Bicomponent superhydrophobic fibers and methods of making the same
By melt-blending nano-SiO2 with PET and treating it with gradient temperature control in alkaline water, a bicomponent superhydrophobic fiber with excellent superhydrophobic properties and good mechanical properties is prepared. This solves the problems of weak bonding force, expensive equipment, complex process and insufficient durability in the existing technology, and is suitable for self-cleaning textiles and oil-water separation materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- WUHAN TEXTILE UNIV
- Filing Date
- 2025-12-17
- Publication Date
- 2026-04-28
AI Technical Summary
Existing methods for preparing superhydrophobic fibers suffer from problems such as weak bonding, expensive equipment, complex processes, poor mechanical properties, and insufficient durability, making it difficult to meet the needs of practical applications.
Hydrophobically modified nano-SiO2 was melt-blended and granulated with PET, and SiO2/PET fibers were prepared by melt spinning. The fibers were then treated in alkaline water at 110-130℃ using a three-stage gradient temperature control process to dissolve the PET on the surface of the fibers, thus constructing a micro-nano composite roughness.
A two-component superhydrophobic fiber with excellent superhydrophobic properties, good mechanical properties and strong durability has been developed, with a static water contact angle ≥155°, which is suitable for self-cleaning textiles, oil-water separation materials and anti-fouling coatings.
Smart Images
Figure CN121344807B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of composite fiber preparation technology, specifically to a two-component superhydrophobic fiber and its preparation method. Background Technology
[0002] Superhydrophobic materials, due to their unique self-cleaning, antifouling, and anti-corrosion properties, have broad application prospects in textiles, construction, medicine, marine engineering, and other fields. A superhydrophobic surface is generally defined as one with a water contact angle greater than 150°. The key to achieving superhydrophobic properties lies in constructing suitable micro / nano rough structures and reducing surface energy.
[0003] Currently, the main methods for preparing superhydrophobic fibers include surface coating, plasma treatment, and chemical vapor deposition. However, these methods have the following problems: 1) The superhydrophobic coating prepared by surface coating has weak adhesion to the substrate and is prone to peeling off during use, leading to a decrease in superhydrophobic performance; 2) Plasma treatment and chemical vapor deposition methods involve expensive equipment and complex processes, making large-scale production difficult; 3) Existing superhydrophobic fibers have poor mechanical properties, making it difficult to meet practical application requirements; 4) The durability of superhydrophobic properties is insufficient, and the performance deteriorates significantly after repeated washing or friction.
[0004] Therefore, there is an urgent need to develop a method for preparing superhydrophobic fibers that is simple to manufacture, has excellent superhydrophobic properties, good mechanical properties, and good durability. Summary of the Invention
[0005] In view of the technical problems existing in the background art, this application provides a method for preparing bicomponent superhydrophobic fibers. The method involves melt-blending and granulating hydrophobically modified nano-SiO2 with PET (polyethylene terephthalate), followed by melt spinning to obtain bicomponent hydrophobic SiO2 / PET fibers. Subsequently, the SiO2 / PET fibers are immersed in alkaline water at 110-130℃ and treated with a three-stage gradient temperature control process for 4-6 hours to dissolve the surface PET layer in the bicomponent fibers, thus obtaining the bicomponent superhydrophobic fibers. Specifically, the three-stage gradient temperature control process involves treating the SiO2 / PET fibers at 110-115℃ (ah), at 115-120℃ (bh), and at 120-130℃ (ch) to construct micro-nano composite roughness on the surface of the bicomponent superhydrophobic fibers.
[0006] Specifically, the surface of the prepared bicomponent superhydrophobic fiber has several nanopores with a diameter of 80-250 nm and protrusions with a height of 10-50 nm, and a pore depth of 1.0-3.0 μm. The surface porosity of the bicomponent superhydrophobic fiber is 25-55%, which ensures the exposure of hydrophobic silica nanoparticles, so that water droplets are in the Cassie-Baxter state, with a static water contact angle ≥155°, and has excellent superhydrophobicity, mechanical properties and durability.
