CN109913821A

CN109913821A - A kind of superhydrophobic film with photothermal effect and preparation method thereof

Info

Publication number: CN109913821A
Application number: CN201910184449.0A
Authority: CN
Inventors: 马菱薇; 李晓刚; 张达威
Original assignee: University of Science and Technology Beijing USTB
Current assignee: University of Science and Technology Beijing USTB
Priority date: 2019-03-12
Filing date: 2019-03-12
Publication date: 2019-06-21
Anticipated expiration: 2039-03-12
Also published as: CN109913821B

Abstract

The invention discloses a superhydrophobic film with photothermal effect and a preparation method thereof. The invention adopts the inclined growth method, firstly depositing a layer of nanostructure with photothermal effect on the surface of the substrate, and then depositing a layer of low surface energy substance on the surface thereof. The photothermal material used is titanium nitride, silver, copper or triiron tetroxide, and the low surface energy material is polytetrafluoroethylene, polyethylene, polypropylene, polystyrene or polyethylene terephthalate. The composite nanostructure prepared by the above method can be used as an anti-icing film, and the hydrophobicity of the substrate can be improved by using low surface energy substances, which can delay or prevent freezing; Ice covered surface. The thin film of the invention has a simple preparation process, has super-hydrophobicity, light heat generation ability, good anti-icing/deicing performance, and has broad application prospects.

Description

A kind of based superhydrophobic thin films and preparation method thereof with photo-thermal effect

Technical field

The present invention relates to a kind of based superhydrophobic thin films and preparation method thereof with photo-thermal effect belong to functional material technology neck Domain.

Background technique

Material surface icing caused a serious security risk to fields such as communications service, railway transportation, aviation and navigations and Property loss.Super-hydrophobic micro-nano material has unique air cushion structure, so that drop is formed on its surface solid-liquid-gas three-phase and is total to Interface is deposited, be conducive to delay or prevents to freeze.But under complicated natural environment, water droplet or water mist can inevitably exist Material surface freezes, it is therefore desirable to quickly remove surface icing using certain method.Common de-icing method has nature deicing Method, mechanical deicing's method and heating deicing method etc., wherein heating has many advantages, such as that highly reliable, process is easy, has good Deicing effect.But the method that equipment is heated with external heat source in actual operation by environment temperature, substrate sizes and Whether the limitation of equal many factors easy to disassemble.The energy of sunlight, laser etc. can be converted into heat by photothermal conversion Can, it is a kind of efficient, environmentally friendly, convenient and fast heating method.Therefore, exploitation have photo-thermal effect based superhydrophobic thin films it is anti-icing, remove The fields such as ice have great importance.

Summary of the invention

The object of the present invention is to provide a kind of based superhydrophobic thin films with photo-thermal effect, and utilize inclination growing method system The method of the standby optothermal material-low-surface energy substance composite nano film.

In order to achieve the above object, The technical solution adopted by the invention is as follows:

A kind of based superhydrophobic thin films with photo-thermal effect, which is characterized in that the film is that have photo-thermal effect by one layer The composite nano film of nanostructure and a layered low-surface energy material composition.

Further, the optothermal material is titanium nitride, silver, copper or ferroso-ferric oxide；The low-surface energy substance is poly- Tetrafluoroethene PTFE, polythene PE, polypropylene PP, polystyrene PS or polyethylene terephtalate.

Further, the photo-thermal nanostructure be straight stick, oblique stick or rifle bar array, deposition thickness be 100~ 2000nm；Low surface energy structures are straight stick, oblique stick or rifle bar array, and deposition thickness is 20~1000nm.

A kind of preparation method of the based superhydrophobic thin films as described above with photo-thermal effect, which is characterized in that including step It is as follows:

(1) the inclination growing method for utilizing electron beam deposition, deposits photo-thermal nanostructure in substrate；

(2) conversion evaporation material deposits low-surface energy substance on the top of photo-thermal nanostructure, obtains composite nanostructure As the based superhydrophobic thin films with photo-thermal effect.

Further, the method for preparing photo-thermal nanostructure using inclination growing method in step (1) are as follows: using nitridation Titanium, silver, copper or ferroso-ferric oxide are target, and electron beam evaporation deposition machine cavity room is evacuated to 10^{- 5}Pa high vacuum below, adjustment Electron beam incident angle is 80~89 °, and keeps sample stage static or at the uniform velocity rotated with the rate of 2~10rpm, utilizes electron beam evaporation plating The photo-thermal nanostructure of 100~2000nm is deposited in substrate.

