CN101537703B

CN101537703B - Method for preparing polymer superhydrophobic surface by CaCO3 template method

Info

Publication number: CN101537703B
Application number: CN2009100980564A
Authority: CN
Inventors: 冯杰; 钟明强; 郑建勇
Original assignee: Zhejiang University of Technology ZJUT
Current assignee: Zhejiang University of Technology ZJUT
Priority date: 2009-04-24
Filing date: 2009-04-24
Publication date: 2011-06-29
Anticipated expiration: 2029-04-24
Also published as: CN101537703A

Abstract

The invention provides a method for preparing a polymer superhydrophobic surface by a CaCO3 template method, comprising the following steps of: firstly adhering a thin CaCO3 layer with the thickness of 0.1 to 20mm and the particles of 800 to 3000 meshes on a plane or a roll surface base; then hot pressing a polymer on the thin CaCO3 layer, and after peeling off a composite layer, and finally immersing the polymer in an acid liquor to corrode the calcium carbonate particles on the surface of the polymer, thus obtaining the polymer superhydrophobic surface with irregular network structure. The invention mainly has the following beneficial effects that the method has simple operation technology, low cost, high efficiency, and good controllability and repeatability, furthermore, the method iseasy for large-area preparation, and provides a simple and effective way for the industrialization of the superhydrophobic surface, thus having wide application value and broad market prospect.

Description

A kind of CaCO＜sub〉3＜/sub〉template prepares the method for polymer super-hydrophobic surface

(1) technical field

The present invention relates to a kind of CaCO ₃Template prepares the method for polymer super-hydrophobic surface.

(2) background technology

In recent years, along with the raising that people require quality of life, the super-hydrophobic and automatically cleaning phenomenon of occurring in nature has caused people's extensive concern.Super hydrophobic surface generally is meant static contact angle with water, and roll angle is less than 10 ° surface greater than 150 °, and result of study shows, the micron-nanometer structure is that to form super hydrophobic surface necessary.Because super hydrophobic surface has broad application prospects at waterproof, antifog, snow defence, aspect such as dustproof, people have developed the technology on multiple constructing super-drainage surface.At present the method for artificial preparation super hydrophobic surface have a variety of, for example etching method, be separated and self-assembly method, hydro-thermal method, chemical deposition and electrodeposition process, sol-gel process, method of electrostatic spinning, mould template method, nano silicon method, etch etc.But raw material that these methods adopted or equipment are relatively more expensive, and perhaps the preparation condition harshness wastes time and energy, and especially is difficult to prepare large-area based superhydrophobic thin films, thereby has limited their practical application.

(3) summary of the invention

The purpose of this invention is to provide a kind of simple, cheap, method that can the large-area preparation super hydrophobic surface.

The technical solution used in the present invention is:

A kind of CaCO ₃Template prepares the method for polymer super-hydrophobic surface, earlier on the plane or roll surface substrate upper berth one deck have certain thickness CaCO ₃Thin layer, hot pressing polymer thereon then, after composite bed was peeled off, the calcium carbonate granule acid etching that immerses at last in the acid solution polymer surfaces fell, and obtains having irregular cancellated polymer super-hydrophobic surface, specifically comprises the steps:

(1) in plane or roll surface substrate, adheres to 800～3000 purpose particle CaCO that a layer thickness is 0.1～20mm ₃Thin layer; Described substrate can be glass, pottery, metal etc.;

(2) hydrophobic polymer of fusion or viscous state is hot-pressed onto CaCO under 160～250 ℃, 50～1000Pa pressure ₃The thin layer surface, cooling forming; The hydrophobic polymer layer thickness can be determined according to actual needs, usually below 10mm.

(3) uncover CaCO from substrate ₃The composite bed of thin layer and polymeric layer immerses solubilized CaCO with composite bed ₃Acidic aqueous solution in, ultrasonic or stir 0.5min～60min and make its surface C aCO ₃Particle generation acid etching, with water flushing, dry (dry up or dry naturally with nitrogen) obtains having the material of super hydrophobic surface.Described acid etching is actual to be CaCO with polymer surfaces ₃The process that particle is removed by chemical reaction.