[0007] In a first aspect, embodiments of this application provide a method for preparing a two-component superhydrophobic fiber, comprising the following steps:
[0008] S1, PET masterbatch is uniformly mixed with hydrophobically modified nano-SiO2 particles, and then melt-extruded and granulated to obtain SiO2 / PET composite masterbatch;
[0009] S2, a bicomponent hydrophobic SiO2 / PET fiber was prepared by melt spinning;
[0010] S3, the SiO2 / PET fibers obtained in step S2 are soaked in alkaline water at 110-130℃ and treated with a three-stage gradient temperature control process for 4-6 hours to dissolve the PET on the surface of the fibers and obtain dual superhydrophobic fibers; the three-stage gradient temperature control process is specifically to treat the SiO2 / PET fibers at 110-115℃ for ah, at 115-120℃ for bh, and at 120-130℃ for ch, where a:b:c=(1-2):(1-1.5):1.
[0011] Furthermore, the value of a ranges from 1 to 2h.
[0012] Furthermore, the heating rate during the three-stage gradient temperature control process is 3-5℃ / h.
[0013] Furthermore, in step S1, the content of nano-SiO2 particles in the SiO2 / PET composite masterbatch is 10-20 wt%.
[0014] Furthermore, the hydrophobically modified nano-SiO2 particles have a particle size of 35-50 nm.
[0015] Furthermore, in step S3, the intrinsic viscosity of the PET masterbatch is 0.68-0.75 dL / g.
[0016] Secondly, embodiments of this application provide a bicomponent superhydrophobic fiber, which is prepared using any of the aforementioned preparation methods.
[0017] Furthermore, the surface of the bicomponent superhydrophobic fiber has several nanopores with a diameter of 80-250 nm, protrusions with a height of 10-50 nm, and a pore depth of 1.0-3.0 μm; the surface porosity of the bicomponent superhydrophobic fiber is 25-55%.
[0018] The beneficial effects of this application are as follows:
[0019] This application provides a method for preparing bicomponent superhydrophobic fibers. By immersing SiO2 / PET fibers in alkaline water at 110-130℃ and treating them using a three-stage gradient temperature control process for 4-6 hours, a micro-nano composite roughness is constructed on the surface of the bicomponent superhydrophobic fibers, achieving excellent superhydrophobic properties with a static water contact angle ≥155°. In this application, the hydrophobically modified nano-SiO2 particles are embedded in the fiber matrix, making them less prone to detachment and ensuring the durability of the superhydrophobic properties. Furthermore, the bicomponent structural design retains the basic mechanical properties of PET fibers, while the reinforcement effect of nano-SiO2 improves the surface roughness of the fibers, achieving a Cassie-Baxter state.
[0020] This application employs a method combining melt spinning and alkali treatment, which is simple and easy to industrialize.
[0021] This bicomponent superhydrophobic fiber can be applied to self-cleaning textiles, oil-water separation materials, anti-fouling coatings, and other fields.
[0022] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of this application more obvious and understandable, the following are specific embodiments of this application. Attached Figure Description
[0023] To more clearly illustrate the technical solution of this application, the accompanying drawings used in this application will be briefly described below. Obviously, the drawings described below are merely some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without any creative effort.
[0024] Figure 1 This is a SEM image of the bicomponent superhydrophobic fiber prepared in Example 1.
[0025] Figure 2 This is a schematic diagram of the structure of the two-component superhydrophobic fiber of this application, wherein the red area refers to PET, the yellow area refers to hydrophobic modified SiO2 nanoparticles, and the dark blue area refers to the morphology of droplets on the fiber surface.
[0026] Figure 3The image shows the hydrophobic effect of the bicomponent superhydrophobic fiber bundles prepared in Example 1.
[0027] Figure 4 The image shows the hydrophobic effect of a single bicomponent superhydrophobic fiber prepared in Example 1.
[0028] Figure 5 This is a SEM image of the bicomponent superhydrophobic fiber prepared in Example 2. Detailed Implementation
[0029] The embodiments of the technical solution of this application will now be described in detail with reference to the accompanying drawings. These embodiments are only used to more clearly illustrate the technical solution of this application and are therefore merely examples, and should not be used to limit the scope of protection of this application.
[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the application; the terms “comprising” and “having”, and any variations thereof, in the specification, claims, and foregoing description of the drawings are intended to cover non-exclusive inclusion.