Further, the method for preparing low-surface-energy nanostructure using inclination growing method in step (2) are as follows: conversion is steamed Hair material is polytetrafluoroethylene (PTFE), polyethylene, polypropylene, polystyrene or polyethylene terephthalate, and adjustment electron beam enters Firing angle is 80~88 °, and keeps sample stage static or at the uniform velocity rotated with the rate of 2~10rpm, heavy on the top of photo-thermal nanostructure The low-surface energy substance of 20~1000nm of product.

The present invention has the following advantages that and the technical effect of high-lighting: the present invention is prepared for one kind using inclination growing technology Super hydrophobic compound film with photo-thermal effect.The low-surface energy substance on surface layer has excellent ultra-hydrophobicity, and drop is super Hydrophobic micro-nano structure surface forms solid-liquid-gas three-phase coexistence interface, is conducive to delay or prevents to freeze；With photothermal conversion Luminous energy can be converted into thermal energy by the nanostructure of energy, and the heat of generation can be with the icing on melted material surface, deicing It is Cheng Gaoxiao, environmental protection, convenient.Thin film preparation process of the invention is simple, has super-hydrophobicity and illumination Thermogenesis, anti-icing/to remove Ice is had excellent performance, and is had broad application prospects.

Detailed description of the invention

Fig. 1 a is the titanium nitride-polytetrafluoroethylene (PTFE) laminated film stereoscan photograph prepared in embodiment 1；Fig. 1 b is real Apply titanium nitride-reflectance curve of the polytetrafluoroethylene (PTFE) laminated film under different angles of light, different wave length prepared in example 1.

Fig. 2 a is the contact angle photo of water on the silver-polystyrene laminated film prepared in embodiment 2；Fig. 2 b is embodiment The roll angle photo of water on the silver prepared in 2-polystyrene laminated film.

Fig. 3 is that copper-polyethylene terephthalate laminated film for preparing is under laser irradiation in embodiment 3, (a) 0 Second, (b) 15 seconds, (c) 30 seconds, (d) 50 seconds when the photo that gradually melts of surface ice sheet.

Specific embodiment

The present invention will be further explained with reference to the examples below.

The present invention is prepared for a kind of based superhydrophobic thin films with photo-thermal effect using inclination growing method.The present invention exists first Substrate surface deposits one layer of nanostructure with photo-thermal effect, then deposits a layered low-surface energy substance on its surface, this is compound Nanostructure can be used as it is anti-/ except ina thin film.Optothermal material used is titanium nitride, silver, copper or ferroso-ferric oxide, low-surface-energy object Matter is polytetrafluoroethylene (PTFE), polyethylene, polypropylene, polystyrene or polyethylene terephthalate.The laminated film utilizes low Surface energy substance improves the hydrophobicity of substrate, can delay or prevent to freeze；Photo-thermal effect produces substrate under illumination condition Raw strong temperature rise, can melt surface icing.Thin film preparation process of the invention is simple, has super-hydrophobicity and illumination heat production energy Power, anti-/ deicing is functional, has broad application prospects.

With reference to the accompanying drawing 1~3 and embodiment the present invention is illustrated.Following embodiments be it is illustrative, no It is restrictive, cannot be limited the scope of protection of the present invention with following embodiments.

Embodiment 1

1. steel disc is polished with sand paper, then it is cleaned by ultrasonic and is dried with acetone, alcohol, deionized water sequence；

2. clean substrate is fixed on the sample stage of electron beam evaporation deposition machine, and by electron beam evaporation deposition machine Chamber is evacuated to 10^{- 5}Pa high vacuum below；

3. the incidence angle for adjusting electron beam is 89 °, and keeps sample stage static, oblique in the titanium nitride of deposition on substrate 200nm Stick array；

4. converting evaporation material as polytetrafluoroethylene (PTFE), the incidence angle for adjusting electron beam is 82 °, and makes sample stage with 2rpm's Rotational speed, in the polytetrafluoroethylene (PTFE) of the top of the oblique stick array of titanium nitride deposition 100nm.

Fig. 1 a is the titanium nitride-polytetrafluoroethylene (PTFE) laminated film stereoscan photograph prepared in embodiment 1；Fig. 1 b is real Apply titanium nitride-reflectance curve of the polytetrafluoroethylene (PTFE) laminated film under different angles of light, different wave length prepared in example 1. Fig. 1 a is it will be clear that the oblique stick array (layer 1) of titanium nitride nano and low-surface energy substance layer (layer 2), two layers of equal discreteness are good It is good.Fig. 1 b illustrates that prepared titanium nitride-polytetrafluoroethylene (PTFE) laminated film all has in visible light and near infrared wavelength region Lower reflectivity, absorptivity are more than 95%, help to convert thermal energy for the luminous energy of absorption.