The described acidic aqueous solution of step (3) is the conventional inorganic acid in this area, and can be one of following or wherein two or more mixtures: (purpose of the pickling aqueous solution is in order to make surface C aCO for hydrochloric acid, sulfuric acid, nitric acid ₃Particle generation acid etching, its concentration does not have specific (special) requirements).

The described hydrophobic polymer of step (2) specifically can be polyethylene, polypropylene or polystyrene for this area routine is used to prepare the polymer of super hydrophobic surface.

Preferably, step (1) particle CaCO ₃Be 800～3000 purpose powdered whitings, be shaped as spherical, block or irregular.

Concrete, described step (1) method is as follows: with CaCO ₃Particle adds water and is made into CaCO ₃The suspension of mass content 1%～30% is got suspension and evenly is poured on the planar substrates, dry (oven dry or dry naturally) obtains surface attachment particle CaCO ₃The planar substrates of thin layer.

Perhaps, described step (1) method is as follows: with CaCO ₃Particle adds water and is made into CaCO ₃The suspension of mass content 1%～30%, with nozzle with CaCO ₃The particle suspension is sprayed onto on the roll surface, and drying obtains surface attachment particle CaCO ₃The roll surface substrate of thin layer.

Concrete, described step (2) method is as follows: in surface attachment particle CaCO is arranged ₃(3～10mm), the control temperature makes hydrophobic polymer fusion or viscosity flow, keeps 0.5s～30min under 50～1000Pa pressure, is cooled to room temperature forming to pile up the one layer of polymeric particle on the planar substrates of thin layer.

Perhaps, described step (2) method is as follows: the hydrophobic polymer of fusion or viscous state is pressed onto surface attachment in 50～1000Pa pressure lower roll particle CaCO ₃In the roll surface substrate of thin layer, be cooled to room temperature forming.

Described hydrophobic polymer is polyethylene, polypropylene or polystyrene, and described hot pressing temperature is controlled at 160～250 ℃.

The present invention can adopt ESEM (SEM) to come observation post to get surperficial microscopic appearance, measures the contact angle of gained surface water with contact angle measurement.

The super-hydrophobicity on surface can be by CaCO among the present invention ₃The compactness of particle thin layer, granular size and hot pressing pressure are controlled.

Beneficial effect of the present invention is mainly reflected in: the present invention uses the CaCO of wide material sources ₃Be raw material, with low cost, method is simple, efficient is high, and controllability and good reproducibility, make that the super hydrophobic surface contact angle reaches more than 150 °, roll angle is stable less than 10 °, hydrophobic performance, and be easy to large-area preparation, for the industrialization of super hydrophobic surface provides a kind of simple, valid approach, therefore be with a wide range of applications and vast market prospect.

(4) description of drawings

Fig. 1 is CaCO ₃Granular formwork method prepares the process schematic diagram of super hydrophobic surface;

Fig. 2 is CaCO ₃The SEM and the contact angle photo on the LLDPE surface of granular formwork method preparation;

Fig. 3 is CaCO ₃The LLDPE surface super-hydrophobic stability curve of granular formwork method preparation;

Fig. 4 is CaCO ₃The SEM and the contact angle photo on the LDPE surface of granular formwork method preparation;

Fig. 5 is CaCO ₃The SEM and the contact angle photo on the HDPE surface of granular formwork method preparation;

Fig. 6 is using CaCO for water droplet ₃Roll moment on the HDPE plane of granular formwork method preparation;

Fig. 7 is CaCO ₃The SEM and the contact angle photo on the PP surface of granular formwork method preparation;

Fig. 8 is CaCO ₃The SEM and the contact angle photo on the PS surface of granular formwork method preparation.

