit excellent treatment performance on dying wastewater. The permeate flux and rejection of GO/PA-NF toward Congo red solution are determined to be 44.2 L/m²h and 100%, respectively. Compared with the PA membrane, GO/PA-NF presents a higher rejection for Na₂SO₄ (99.4%) and a lower rejection for NaCl (less than 20%), which shows that the NF membranes have a better divalent/monovalent salt separation performance. This study highlights the superior performance of GO/PA-NF and shows its high potential for application in wastewater treatment.     

细菌纤维素/热塑性聚氨酯复合气凝胶纤维制备及性能

使用绿色有机材料细菌纤维素(BC),并掺杂增强材料热塑性聚氨酯弹性体(TPU)经过湿法纺丝制备复合气凝胶纤维,通过傅里叶变换红外光谱(FTIR)、X射线衍射光谱(XRD)、热重分析(TG)、扫描电子显微镜(SEM)、全自动比表面孔隙度分析仪和单丝强力仪对制备的气凝胶纤维进行结构分析和性能表征,结果表明复合气凝胶纤维具有多孔结构,良好的力学性能和隔热性能,断裂强度达到24.69Mpa,断裂伸长为38.54%。     

Preparation and characterization of cellulose triacetate membranes via thermally induced phase separation

A series of cellulose triacetate (CTA) membranes were prepared via thermally induced phase separation (TIPS) process with dimethyl sulfone (DMSO2) and polyethylene glycol (PEG400) as a crystallizable diluent and an additive, respectively. The phase separation behavior of CTA/DMSO2/PEG400 ternary system was investigated in detail by optical microscopy, differential scanning calorimetry and wide angle X‐ray diffraction. This ternary system dynamically undergoes solid‐solid phase separation and thus the CTA membranes possess cellular, lacy, plate‐, or even ellipse‐shaped pores. However, we can modulate the pore structure, porosity, water flux, and mechanical properties of the membranes by varying polymer concentration, composition of the mixed diluent, and cooling condition. Due to the intrinsic hydrophilicity, the prepared CTA membranes have better antifouling property than polysulfone membranes. These porous membranes were used as supports to fabricate thin‐film composite forward osmosis (FO) membranes, which show good water permeability and selectivity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44454.     

离子液体改性石墨烯/聚氨酯弹性体复合材料的制备及形状记忆性能

采用1-丁基-3甲基咪唑四氟硼酸盐离子液体对石墨烯表面进行功能化修饰,用溶液共混法将离子液体改性石墨烯(IG)填入热塑性聚氨酯弹性体(TPU)制备IG/TPU复合材料,并考察了IG用量对IG/TPU复合材料形状记忆性能的影响.结果表明,纯TPU没有表现出光响应形状记忆性能,在激光照射下几乎没有回复.而IG的加入能显著提...     

Preparation of porous membrane by combined use of thermally induced phase separation and immersion precipitation

By immersion in the cooled nonsolvent, PMMA porous membrane was prepared by the combined use of thermally induced phase separation (TIPS) and immersion precipitation. As nonsolvent, water with low mutual affinity with cyclohexanol (diluent) and methanol with high affinity were used. In the case of water, the porous structure was formed by TIPS immediately after the immersion. Near the top surface contacted with the nonsolvent, the thin skin layer was formed due to the outflow of the diluent. After the long immersion period, macrovoids were formed near the top surface due to the penetration of the nonsolvent. Thus, TIPS and the immersion precipitation occurred serially. On the contrary, TIPS and the immersion precipitation occurred simultaneously in the case of methanol because the inflow of methanol was fast. Therefore, the membrane obtained after the short immersion period had the larger pores near the top surface due to the nonsolvent induced phase separation and the smaller pores near the bottom surface due to TIPS. These two modes of the phase separations were confirmed by the changes in light transmittance through the polymer solutions.     

High-performance thermoplastic polyurethane nanocomposites induced by hybrid application of functionalized graphene and carbon nanotubes

A hybrid polymeric system containing carbon nanofillers with different geometrical dimensions is proposed for strategic applications, particularly for electrical properties. Two different carbon nanofillers including functionalized multiwalled carbon nanotubes (fCNTs) and functionalized graphene nanoplatelets (fGnPs) were added to thermoplastic polyurethane (TPU) to prepare single and hybrid nanofiller filled TPU through solution mixing. Sufficient exfoliation of the fGNPs in the single nanocomposites was confirmed by X-ray diffraction, while single filler and hybrid TPU nanocomposites containing fCNTs showed some re-aggregation of these nanofillers. Linear rheology together with scanning electron microscopy revealed a proper exfoliation and dispersion degree for fGnPs and fCNTs, respectively. We have shown that simultaneous addition of fCNTs–fGnPs in the form of a hybrid system into the TPU made a large surface area available and strong interfacial interactions were formed between the hybrid network and the TPU matrix. This in turn led to electrical, thermal and mechanical properties, which were superior to those predicted by the mixture law. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48520.     

