CN107916400A - A kind of titanium dioxide plastic film and its processing method - Google Patents

A kind of titanium dioxide plastic film and its processing method Download PDF

Info

Publication number
CN107916400A
CN107916400A CN201711349122.1A CN201711349122A CN107916400A CN 107916400 A CN107916400 A CN 107916400A CN 201711349122 A CN201711349122 A CN 201711349122A CN 107916400 A CN107916400 A CN 107916400A
Authority
CN
China
Prior art keywords
film layer
plastic film
titanium dioxide
film
fine aluminium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201711349122.1A
Other languages
Chinese (zh)
Inventor
王娟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui Industrial Economy Vocationl Technical College
Original Assignee
Anhui Industrial Economy Vocationl Technical College
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anhui Industrial Economy Vocationl Technical College filed Critical Anhui Industrial Economy Vocationl Technical College
Priority to CN201711349122.1A priority Critical patent/CN107916400A/en
Publication of CN107916400A publication Critical patent/CN107916400A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Electrochemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a kind of titanium dioxide plastic film and its processing method, titanium dioxide plastic film includes macromolecule plastic film, the fine aluminium film layer for being covered in the macromolecule plastic film surface, the aluminum oxide film layer of the loose structure generated by the surface of the fine aluminium film layer by oxidation processes and the titanium oxide film layer for being deposited on the pellumina layer surface.The present invention by setting fine aluminium film layer on a plastic film, and by the aluminum oxide film layer of fine aluminium film layer generation loose structure, transition is carried out with this, so as to form the titanium oxide film layer of nanoscale, loose structure on a plastic film, adhesive force and the preferable titanium dioxide plastic film material of pliability are obtained.

Description

A kind of titanium dioxide plastic film and its processing method
Technical field
The present invention relates to titanium dioxide film materials field, relates in particular to a kind of titanium dioxide plastic film and its adds Work method.
Background technology
Titanium dioxide film materials can produce strong oxidizing property free radical under the irradiation of ultraviolet light, these Active Radicals Produceds Energy decomposing organic compounds, have sterilization, automatic cleaning action, while in ultraviolet light, material surface produces super hydrophilic spy Property.
TiO2Photocatalysis and its crystal habit and particle size have directly related property, with Detitanium-ore-type crystal form, receive Metrical scale particle best results, Detitanium-ore-type tool photohole potential bigger, oxidisability is stronger, and the particle of nanoscale is because of amount Sub- effect and skin effect, have the effect for being significantly superior to large scale particle.At the same time it has also been found that titanium deoxid film material When material surface is loose structure, its film layer can keep super hydrophilic characteristic for a long time, therefore prepare nanoscale, porous, Detitanium-ore-type Titanium dioxide film materials become industrial hot spot.
The method of synthesis nano-titanium dioxide film is many both at home and abroad at present, mainly has sol-gel process, outside molecular beam Prolong, chemical vapour deposition technique, spray pyrolysis method, sputtering sedimentation etc..The titanium deoxid film of current most of business is all adopted Prepared with colloidal sol-glue method.
But the above method is each to have some shortcomings, sol-gel process, molecular beam epitaxy, chemical vapour deposition technique, spraying heat by oneself The shortcomings that solution is that one is needed in coating process about in 500~600 DEG C of the process for thermally decomposing organic matter, high temperature limitation base The selectivity of piece material；Sputtering sedimentation especially magnetron sputtering is a kind of new, low-temperature sputter film plating process, prepared by such a method Film has the advantages that high quality, good associativity and intensity, but because sputter procedure is the deposition process of atom, this process is difficult To form the loose structure of nanoscale, so titanium deoxid film porosity prepared by the method is low, it is impossible to give full play to dioxy Change the photocatalysis effect of titanium film.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of with nanoscale, the titanium dioxide film of loose structure Layer, adhesive force and the preferable titanium dioxide plastic film of pliability and its processing method.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that：A kind of titanium dioxide plastic film, including Macromolecule plastic film, the fine aluminium film layer for being covered in the macromolecule plastic film surface, the surface warp by the fine aluminium film layer The aluminum oxide film layer of the loose structure of peroxidating processing generation and the titanium dioxide film for being deposited on the pellumina layer surface Layer.