(5) specific embodiment

The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:

Embodiment 1:

CaCO on the substrate of glass ₃Thin layer preparation:, be bonded on the clean hydrophilic glass sheet with double faced adhesive tape with the blade framework that to carve a size on dimethyl silicone polymer (PDMS) sheet be 4cm*4cm.Take by weighing the CaCO of 10g again ₃It is 10% aqueous suspension that particle (1500 order) is made into solid content, gets the 5mL suspension and is poured on the slide, puts into baking oven, 160 ℃ down baking take out after 5 minutes, obtain the surface and be covered with one deck CaCO ₃The substrate of glass of thin layer.

Hot pressing LLDPE on the substrate of glass: the LLDPE particle (LLDPE of piling up the about 3mm of a layer thickness in the above on the substrate of glass that makes, Shanghai Secco Petrochemical Co., Ltd.), itself and the clean glass of another piece are put into 200 ℃ of baking oven heating 10 minutes together, again clean glass plate is covered on fusion LLDPE, take out cooling forming after 10 minutes with insulation in two clip baking oven fortunately.

CaCO ₃The acid etching of-LLDPE: on the good substrate of glass of cooling, uncover CaCO ₃-LLDPE film immerses in the hydrochloric acid solution of 30% (w/w), and ultrasonic (KQ2200) 30 minutes, the washing back dried up with nitrogen and obtains based superhydrophobic thin films for ultrasonic cleaner, Kunshan Ultrasonic Instruments Co., Ltd..The preparation process schematic diagram is seen Fig. 1, film surface micro-structural and Static Water contact angle are as shown in Figure 2, show that the porous surface with little-Na second order structure has super-hydrophobicity, contact angle is up to more than 150 °, the stability of contact angle as shown in Figure 3, the hydrophobic performance that shows this super hydrophobic surface is more stable, and water droplet is placed in the above for a long time, and contact angle is constant.

Embodiment 2:

The CaCO of glass surface ₃The thin layer preparation is as embodiment 1.

Hot pressing LDPE on the substrate of glass: the LDPE particle (low density polyethylene (LDPE) of piling up the about 6mm of a layer thickness in the above on the substrate of glass that makes, the Shanghai petrochemical industry, N220), itself and the clean glass plate of another piece are put into 200 ℃ of baking oven heating 10 minutes together, again clean glass plate is covered on LDPE, with being incubated taking-up in 5 minutes, cooling forming in two clip baking oven fortunately again.

CaCO ₃The acid etching of-LDPE: on the good substrate of glass of cooling, uncover CaCO ₃-LDPE film is put into 30% hydrochloric acid solution, leaves standstill 30 minutes, and the washing back dries up with nitrogen and obtains based superhydrophobic thin films, and surface micro-structure and Static Water contact angle are seen Fig. 4.

Embodiment 3:

The CaCO of glass surface ₃The thin layer preparation is as embodiment 1.

Hot pressing HDPE on the substrate of glass: the HDPE particle (high density polyethylene (HDPE) of piling up the about 5mm of a layer thickness in the above on the substrate of glass that makes, Shanghai Secco Petrochemical Co., Ltd.), itself and the clean glass plate of another piece are put into 200 ℃ of baking oven heating 10 minutes together, again clean glass plate is covered on HDPE, with being incubated taking-up in 5 minutes, cooling forming in two clip baking oven fortunately again.

CaCO ₃The acid etching of-HDPE: on the good substrate of glass of cooling, uncover CaCO ₃-HDPE film is put into 30% hydrochloric acid solution, leaves standstill 30 minutes, and the washing back dries up with nitrogen and obtains based superhydrophobic thin films, and surface micro-structure and Static Water contact angle are seen Fig. 5, and surperficial water droplet rolling photo is seen Fig. 6.

Embodiment 4:

The CaCO of glass surface ₃The thin layer preparation is as embodiment 1.

