3.1. Infrared spectroscopy and thermogravimetric analysis
FTIR is mainly used to analyze the structure and functional groups of polymer main chain. The FTIR spectra of pure PU and pure CA nanofiber membranes and CA/PU blend nanofiber membrane are shown in Fig. 2a. The absorption peaks at 2944cm− 1 and 1433cm− 1 are the asymmetric tensile vibration peak and bending vibration peak of CH2 respectively, and the absorption peak at 1730cm− 1 is the carbonyl C = O stretching vibration peak. These absorption peaks are characteristic peaks of the same functional groups of CA and PU. The absorption peak at 3334 cm− 1 is caused by the stretching vibration of N-H, and the absorption peak at 1528 cm− 1 belongs to the bending vibration of N-H. These absorption peaks are the characteristic peaks of PU (Riaz et al. 2016; Yin et al. 2018; Tan et al. 2015). The absorption peak at 3465cm− 1 is the stretching vibration peak of O-H, which belongs to the characteristic peak of CA (Zhang et al. 2021). After PU and CA were blended, the strength of the stretching vibration peak and bending vibration peak of N-H decreased, while the stretching vibration peak of O-H moved to the high wave number direction, which may be caused by the formation of hydrogen bond between the hydroxyl group of CA and the amino group of PU.
In industrial applications, it is necessary for the membrane to have good thermal stability. The thermal behavior of nanofiber membrane was evaluated by thermogravimetric (TG) analysis. The results are shown in Fig. 2b. The thermal decomposition of pure CA nanofiber membrane occurs between 282°C and 384°C, and the maximum decomposition temperature is 354°C. This weight loss of CA membrane material comes from the degradation of cellulose acetate chain, that is, the pyrolysis of polymer skeleton, followed by the deacetylation of CA (Arthanareeswaran et al. 2004; Lucena et al. 2003). The thermal decomposition process of pure PU nanofiber membrane is complex. The initial decomposition temperature is 280°C, and there are two maximum decomposition temperatures, 324°C and 374°C respectively. Because the aromatic ring system has a destabilizing effect on the carbamate bond, the hard segment of PU begins to degrade first, and the degradation rate is the highest at 324°C. After that, the soft segment of PU was decomposed, and the degradation rate reached the maximum at 374°C (Zavastin et al. 2010; Coutinho et al. 2003; Petrović et al. 1994). After the blending of PU and CA, the two maximum thermal decomposition temperatures of CA/PU nanofiber membrane are significantly higher than those of pure PU membrane, which are 356°C and 394°C respectively. This may be because the carbamate bond of PU is easier to degrade than that of cellulose acetate chain, which has a greater impact on the thermal stability of the blended nanofiber membrane. The positive shift of DTG peak and the increase of residue at 450°C also show that the thermal stability of CA/PU blend nanofiber membrane has been improved (Riaz et al. 2016; Iqhrammullah et al. 2020).
3.2. Membrane morphology
Figure 3a, b and c are SEM photos of the surfaces of CA, CA/PU and PU nanofiber membranes, respectively. It can be seen from the photos that there are obvious differences in the morphology of nanofibers constituting CA, CA/PU and PU membranes. The nanofiber diameter of PU membrane is fine and the number of fibers per unit area is large (Fig. 3c), while the nanofiber diameter of CA/PU membrane is coarse and uniform (Fig. 3b). The diameter distribution ranges of nanofibers of CA, CA/PU and PU membranes are 106-432nm, 215-542nm and 77-184nm respectively, and the average diameters are 243nm, 351nm and 124nm separately (Fig. S1). There is adhesion between the nanofibers of PU membrane, which may be related to the high boiling point of DMAc solvent used in electrospinning. The volatilization speed of solvent with high boiling point is slow, resulting in adhesion at the fiber contact point (Tang, Chen, and Liu 2008). The interaction between polymer molecular chains is one of the main factors affecting the average diameter of electrospun nanofibers. After CA and PU are blended, due to the easy formation of hydrogen bonds between hydroxyl, carbonyl and amide groups of CA and PU, the interaction between molecular chains is enhanced, and the stress relaxation time of CA/PU blend polymer solution is increased, which leads to the formation of large-diameter fibers during electrospinning (Fong, Chun, and Reneker 1999; Yao et al. 2008).