Further, the porosity of the aluminum oxide film layer is 60~65%, and aperture is 0.25~0.6 μm.
Further, the thickness of the macromolecule plastic film is 10~80 μm, the thickness of the fine aluminium film layer for 25~ 500nm, the thickness of the aluminum oxide film layer is 25~500nm.
The processing method of above-mentioned titanium dioxide plastic film, comprises the following steps：
(1) processing of fine aluminium film layer
For the macromolecule plastic film of polarity, directly fine aluminium film layer is coated on the surface of macromolecule plastic film；
For nonpolar macromolecule plastic film, sided corona treatment is first carried out to the surface of macromolecule plastic film, then The surface of macromolecule plastic film coats fine aluminium film layer；
(2) processing of aluminum oxide film layer
Using fine aluminium film layer as anode, it is placed in aqueous sulfuric acid, passes to direct current, fine aluminium film layer is carried out at anodic oxidation Reason, the surface oxidation of fine aluminium film layer is made by electrolysis, generates the aluminum oxide film layer of loose structure；
(3) processing of titanium oxide film layer
In the surface deposition of titanium oxide of aluminum oxide film layer, titanium oxide film layer is made.
In the present invention, macromolecule plastic film generally selects 10~80 μm of thickness, when selecting polar plas film, than As BOPET, BOPA can directly carry out it is vacuum aluminum-coated, it is pure coating and for the non-polar plastic film such as BOPP, CPP, PE Need to carry out sided corona treatment to film surface before aluminum membranous layer.
The concrete technology of sided corona treatment is：Platinum profit JBL-1000K corona treatments, which are praised, using Nanjing carries out sided corona treatment, electricity Dizzy technique uses AC220V (± 20%) stabilized power source, single head or multiple head electrode, and electrode gap control carries out film in 1~2mm Single or double processing, processing voltage range is between 10000~20000V.The output power range 1000 of corona treatment~ 13000VA, 10~25kHz of frequency-tuning range of corona treatment.Non-polar plastic film surface can be made by sided corona treatment Tension force reaches 38~42dyn/cm or surface free energy reaches 3.8~4.0*10-6J/cm2More than.Sided corona treatment power is to determine The principal element of degree for the treatment of, processing speed are 25~80m/min, and the material ranges that sided corona treatment is applicable in are wide, available for poly- second Alkene, polypropylene, polyvinyl chloride, polyamide, polyester, makrolon, fluoroplastics, and various corresponding copolymers etc.；During processing Between it is short, speed is fast, be adapted to continuous production；And easy to operate, control is easily；Sided corona treatment pertains only to the extremely shallow model of plastic surface layer Enclose, generally only nanometer scale, have no substantial effect on the mechanical performance of product.
In the present invention, coat fine aluminium film layer and use vacuum evaporation process, i.e., under vacuum, using the method for evaporation By aluminium lamination direct plating on base film surface in a manner of in-situ deposition.Specific technological process：Base material unreels → vacuumizes → Heating evaporation boat → send aluminium wire → evaporation → cooling → winding.Width is placed in very for 800~2000mm reel plastic films In empty room, vacuum 1.3 × 10 is evacuated to-2~1.3 × 10-5Pa, preferably vacuum are not less than 4 × 10-4MPa, by evaporation boat 1300~1400 DEG C of heating, then continuously send the aluminium wire that purity is 99.9% to evaporation boat, and retractable volume speed 200~ 350m/min, aluminium wire 0.4~1.0m/min of wire feed rate, open cooling source, operating temperature range -15~35 of cooling system DEG C, cooling time is less than 25min, aluminium wire continuously melted, evaporated on evaporation boat, and the aluminium atom after evaporation is in polymer plastic Expect the surface of film, a layer thickness is formed after cooling in 25~500nm fine aluminium film layers.