[0031] In the description of the embodiments of this application, technical terms such as "first" and "second" are used only to distinguish different objects and should not be construed as indicating or implying relative importance or implicitly specifying the number, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, "multiple" means two or more, unless otherwise explicitly defined.
[0032] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.
[0033] In the description of the embodiments of this application, the term "and / or" is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. Additionally, the character " / " in this document generally indicates that the preceding and following related objects have an "or" relationship. Those skilled in the art can understand the specific meaning of the above terms in the embodiments of this application according to the specific circumstances.
[0034] In a first aspect, embodiments of this application provide a method for preparing a two-component superhydrophobic fiber, comprising the following steps:
[0035] S1. PET masterbatch is uniformly mixed with hydrophobically modified nano-SiO2 particles, and then melt-extruded and granulated to obtain SiO2 / PET composite masterbatch.
[0036] Among them, the hydrophobically modified nano-SiO2 particles have a particle size of 35-50nm.
[0037] The intrinsic viscosity of PET masterbatch is 0.68-0.75 dL / g.
[0038] In the SiO2 / PET composite masterbatch, the content of nano-SiO2 particles accounts for 10-20 wt%.
[0039] As the SiO2 particle content increases, the number of pores on the surface of the bicomponent fiber increases and the roughness increases after the alkaline water treatment in step S3. When the SiO2 particle content is too high, particle agglomeration increases, forming a small number of large pores and the roughness decreases.
[0040] S2, a bicomponent hydrophobic SiO2 / PET fiber was prepared by melt spinning;
[0041] S3. The SiO2 / PET fibers obtained in step S2 are soaked in alkaline water at 110-130℃ and treated with a three-stage gradient temperature control process for 4-6 hours to dissolve the PET on the surface of the fibers, thus obtaining dual superhydrophobic fibers.
[0042] The three-stage gradient temperature control process involves treating SiO2 / PET fibers at 110-115℃ (ah), 115-120℃ (bh), and 120-130℃ (ch), with a:b:c = (1-2):(1-1.5):1.
[0043] The value of a ranges from 1 to 2h.
[0044] The heating rate during the three-stage gradient temperature control process is 3-5℃ / h.
[0045] Secondly, this application also provides a bicomponent superhydrophobic fiber, which is prepared using any of the aforementioned technical solutions.
[0046] The surface of the bicomponent superhydrophobic fiber has several nanopores with a diameter of 80-250 nm and protrusions with a height of 10-50 nm, and the pore depth is 1.0-3.0 μm; the surface porosity of the bicomponent superhydrophobic fiber is 25-55%.
[0047] The following are some specific embodiments. It should be noted that the embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.
[0048] Example 1
[0049] Example 1 provides a method for preparing a two-component superhydrophobic fiber, comprising the following steps:
[0050] S1, Preparation of hydrophobically modified nano-SiO2 particles:
[0051] 10g of 50nm nano-SiO2 particles were dispersed in 200mL of anhydrous ethanol and ultrasonically dispersed for 30min. 5mL of hexadecyltrimethoxysilane was added, and the mixture was refluxed at 60℃ for 6h. After the reaction was completed, the mixture was centrifuged, washed three times with ethanol, and vacuum dried at 80℃ for 12h to obtain hydrophobically modified nano-SiO2 particles.
[0052] Preparation of SiO2 / PET composite masterbatch:
[0053] 2 kg of PET masterbatch was vacuum dried at 120°C for 4 hours.
[0054] 200g of hydrophobically modified nano-SiO2 particles were mixed with 1.8kg of dry PET masterbatch at a mass fraction of 10wt% using a twin-screw extruder. The mixture was then melt-blended at 270℃ and extruded to granulate, yielding a SiO2 / PET composite masterbatch.
[0055] S2, the SiO2 / PET composite masterbatch was vacuum dried at 120℃ for 4 hours. Hydrophobic SiO2 / PET fibers with a diameter of approximately 20 μm were prepared using a melt spinning apparatus with a spinning temperature of 270℃ and a spinning speed of 2000 m / min.
[0056] S3, prepare a 3 mol / L sodium hydroxide solution.
[0057] Hydrophobic SiO2 / PET fibers are immersed in an alkaline solution (sodium hydroxide solution) and treated with a three-stage gradient temperature control process to dissolve the PET on the surface of the fibers, thus obtaining dual superhydrophobic fibers.
