Sunshine Factory, Co., Ltd. > Applications > ZrP for PolymerZrP for Polymer
A hierarchical, self-healing, and superhydrophobic hybrid membrane
1.INTRODUCTION
Here, there are researchers report the ability of lyotropic Zirconium Phosphate(ZrP) platelets to assemble into a super hydrophobic hierarchical architecture on fabrics that autonomously and recurrently heal damage of chemical oxidation at room temperature.
Their approach was predicated on the structural orientations of ZrP which generate robust layers to protect and separate the healing agent, to prevent the penetration of oxidative species.
2D platelets were produced by in situ growth of lyotropic ZrP on one-dimensional textile fibers governed by structural orientation.
Taking advantage of the strong bonding of ZrP with amine species, they introduced the healing agent octadecyl-amine (ODA) into the layered architecture of ZrP.
Therefore,the ZrP-functionalized hybrid membrane (ZrPM) revealed a complex, graded structure consisting of hydrophobic ODA,supported in the layered architecture, lyotropic ZrP platelets,aligned parallel to the fiber surface, and textile platform(Scheme 1).Schematic Demonstration of Hierarchical Structure in ZrPM.
The robust layers of ZrP platelets prevented the permeation and penetration of oxidative species, protecting healing reagents from chemical oxidation.
During repairing, the healing reagent was able to transport to the hybrid membrane surface, restoring the wettability. Meanwhile, the ZrP-coated superhydrophobic fabric demonstrated efficient oil-water separation with good durability, making it applicable to practical applications.
2. RESULTS AND DISCUSSION
2.1. Synthesis and Surface Chemistry of ZrPM.
Figure 1.Synthesis and analysis of ZrPM. (a) Schematic representations of ZrPM preparation. (b) Phase diagrams for simulated discotic systems.(c,d) High-resolution (c) C1s and (d) Zr3d spectra of ZrPM. (e) N1s spectra of pristine fabrics and ZrPM.
Figure 2. Morphological analysis of membranes. (a−c) SEM images of (a) textile, (b) ZrP-coated textile, and (c) ZrPM. (d−f) High-magnification SEM images of (d) textile, (e) ZrP-coated textile, and (f) ZrPM. The scale bars of insets are 2 μm for (e) and (f). (g) High-magnification SEM image of individual ZrP-coated fiber along with EDS mappings of (h) C, (i) Zr, and (j) P.
2.2. Oil−Water Separation and Flux Performance.
Figure 3. Wettability and separating efficiencies of the ZrPM. (a)Images of water CA (inset: oil CA). (b) CA values of H 2 O, 0.1 M NaCl, 1 M NaCl, and saturated NaCl solutions on ZrPM. (c) Separation apparatus upon adding the oil−water mixture. (d) Dodecane infiltrates through ZrPM while aqueous phase is separated(water is dyed blue, Supporting Information Movie S1). (e) Microscopic images of aqueous phase before (up) and after filtration (down). (f) The separating efficiency of ZrPM in presence of various salts. (g) The separating efficiency of ZrPM in acidic, neutral, and alkaline environments.
Figure 4. Durability and flux test of the ZrPM. (a) Separating efficiency of ZrPM over 25 cycles. (b) Water CAs of ZrPM over different cycles. (c) Volumetric flux rates of ZrPM with various types of oils.
2.3. Self-Healing Performance.
Figure 5. Self-healing ability of the ZrPM. (a−c) Water CA (a) of the ZrPM, (b) of plasma-treated fabrics before, and (c) after healing at room temperature for 48 h. (d−i) Images of liquid drops of (d−f) water and (g−i) oil placed on different surfaces (inset: images of water drops on ZrPM after thermal healing). (j) Separation efficiencies of the above three kinds of membranes (insets: images of separated aqueous phases accordingly).(k) The water CAs of membranes over different etching−healing cycles.
Figure 6. Proposed self-healing mechanism of ZrPM. (a) As-prepared ZrPM fiber. (b) Cross-sectional ZrPM fiber. (c) Surface-damaged ZrPM. (d) Surface-damaged ZrPM during self-healing process. (e) Surface-healed ZrPM. After the outmost layer of ODA was oxidized by the air plasma,ZrPM formed a hydrophilic surface that was thermodynamically unstable due to high surface energy.
3. CONCLUSION
In conclusion, they developed a hierarchical, self-healing, and Super hydrophobic hybrid membrane via an in situ growth of lyotropic ZrP nanoplates on fabrics.
They demonstrated that the concept of hierarchical assembly of anisotropic nanoparticles can be generalized to design structural materials with recurrent self-healing behavior.
The surface chemistry of ZrPM was confirmed by XPS, and the graded structure was confirmed by SEM analysis. In consequence of the lamellar arrangement structure of ZrP, the ZrPM not only separated oil and water in harsh environments but also showed good durability with high separation efficiencies.
Furthermore, we demonstrated that the ZrPM, after damaged by air-plasma, can restore its hydro-phobicity automatically and repeatedly.
This unique self-healing behavior suggested strong potential for significantly prolonging the duration of hydrophobic membranes against possible oxidation or strong UV light.
The present approach is facile without involving highly toxic reagents or expensive catalysts, indicating strong potential for a wide range of applications such as water treatment, fuel purification,and the cleanup of oil spills.