Hot pressing PP on the substrate of glass: the PP particle (polypropylene of piling up the about 8mm of a layer thickness in the above on the substrate of glass that makes, China's Zhenghai cracking, T30S), itself and the clean glass plate of another piece are put into 200 ℃ of baking oven heating 10 minutes together, again with clean glass cover on PP, with being incubated taking-up in 5 minutes, cooling forming in two clip baking oven fortunately again.

CaCO ₃The acid etching of-PP: on the good substrate of glass of cooling, uncover CaCO ₃-PP film is put into 30% hydrochloric acid solution, leaves standstill 30 minutes, and the washing back dries up with nitrogen and obtains based superhydrophobic thin films, and surface micro-structure and Static Water contact angle are seen Fig. 7.

Embodiment 5:

The CaCO of glass surface ₃The thin layer preparation is as embodiment 1.

Hot pressing PS on the substrate of glass: the PS (polystyrene of piling up the about 10mm of a layer thickness in the above on the substrate of glass that makes, Yanshan Mountain branch company of China Petrochemical Industry, 666D) particle, itself and the clean glass plate of another piece are put into 230 ℃ of baking oven heating 20 minutes together, again clean glass plate is covered on PS, with being incubated taking-up in 5 minutes, cooling forming in two clip baking oven fortunately again.

CaCO ₃The acid etching of-PS: on the good substrate of glass of cooling, uncover CaCO ₃-PS sheet is put into 30% hydrochloric acid solution, leaves standstill 30 minutes, and the washing back dries up with nitrogen and obtains the height hydrophobic surface, and its micro-structural and Static Water contact angle are seen Fig. 8.

Claims

1. CaCO ₃Template prepares the method for polymer super-hydrophobic surface, and described method comprises:

(1) in plane or roll surface substrate, adheres to 800～3000 purpose particle CaCO that a layer thickness is 0.1～20mm ₃Thin layer;

(2) hydrophobic polymer of fusion or viscous state is hot-pressed onto CaCO under 160～250 ℃, 50～1000Pa pressure ₃The thin layer surface, cooling forming;

(3) uncover CaCO from substrate ₃The composite bed of thin layer and polymeric layer immerses solubilized CaCO with composite bed ₃Acidic aqueous solution in, ultrasonic or stir 0.5min～60min, with the water flushing, drying obtains having the material of super hydrophobic surface.

2. the method for claim 1 is characterized in that the described acidic aqueous solution of step (3) is one of following or wherein two or more mixture: hydrochloric acid, sulfuric acid, nitric acid.

3. the method for claim 1 is characterized in that the described hydrophobic polymer of step (2) is polyethylene, polypropylene or polystyrene.

4. the method for claim 1 is characterized in that described step (1) method is as follows: with CaCO ₃Particle adds water and is made into CaCO ₃The suspension of mass content 1%～30% is got suspension and evenly is poured on the planar substrates, and drying obtains surface attachment particle CaCO ₃The planar substrates of thin layer.

5. the method for claim 1 is characterized in that described step (1) method is as follows: with CaCO ₃Particle adds water and is made into CaCO ₃The suspension of mass content 1%～30%, with nozzle with CaCO ₃The particle suspension is sprayed onto on the roll surface, and drying obtains surface attachment particle CaCO ₃The roll surface substrate of thin layer.

6. the method for claim 1 is characterized in that described step (2) method is as follows: in surface attachment particle CaCO is arranged ₃Pile up the one layer of polymeric particle on the planar substrates of thin layer, the control temperature makes hydrophobic polymer fusion or viscosity flow, keeps 0.5s～30min under 50～1000Pa pressure, is cooled to room temperature forming.

7. the method for claim 1 is characterized in that described step (2) method is as follows: the hydrophobic polymer of fusion or viscous state is pressed onto surface attachment in 50～1000Pa pressure lower roll particle CaCO ₃In the roll surface substrate of thin layer, be cooled to room temperature forming.

8. as claim 6 or 7 described methods, it is characterized in that described hydrophobic polymer is polyethylene, polypropylene or polystyrene.