Figure 3d, e and f are SEM photos of brittle fracture surfaces of CA, CA/PU and PU nanofiber membranes, respectively. Obvious nanofibers can be seen on the fracture surfaces of CA and CA/PU membranes separately, while the fracture surface of PU membrane shows a honeycomb structure composed of adhesive bead fibers. This is because when electrospinning at low concentration, the chain entanglement makes the jet unstable, and the diameter of the jet shrinks under the action of surface tension, making the solution form bead fiber or bead (Cui et al. 2020). Figure 3g is a brittle fracture surface photo of PU-(CA/PU)-CA sandwich nanofiber Janus membrane. From Fig. 3g, three-layer membrane structure can be identified. The upper layer is CA nanofiber membrane, the middle layer is CA/PU blend nanofiber membrane, and the lower layer is PU nanofiber membrane.
3.3. Wettability of CA, CA/PU and PU nanofiber membranes
The wettability of membrane is usually characterized by the contact angle of liquid on the membrane surface. The test results of contact angle are shown in Fig. 4a. The water contact angle (WCA) of CA nanofiber membrane is 64.3°, which may be caused by the hydrophilicity of ester groups and incompletely esterified hydroxyl groups of CA molecular chain (Zhang et al. 2021). The WCA of PU nanofiber membrane is 123.8°, indicating that PU membrane is hydrophobic. The WCA of CA/PU blend nanofiber membrane is 88.7°, which can be understood that CA/PU membrane is also hydrophilic, but the hydrophilicity is not as strong as CA membrane. The oil contact angle (OCA) test results of CA, CA/PU and PU nanofiber membranes are all 0°, indicating that the three membranes are super lipophilic (Su et al. 2021; Qing et al. 2017).
In order to further understand the wettability of liquid on nanofiber membranes, water dyed blue and oil (cyclohexane) dyed yellow were dropped onto different nanofiber membranes, and the wetting process was recorded with a camera. Results as shown in Fig. 4b, both water and cyclohexane can spread and wet rapidly on the surface of CA nanofiber membrane. CA membrane shows good hydrophilicity and lipophilicity and less wetting time (twb). Cyclohexane can also spread and wet on the surface of PU membrane and CA/PU membrane, and the wetting time (twt) of cyclohexane on PU membrane is greater than wetting time (twm) on CA/PU membrane, both of which are greater than that on CA membrane (twt > twm > twb). Water has a certain degree of wetting on the surface of CA/PU membrane, but not on the surface of PU membrane. The wettability test results show that the wettability of water to CA, CA/PU and PU nanofiber membranes is significantly different.
PU-(CA/PU)-CA Janus membrane with nanofiber transition sandwich structure is composed of hydrophobic PU nanofiber membrane (top layer), CA/PU blend nanofiber membrane (middle transition layer) and hydrophilic CA nanofiber membrane (bottom layer). The directional transmission of water from top layer to bottom layer can be realized by using the difference of wettability. The photos of water droplets passing through PU-(CA/PU)-CA membranes with different thicknesses are shown in Fig. 4c. Water droplets can quickly pass-through membranes M50 and M80 with thickness of 50 µm and 80 µm respectively. This is because when the top PU hydrophobic layer is thin, under the action of gravity (Fw), water droplets can easily contact the transition layer and hydrophilic bottom layer through the hydrophobic layer. The downward hydrophilic force (F2) and Fw jointly overcome the upward hydrophobic force (F1), so that water droplets can pass through PU-(CA/PU)-CA nanofiber membrane (Fig. 4d). With the increase of top layer thickness, the chance of water droplets contacting the transition layer and hydrophilic bottom layer decreases under the action of gravity. F1 prevents water droplets from continuing to pass through PU-(CA/PU)-CA nanofiber membrane. When the membrane thickness is 150 µm (M150), F1 and Fw are balanced, and the water droplets stay on the top layer of PU and cannot pass through the PU-(CA/PU)-CA nanofiber membrane (Fig. 4d). On the contrary, when water droplets penetrate from the CA side of PU-(CA/PU)-CA nanofiber membrane, they first contact with hydrophilic CA nanofiber membrane, and the water droplets will spread rapidly and diffuse into CA nanofiber membrane through capillary force (Fc). The hydrophobic force F1 of PU layer will also prevent water droplets from further passing through PU-(CA/PU)-CA nanofiber membrane (Fig. 4e) (Wu et al. 2012). Therefore, PU-(CA/PU)-CA nanofiber membrane can realize the directional transmission of water from the top PU membrane to the bottom CA membrane.