Embodiment 2

1. aluminium flake is polished with sand paper, then it is cleaned by ultrasonic and is dried with acetone, alcohol, deionized water sequence；

3. the incidence angle for adjusting electron beam is 85 °, and makes sample stage with the rotational speed of 4rpm, in deposition on substrate The straight stick array of the silver of 1000nm；

4. converting evaporation material as polystyrene, the incidence angle for adjusting electron beam is 85 °, and turns sample stage with 5rpm Speed rotation, in the polystyrene of the top deposition 500nm of silver-colored straight stick array.

Fig. 2 is the contact angle and roll angle photo of water on the silver-polystyrene laminated film prepared in embodiment 2.Due to The surface of polystyrene can be very low, and the porosity of nanorod structure is very big, therefore pipe/polyhenylethylene nano structure is with very big Roll angle~2 ° of water contact angle~156.2 ° and very little.This advantageously reduces the probability that drop stops on the surface of the material, can be with Delay or prevents to freeze.

Embodiment 3

1. magnesium alloy plate is polished with sand paper, then it is cleaned by ultrasonic and is dried with acetone, alcohol, deionized water sequence；

3. the incidence angle for adjusting electron beam is 82 °, and makes sample stage with the rotational speed of 10rpm, in deposition on substrate The straight stick array of the copper of 2000nm；

4. converting evaporation material as polyethylene terephtalate, the incidence angle for adjusting electron beam is 88 °, and is made Sample stage is static, in the PET of the top of the straight stick array of copper deposition 1000nm.

Fig. 3 be with the copper prepared in embodiment 3-polyethylene terephtalate laminated film under laser irradiation, The photo that surface ice sheet gradually melts.Since the nanostructure of copper has surface plasma volume property, in the photograph of certain wavelength light Surface plasma body resonant vibration can occur under penetrating, convert light energy into thermal energy, the heat that photo-thermal effect generates can be with melted material Surface icing.

Claims

1. a super-hydrophobic film with photothermal effect, is characterized in that, this film is the composite nano-film that one layer has the nanostructure with photothermal effect and one layer of low surface energy material composition.

2. The superhydrophobic film with photothermal effect as claimed in claim 1, wherein the photothermal material is titanium nitride, silver, copper or ferric oxide; the low surface energy material is polytetrafluoroethylene Ethylene PTFE, polyethylene PE, polypropylene PP, polystyrene PS or polyethylene terephthalate PET.

3. a super-hydrophobic film with photothermal effect as claimed in claim 1, is characterized in that, photothermal nanostructure is straight rod, oblique rod or helical rod array, and deposition thickness is 100～2000nm; Low surface energy structure is Arrays of straight rods, inclined rods or helical rods with a deposition thickness of 20 to 1000 nm.

4. the preparation method of the super-hydrophobic film with photothermal effect as claimed in claim 1-3, is characterized in that, comprises the steps as follows:

(1) Deposition of photothermal nanostructures on the substrate by the oblique growth method of electron beam deposition;

(2) Converting the evaporation material, depositing low surface energy substances on the top of the photothermal nanostructure, and obtaining the composite nanostructure as a superhydrophobic film with photothermal effect.

5. the preparation method of the super-hydrophobic thin film with photothermal effect as claimed in claim 4, is characterized in that, utilizes the inclined growth method in step (1) to prepare the method for photothermal nanostructure: adopt titanium nitride, silver , copper or ferric tetroxide as the target material, pump the chamber of the electron beam evaporation coating machine to a high vacuum below ^10-5 Pa, adjust the incident angle of the electron beam to 80-89°, and make the sample stage static or at 2- The photothermal nanostructures of 100-2000 nm were deposited on the substrate by electron beam evaporation with uniform rotation at a rate of 10 rpm.

6. the preparation method of the super-hydrophobic thin film with photothermal effect as claimed in claim 4, is characterized in that, utilizes the method of inclined growth method to prepare low surface energy nanostructure in step (2) as: conversion evaporation material is polymer tetrafluoroethylene, polyethylene, polypropylene, polystyrene or polyethylene terephthalate, adjust the incident angle of the electron beam to 80-88°, and make the sample stage stand still or rotate at a constant speed of 2-10rpm, A low surface energy substance of 20-1000 nm is deposited on the top of the photothermal nanostructure.