[0058] Specifically, SiO2 / PET fibers were treated at 110℃ for 2 hours, at 120℃ for 2 hours, and at 130℃ for 2 hours. After treatment, the fibers were thoroughly washed with deionized water until neutral and then vacuum dried at 60℃ to obtain bicomponent superhydrophobic fibers.
[0059] Please see Figures 1 to 2 As shown, the surface of the bicomponent superhydrophobic fiber prepared in Example 1 has several nanopores with a diameter of 80-250 nm, protrusions with a height of 10-50 nm, a pore depth of 1.0-3.0 μm, and a surface porosity of 55%.
[0060] Tests showed that the bicomponent superhydrophobic fiber prepared in Example 1 had a breaking strength of 5.2 cN / dtex and an elastic modulus of 13 GPa.
[0061] Figure 3 and Figure 4 The image shows the hydrophobic effect of the bicomponent superhydrophobic fiber prepared in Example 1. It can be seen that neither a single fiber nor a fiber cluster is water-repellent, demonstrating excellent hydrophobic properties.
[0062] Example 2
[0063] The difference between Example 2 and Example 1 is that in step S2, the content of nano-SiO2 particles in the SiO2 / PET composite masterbatch is 20wt%, while the rest is the same as in Example 1, and will not be repeated here.
[0064] SEM image of the bicomponent superhydrophobic fiber prepared in Example 2 is shown below. Figure 5 As shown.
[0065] As can be seen, the surface of the bicomponent superhydrophobic fiber has several pores with a diameter of 1-3 μm and protrusions with a height of 100-200 nm.
[0066] The bicomponent superhydrophobic fiber prepared in Example 2 has a breaking strength of 4.0 cN / dtex and an elastic modulus of 10 GPa.
[0067] Comparative Example 1
[0068] The difference between Comparative Example 1 and Example 1 is that in step S4, the SiO2 / PET fibers are treated at 85°C for 2 hours, at 90°C for 1 hour, and at 95°C for 3 hours, with a heating rate of 5°C / hour. The rest is the same as in Example 1 and will not be repeated here.
[0069] Comparative Example 2
[0070] The difference between Comparative Example 2 and Example 1 is that step S3 was not performed. Everything else is the same as in Example 1, and will not be repeated here.
[0071] Experiments show that the composite fiber prepared in Comparative Example 2 has a smooth, non-porous surface and a specific surface area of 29 m². 2 / g, with a tensile strength of 5.5cN / dtex and an elastic modulus of 15GPa.
[0072] Comparative Example 3
[0073] The difference between Comparative Example 3 and Example 1 is that in step S3, SiO2 / PET fibers were directly soaked in 80°C hot water for 6 hours. The rest is the same as in Example 1 and will not be repeated here.
[0074] Comparative Example 4
[0075] The difference between Comparative Example 4 and Example 1 is that in step S3, SiO2 / PET fibers were directly soaked in 95°C hot water for 6 hours. The rest is the same as in Example 1, and will not be repeated here.
[0076] Comparative Example 5
[0077] The difference between Comparative Example 5 and Example 1 is that in step S3, a gradient cooling process is used, specifically a three-stage gradient temperature control process of 95℃→90℃→80℃. The SiO2 / PET fibers are treated at 95℃ for 3 h, at 90℃ for 1 h, and at 80℃ for 2 h. The heating rate is 5℃ / h. The rest is the same as in Example 1, and will not be repeated here.
[0078] The hydrophobic properties of the composite fibers prepared in Examples 1-2 and Comparative Examples 1-5 were tested according to the FZ / T 50040-2018 Test Method for Hydrophilic Properties of Short Chemical Fibers. The test results are shown in Table 1.
[0079] Table 1. Performance summary of Examples 1-2 and Comparative Examples 1-5
[0080]
[0081] Comparing Example 1 with Comparative Example 1, it can be seen that when the temperature treatment time in the third stage is too long, the pores become too deep, causing the silica to fall off and form large pores without protrusions, reducing the roughness and thus decreasing the hydrophobicity.
[0082] Comparing Example 1 and Comparative Example 2, it can be seen that without the three-stage heating treatment, the fiber skin surface has no porous structure, and the silica encapsulated by PET cannot be exposed. Only a small amount of silica particles on the outer layer play a role in improving the roughness.