3.4. Oil water separation capacity of membrane
The wettability difference of PU-(CA/PU)-CA nanofiber membrane can also be used for oil-water separation. As shown in Fig. 5a, methyl blue (blue) and 4-aminoazobenzene (yellow) were dissolved in water phase and oil phase (cyclohexane) respectively for dyeing, then the blue water phase and yellow oil phase were mixed, and then the oil-water mixture was poured into a separator equipped with PU-(CA/PU)-CA nanofiber membrane. When the oil-water mixture contacts the hydrophobic top layer of the membrane, the water in the lower layer of the mixture flows into the flask through the PU-(CA/PU)-CA nanofiber membrane driven by the transmembrane pressure, but the oil is blocked on the membrane, so as to realize the oil-water separation (Video S1).
As an effective oil-water separation material, two important conditions must be met, namely, high separation flux and high separation efficiency (Zhang, Zhang, et al. 2019; Su et al. 2021). Therefore, we studied the relationship between transmembrane pressure (Pt), membrane thickness and hydraulic permeability (Lp) and oil-water separation efficiency (Es). Figure 5b shows the relationship between Es, Lp and Pt of membrane M80. It can be seen from Fig. 5b that when Pt is small, the Es of membrane is very high (≥ 99%), but Lp is small. When Pt reaches 0.3 bar, Es remains above 99%, while Lp increases to 3.4×104 L/(m2 h bar). With the further increase of Pt, Lp gradually increased, but the Es of the membrane decreased sharply. When Pt reaches 0.5 bar, Es is 0, and the membrane loses the ability of oil-water separation. This is because large Pt enables the oil phase to pass through the nanofiber membrane, which makes the membrane lose the function of oil-water separation. Therefore, appropriate Pt is the key to ensure high Es and high Lp of the membrane. In view of this, we selected 0.3 bar as the Pt for membrane M80.
Using the same method, the Pt used for membranes M50, M120 and M150 were determined to be 0.1 bar, 0.4 bar and 0.6 bar respectively. Membranes with different thicknesses correspond to different Pt, and the greater the thickness of the membrane, the higher the corresponding Pt. The Es and Lp of membranes with different thicknesses under different Pt are shown in Fig. 5c. As can be seen from Fig. 5c, the Es of membranes with different thickness is higher, more than 98.5%, and the greater the membrane thickness, the higher the Es, when the membrane thickness is 150 µm (M150), the Es increases to 99.5%. Lp decreased significantly with the increase of membrane thickness. When the membrane thickness was 150 µm, Lp was only 0.15×104 L/(m2 h bar). Thus, for the sake of achieving high Lp and high Es simultaneously, the membrane thickness should be reduced as much as possible while ensuring that Es meets the requirements. Here, we selected the membrane with thickness of 50 µm (M50) for follow-up test.