Article in ACS Applied Materials & Interfaces · June 2018
Here, there are researchers report the ability of lyotropic Zirconium Phosphate(ZrP) platelets to assemble into a super hydrophobic hierarchical architecture on fabrics that autonomously and recurrently heal damage of chemical oxidation at room temperature.
Their approach was predicated on the structural orientations of ZrP which generate robust layers to protect and separate the healing agent, to prevent the penetration of oxidative species.
2D platelets were produced by in situ growth of lyotropic ZrP on one-dimensional textile fibers governed by structural orientation.
Taking advantage of the strong bonding of ZrP with amine species, they introduced the healing agent octadecyl-amine (ODA) into the layered architecture of ZrP.
Therefore,the ZrP-functionalized hybrid membrane (ZrPM) revealed a complex, graded structure consisting of hydrophobic ODA,supported in the layered architecture, lyotropic ZrP platelets,aligned parallel to the fiber surface, and textile platform(Scheme 1).Schematic Demonstration of Hierarchical Structure in ZrPM.
The robust layers of ZrP platelets prevented the permeation and penetration of oxidative species, protecting healing reagents from chemical oxidation.
During repairing, the healing reagent was able to transport to the hybrid membrane surface, restoring the wettability. Meanwhile, the ZrP-coated superhydrophobic fabric demonstrated efficient oil-water separation with good durability, making it applicable to practical applications.
2. RESULTS AND DISCUSSION
2.1. Synthesis and Surface Chemistry of ZrPM.
Figure 1.Synthesis and analysis of ZrPM. (a) Schematic representations of ZrPM preparation. (b) Phase diagrams for simulated discotic systems.(c,d) High-resolution (c) C1s and (d) Zr3d spectra of ZrPM. (e) N1s spectra of pristine fabrics and ZrPM.
Figure 2. Morphological analysis of membranes. (a−c) SEM images of (a) textile, (b) ZrP-coated textile, and (c) ZrPM. (d−f) High-magnification SEM images of (d) textile, (e) ZrP-coated textile, and (f) ZrPM. The scale bars of insets are 2 μm for (e) and (f). (g) High-magnification SEM image of individual ZrP-coated fiber along with EDS mappings of (h) C, (i) Zr, and (j) P.
2.2. Oil−Water Separation and Flux Performance.
Figure 3. Wettability and separating efficiencies of the ZrPM. (a)Images of water CA (inset: oil CA). (b) CA values of H 2 O, 0.1 M NaCl, 1 M NaCl, and saturated NaCl solutions on ZrPM. (c) Separation apparatus upon adding the oil−water mixture. (d) Dodecane infiltrates through ZrPM while aqueous phase is separated(water is dyed blue, Supporting Information Movie S1). (e) Microscopic images of aqueous phase before (up) and after filtration (down). (f) The separating efficiency of ZrPM in presence of various salts. (g) The separating efficiency of ZrPM in acidic, neutral, and alkaline environments.
Figure 4. Durability and flux test of the ZrPM. (a) Separating efficiency of ZrPM over 25 cycles. (b) Water CAs of ZrPM over different cycles. (c) Volumetric flux rates of ZrPM with various types of oils.
2.3. Self-Healing Performance.
Figure 5. Self-healing ability of the ZrPM. (a−c) Water CA (a) of the ZrPM, (b) of plasma-treated fabrics before, and (c) after healing at room temperature for 48 h. (d−i) Images of liquid drops of (d−f) water and (g−i) oil placed on different surfaces (inset: images of water drops on ZrPM after thermal healing). (j) Separation efficiencies of the above three kinds of membranes (insets: images of separated aqueous phases accordingly).(k) The water CAs of membranes over different etching−healing cycles.
Figure 6. Proposed self-healing mechanism of ZrPM. (a) As-prepared ZrPM fiber. (b) Cross-sectional ZrPM fiber. (c) Surface-damaged ZrPM. (d) Surface-damaged ZrPM during self-healing process. (e) Surface-healed ZrPM. After the outmost layer of ODA was oxidized by the air plasma,ZrPM formed a hydrophilic surface that was thermodynamically unstable due to high surface energy.
3. CONCLUSION
In conclusion, they developed a hierarchical, self-healing, and Super hydrophobic hybrid membrane via an in situ growth of lyotropic ZrP nanoplates on fabrics.
They demonstrated that the concept of hierarchical assembly of anisotropic nanoparticles can be generalized to design structural materials with recurrent self-healing behavior.
The surface chemistry of ZrPM was confirmed by XPS, and the graded structure was confirmed by SEM analysis. In consequence of the lamellar arrangement structure of ZrP, the ZrPM not only separated oil and water in harsh environments but also showed good durability with high separation efficiencies.
Furthermore, we demonstrated that the ZrPM, after damaged by air-plasma, can restore its hydro-phobicity automatically and repeatedly.
This unique self-healing behavior suggested strong potential for significantly prolonging the duration of hydrophobic membranes against possible oxidation or strong UV light.
The present approach is facile without involving highly toxic reagents or expensive catalysts, indicating strong potential for a wide range of applications such as water treatment, fuel purification,and the cleanup of oil spills.
Article in ACS Applied Materials & Interfaces · June 2018
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