In the present invention, by anodized, it is 25~500nm that fine aluminium film surface, which can obtain thickness, high porosity, The water white transparency aluminum oxide film layer of strong adsorption, and pure water cleaning, drying, winding are carried out to the plastic film after processing, so as to It is as shown in table 1 below in the processing of follow-up titanium oxide film layer, the process conditions of anodized：
The process conditions of 1 anodized of table
Formula and process conditions Parameter setting
Decomposition voltage AC (V) 18~25
Aqueous sulfuric acid concentration (g/L) 180~230g/L
Electrolyte solution temperature (DEG C) 10~20
Anodic current density (A/dm2) 0.8~1.5
Aluminium ion concentration Al3+ (g/L) <20
Unreel speed (m/min) 10-50
Processing time (min) 0.5~2
Stirring means Compressed air
Cathode area/annode area 1.5：1
Drying temperature (DEG C) 40~60
Selection process is as follows：Aqueous sulfuric acid is increased as electrolyte solution, concentration rise, the dissolution velocity of film, film The speed of growth reduces, and the porosity of film is high, strong adsorption force.Oxidation membrane porosity is can adjust by adjusting sulfuric acid concentration, it is preferably dense Spend for 20%；Electrolyte temperature influences coating mass very big, temperature rise, the dissolution velocity increasing of film, and thickness reduces.Cause Aluminum layer thickness is very thin, and to ensure oxidation effectiveness, for preferable temperature when between 10~20 DEG C, the oxide-film generated is porous, Adsorption capacity is strong；Current density raises, and layer-growth rate can raise, and oxidization time shortens, and the hole of produced film is more, porosity Height, and hardness and wearability rise, the present invention preferably current density 1.5A/dm2, anodizing process with sulfuric acid as major salt is simple, and solution is steady It is fixed, it is easy to operate, it is allowed to which that impurity level is wider, and power consumption is few, and cost is low, applied widely.
In the present invention, make titanium oxide film layer and use magnetron sputtering method, magnetron sputtering has low temperature, at a high speed two big spies Point, is adapted to the sputtering sedimentation TiO on the not high plastic substrate film of temperature tolerance2.Its process is that plastic film coil is put into coiling In vacuum coating equipment vacuum chamber, with more than 99.5% titanium dioxide titanium target of purity, target chamber is put into, range is adjusted to 60~90mm, takes out Vacuum is to 2 × 10-4~2 × 10-5Pa, opens radio-frequency power supply, 150~400W of radio-frequency power, 25~35MHz of frequency, is passed through argon Gas, 20~60mL/min of argon flow amount, adjusting radio-frequency power separates reative cell aura, adjusts gas pressure in vacuum to predetermined value After 0.2~0.8Pa, sputter coating, TIO are carried out2The deposition of film is 5~10nm/min, and 1~2min of processing time, unreels speed Spend 0.5~3m/min.
Beneficial effects of the present invention are embodied in：
The present invention by setting fine aluminium film layer on a plastic film, and by the pellumina of fine aluminium film layer generation loose structure Layer, transition is carried out with this, so as to form the titanium oxide film layer of nanoscale, loose structure on a plastic film, is obtained attached Put forth effort and the preferable titanium dioxide plastic film material of pliability.
The processing method technique of the present invention is simple, easily implements, and it is 60~65% that can effectively make porosity, and aperture is 0.25~0.6 μm of aluminum oxide film layer, ensures to obtain nanoscale, the titanium oxide film layer of loose structure, has extraordinary Application prospect.
The present invention is sunk using macromolecule membrane as basement membrane, while using pellumina as nanoscale foraminous die plate Product TIO2Afterwards, super hydrophilic, the self-cleaning film using titanium dioxide as functional coating, this method tool can be manufactured at low temperature There is the characteristics of low temperature moulding, nanoporous coating structure, film has that automatically cleaning effect is good, superpower hydrophilic, anti-fog performance.
Embodiment
With reference to embodiment, the invention will be further described：
Various raw materials, are such as not specifically noted used in following embodiments, are commercial product well known in the art.