In order to further evaluate the oil-water separation ability of PU-(CA/PU)-CA nanofiber membrane, different kinds of oil/water mixtures were selected for separation experiments and compared with 50 µm thick PU-CA nanofiber membrane without transition interlayer. As shown in Fig. 5d, PU-(CA/PU)-CA nanofiber membrane M50 can successfully separate oil/water mixtures such as n-hexane/water, cyclohexane/water, petroleum ether/water and vegetable oil/water, and both Es and Lp are high. The Es and Lp of petroleum ether/water with poor oil-water separation also reached 97.1% and 7.85×104 L/(m2 h bar), respectively. The Es of PU-CA nanofiber membrane for different kinds of oil-water mixtures is equivalent to that of PU-(CA/PU)-CA membrane, while Lp is lower than that of PU-(CA/PU)-CA membrane, which may be due to the PU layer thickness (25 µm) of PU-CA membrane is greater than that (20 µm) of PU-(CA/PU)-CA membrane (Zhang, Ge, et al. 2019).
In addition, the reusability and cyclic separation efficiency of PU-(CA/PU)-CA nanofiber membrane were also tested with cyclohexane/water mixture. As shown in Fig. 5e, after 30 cycles of separation experiments, PU-(CA/PU)-CA nanofiber membrane M50 still maintained high Es (97.2%) and Lp (8.34×104 L/(m2 h bar)). Compared with the initial Es (98.5%) and Lp (10.19×104 L/(m2 h bar)) of the membrane M50, the Es and Lp of the membrane M50 after 30 cycles of use decreased, which may be because the lipophilicity of the top PU nanofiber membrane is easy to make the oil adhere to the membrane surface, and the dissolution and corrosion of cyclohexane on the PU nanofiber membrane reduces the Es and Lp of the membrane (Pan et al. 2017). The cyclic separation experiment shows that PU-(CA/PU)-CA nanofiber membrane has high reusability.
Figure 5f is SEM photos of CA, CA/PU and PU membrane surfaces after 30 oil-water separation cycle experiments, respectively. It can be seen from Fig. 5f that the nanofibers of the repeatedly used PU membrane swell and adhere, which may be caused by the lipophilic PU membrane adsorbing oil (cyclohexane), and cyclohexane partially dissolving the PU nanofibers. The nanofibers of CA membrane and CA/PU blend membrane basically maintain their original morphology after repeated recycling, which may be because the hydrophilicity of CA membrane and CA/PU blend membrane forms a protective water layer on the membrane surface to avoid oil fouling (Lv et al. 2017; De Guzman et al. 2021). This also indicates that the antifouling performance of CA/PU nanofiber membrane is improved after CA and PU are blended.
3.5. Tensile test of membrane
In order to understand the influence of the composition and structure of nanofiber membrane on the mechanical properties of the membrane, tensile tests were carried out on pure PU membrane, pure CA membrane, CA/PU blend membrane, PU-CA bilayer Janus membrane without interlayer and PU-(CA/PU)-CA transition interlayer Janus membrane, and the results are shown in Fig. 6. The tensile strength (Ts) and elongation at break (Eb) of pure PU nanofiber membrane were the largest, which were 3.59 MPa and 135.51%, respectively, while the Ts and Eb of pure CA nanofiber membrane were lower, which were 0.89 MPa and 8.99%, separately. After CA and PU were blended, the Ts and Eb of CA/PU blend nanofiber membrane were more than twice that of pure CA nanofiber membrane, which were 1.93 MPa and 19.93% respectively. It shows that CA/PU blend nanofiber membrane has the characteristics of high strength of PU membrane and low elongation at break of CA membrane. It can also be seen from Fig. 6 that the Ts and Eb of PU-(CA/PU)-CA membrane with CA/PU blend nanofiber membrane as transition interlayer are 1.41 MPa and 33.22%, which are 95.8% and 67.9% higher than that of PU-CA membrane with double-layer structure without transition interlayer, separately. This indicates that PU-(CA/PU)-CA transition sandwich Janus membrane has better strength and toughness than PU-CA bilayer Janus membrane.