Preparation and characterization of PES/CA microporous membranes via reverse thermally induced phase separation process

The blend polyethersulfone (PES)/cellulose acetate (CA) flat‐sheet microporous membranes were prepared by reverse thermally induced phase separation (RTIPS) process. The effects of CA content and coagulation bath temperature on membrane structures and properties were investigated in terms of membrane morphology, water contact angle, permeation performance, and mechanical properties. The cloud point results indicated that the cloud point decreased with the increasing content of CA. When the coagulation bath temperature was lower than the cloud point, the membrane formation process underwent nonsolvent induced phase separation (NIPS) process and dense skin layer and finger‐like structure were formed in membranes. These membranes had lower pure water flux and poor mechanical properties. But when the coagulation bath temperature was higher than the cloud point, the membrane formation process underwent RTIPS process. The porous top surface as well as porous cross‐section of the membranes were formed. Therefore, high pure water flux and good mechanical properties were obtained. The contact angles results indicated that the hydrophilicity of the prepared membranes improved obviously with the addition of CA. When the content of CA was 0.5 wt% and the membrane formation temperature was 323K, the PES/CA microporous membrane which was prepared via the RTIPS process displayed a optimal permeability of the pure water flux of 816 L m^?2 h^?1 and the BSA rejection rate of 49.5%, which showed an increase of 48.9% and 23.6% than that of pure PES membrane, respectively. Moreover, the mechanical strengths of the membranes obtained by RTIPS process were better than those membranes prepared by NIPS process. POLYM. ENG. SCI., 58:180–191, 2018. © 2017 Society of Plastics Engineers     

Porous cellulose acetate membrane prepared by thermally induced phase separation

Microporous cellulose acetate membranes were prepared by a thermally induced phase separation (TIPS) process. Two kinds of cellulose acetate with acetyl content of 51 and 55 mol % and two kinds of diluents, such as 2‐methyl‐2,4‐pentandiol and 2‐ethyl‐1,3‐hexanediol, were used. In all polymer‐diluent systems, cloud points were observed, which indicated that liquid–liquid phase separation occurred during the TIPS process. The growth of droplets formed after the phase separation was followed using three cooling conditions. The obtained pore structure was isotropic, that is, the pore size did not vary across the membrane. In addition, no macrovoids were formed. These pore structures were in contrast with those usually obtained by the immersion precipitation method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3951–3955, 2003     

Reaction induced phase separation in semicrystalline thermoplastic/epoxy resin blends

The phase separation behaviour and phase morphology of blends of 4,4′-diaminodiphenyl sulphone cured diglycidyl ether of bisphenol-A with poly(ε-caprolactone) were investigated by means of scanning electron microscopy, small angle light scattering and optical microscopy. The components are miscible prior to curing. High-temperature isothermal curing induces phase separation. Blends with near to critical concentrations demix via spinodal decomposition. The associated co-continuous morphology is only preserved in the actual critical compositions whereas for off-critical compositions it rapidly breaks up into spherical particles. The proceeding reaction in the separated phases induces a secondary phase separation. Occasionally, tertiary phase separation is observed as well. Off-critical compositions that are further away on either side from the critical point, phase separate via the direct formation of spherical particles, most likely as a result of the dynamic asymmetry of these blends. The influence of the amount, the molar mass of PCL and the cure temperature is discussed.     

氧化石墨烯/二氧化硅复合材料的制备及吸附性能

以改进的Hummers法制备的氧化石墨烯溶液为原料,十六烷三甲基溴化铵为模板剂,正硅酸乙酯为硅源,采用软模板法制备了氧化石墨烯/二氧化硅复合材料。借助红外光谱仪、扫描电子显微镜、X射线衍射仪对样品的物质结构和微观形貌进行分析表征。以亚甲基蓝模拟染料废水,石墨烯/二氧化硅复合材料为吸附剂,研究其在不同吸附时间、反应温度、ρ(亚甲基蓝)、吸附剂投加量、体系pH值下,对体系吸附量和去除率的影响。结果表明,复合材料出现了C—O—Si的特征峰,说明石墨烯与二氧化硅复合成功;且复合材料在温度为35℃,搅拌时间为90 min,pH=4,ρ(亚甲基蓝)=5 mg/L,投加量为50 mg时吸附性能最好,吸附量为22.75 mg/g,去除率为91%。     

氧化石墨烯/水性聚氨酯复合薄膜的制备及性能研究

以自制的GO(氧化石墨烯)为填料,WPU(水性聚氨酯)为基体,采用溶液共混和流延成膜法制备了GO/WPU复合薄膜。着重考察了GO含量对GO/WPU复合薄膜力学性能和导热性能等影响。研究结果表明:随着GO含量的增加,复合薄膜的拉伸强度增强、导热系数增大;当w(GO)=4%(相对于复合薄膜质量而言)时,复合薄膜的拉伸强度(20.6 MPa)相对最大、导热系数[为0.208 W/(m·K)]相对最高[这是由于GO均匀分散在PU(聚氨酯)基体中,形成了连续褶皱状网络结构的缘故]。