[0083] Comparing Example 1 and Comparative Example 3, it can be seen that when only a relatively low temperature is used for treatment, a small number of pores are formed on the surface of the fiber skin, the pore size is small, the nano-sized protrusions are low, the roughness is low, and the hydrophobicity is reduced.
[0084] Comparing Example 1 and Comparative Example 4, it can be seen that when only a relatively high temperature is used for treatment, the long-term high-temperature treatment causes PET itself to begin to dissolve, in addition to the weak interface where silicon dioxide and PET come into contact. As a result, a large number of large pores are formed, making it impossible to form nano-sized protrusions and reducing hydrophobicity.
[0085] Comparing Example 1 with Comparative Example 5, it can be seen that the initial temperature is too high, which causes the hydrophilic PET itself to begin to dissolve in addition to the weak interface where silica and hydrophilic PET come into contact, forming a small number of small pores. Once pores appear, they will continue to grow larger under continuous high temperature treatment, eventually forming a large number of large pores, making it impossible to form nano-sized protrusions and reducing hydrophobicity.
[0086] According to AATCC 61-2013e(2020) Colorfastness to Laundering: Accelerated standard, the composite fibers prepared in Examples 1-2 and Comparative Examples 1-5 were subjected to 50 standard washes. The fiber surface was imaged using a scanning electron microscope (SEM) under the same magnification and sampling conditions, and the number density of silica particles per unit area (particles / μm) was statistically analyzed by image analysis. 2 ), denoted as n0; after washing, obtain n using the same method. 50 The durability of the coating is characterized by the particle retention rate R, calculated as R = (n 50 / n0)×100%. The hydrophobic properties of the samples after washing were also tested, expressed as wicking height. The data are shown in Table 2.
[0087] Table 2. SiO2 particle retention and hydrophobicity of fibers after 50 standard washes
[0088]
[0089] As shown in the table above, the bicomponent superhydrophobic fiber prepared in this application has good wash resistance, and the SiO2 particle retention rate reaches 95-98% after 50 standard washes.
[0090] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.
Claims
1. A method for preparing a bicomponent superhydrophobic fiber, characterized in that, Includes the following steps: S1, PET masterbatch is uniformly mixed with hydrophobically modified nano-SiO2 particles, and then melt-extruded and granulated to obtain SiO2 / PET composite masterbatch; the content of nano-SiO2 particles in the SiO2 / PET composite masterbatch is 10-20 wt%. S2, bicomponent hydrophobic SiO2 / PET fibers were prepared by melt spinning; S3, the SiO2 / PET fibers obtained in step S2 are soaked in alkaline water at 110-130℃ and treated with a three-stage gradient temperature control process for 4-6 hours to dissolve the PET on the surface of the fibers and obtain dual superhydrophobic fibers; the three-stage gradient temperature control process is specifically to treat the SiO2 / PET fibers at 110-115℃ for ah, at 115-120℃ for bh, and at 120-130℃ for ch, where a:b:c=(1-2):(1-1.5):
1.
2. The method for preparing bicomponent superhydrophobic fibers according to claim 1, characterized in that, The value of a ranges from 1 to 2h.
3. The method for preparing bicomponent superhydrophobic fibers according to claim 1, characterized in that, The heating rate during the three-stage gradient temperature control process is 3-5℃ / h.
4. The method for preparing bicomponent superhydrophobic fibers according to claim 1, characterized in that, The hydrophobically modified nano-SiO2 particles have a particle size of 35-50 nm.
5. The method for preparing bicomponent superhydrophobic fibers according to claim 1, characterized in that, In step S3, the intrinsic viscosity of the PET masterbatch is 0.68-0.75 dL / g.
6. A bicomponent superhydrophobic fiber, characterized in that, The bicomponent superhydrophobic fiber is prepared by any one of the preparation methods described in claims 1-5.
7. The bicomponent superhydrophobic fiber according to claim 6, characterized in that, The surface of the bicomponent superhydrophobic fiber has several nanopores with a diameter of 80-250 nm and protrusions with a height of 10-50 nm, and the pore depth is 1.0-3.0 μm; the surface porosity of the bicomponent superhydrophobic fiber is 25-55%.