Embodiment 1
The preparation of titanium dioxide plastic film
Titanium dioxide plastic film includes macromolecule plastic film, is covered in the fine aluminium on the macromolecule plastic film surface Film layer, pass through the aluminum oxide film layer for the loose structure that oxidation processes generate by the surface of the fine aluminium film layer and be deposited on institute The titanium oxide film layer of pellumina layer surface is stated, its preparation method comprises the following steps：
(1) processing of fine aluminium film layer
20 μm of thickness, the PE plastic films of width 1000mm are selected, platinum profit JBL-1000K corona treatments are praised using Nanjing Sided corona treatment is carried out, treatment process uses AC220V (± 20%) constant voltage dc source, 6 tip electrodes, electrode gap 2mm, to thin Film carries out continuous single side sided corona treatment, and processing voltage range is in 15000V, the output power 6000VA of corona treatment, at corona The frequency 15kHz of reason machine, processing speed 60m/min, processing rear film surface tension can reach 38mN/m~42mN/m；
PE films after sided corona treatment are placed in sincere CCZK-RC vacuum roll coaters of speeding, using vacuum evaporation process, Aluminize to PE film coronas face, vacuum chamber is first evacuated to vacuum 5 × 10-4Pa, evaporator temperature are controlled at 1300 DEG C, will Diameter 2mm, the aluminium wire that purity is 99.9% are continuously sent to evaporation boat, the work of aluminium wire cooling system with the wire feed rate of 0.4m/min - 10 DEG C of temperature, control PE films retractable volume speed 240m/min, makes aluminium wire continuously melt, evaporate on evaporation boat, in film Surface forms a layer thickness 300nm fine aluminium film layers；
(2) processing of aluminum oxide film layer
Metallized film is sent into the aqueous sulfuric acid groove of mass fraction 200g/L, passes to 25V direct currents, control electrolyte 15 DEG C of solution temperature, Al3+Ion concentration 10g/L, anodic current density 1.0A/dm2, and compressed air is passed through in a cell, Oxidation efficiency and uniformity are promoted by air agitation, processing time 10min, obtains 100nm thickness water white transparency aluminum oxide film layers；
The aluminum oxide film layer of acquisition has nano-scale loose structure, and adsorptivity is preferable, this layer of aluminum oxide film layer, which becomes, to be received Rice TIO2Support template, while on film clarity substantially without influence, after the completion of oxidation processes, using room temperature pure water to film Cleaned, until electrolyte noresidue, using being wound after 50 DEG C of hot-air seasonings, winds and unreel speed 20m/min；
The porosity of aluminum oxide film layer made from the present embodiment is 63%, and aperture is 0.45 μm；
(3) processing of titanium oxide film layer
Method using smooth vacuum GRJR series roll and vacuum plated film machines by magnetron sputtering plating, in aluminum oxide film layer Surface depositing Ti O2Film, concrete technology sequence are：TiO is used using shielding power supply2Film radio-frequency power supply, target are empty using DETECH Between plane magnetic control TiO2Sputtering target, target purity 99.99%, technique and condition are：Vacuum 1.1 × 10-5Pa, radio-frequency power supply work( Rate 300W, frequency 30MHz, operating air pressure 0.1Pa, magnetic field intensity 120G, argon flow amount 30ml/min, range 80mm, TiO2 The deposition of film is 5nm/min, rolling speed 10m/min, 10~15 DEG C of target cooler-water temperature, hydraulic pressure 2.0 × 105Pa, stream Measure 20L/min.
Embodiment 2
The preparation of titanium dioxide plastic film
Titanium dioxide plastic film includes macromolecule plastic film, is covered in the fine aluminium on the macromolecule plastic film surface Film layer, pass through the aluminum oxide film layer for the loose structure that oxidation processes generate by the surface of the fine aluminium film layer and be deposited on institute The titanium oxide film layer of pellumina layer surface is stated, its preparation method comprises the following steps：
(1) processing of fine aluminium film layer
10 μm of thickness, the BOPET plastic films of width 1000mm are selected, film is placed in sincere CCZK-RC vacuum volume of speeding Around coating machine, using vacuum evaporation process, aluminize to BOPET Plastic film surfaces, vacuum chamber is first evacuated to vacuum 1.3 ×10-2Pa, evaporator temperature are controlled at 1350 DEG C, and diameter 2mm, purity is fast with the wire feed of 0.4m/min for 99.9% aluminium wire Degree is continuous to be sent to evaporation boat, -10 DEG C of aluminium wire cooling system operating temperature, and control retractable volume speed 350m/min, is steaming aluminium wire Continuously melt, evaporate on hair boat, a layer thickness 25nm fine aluminium film layers are formed in film surface；
(2) processing of aluminum oxide film layer
Metallized film is sent into the aqueous sulfuric acid groove of mass fraction 180g/L, passes to 18V direct currents, control control electricity 10 DEG C of electrolyte solution temperature, Al3+Ion concentration 10g/L, anodic current density 0.8A/dm2, and it is empty to be passed through compression in a cell Gas, promotes oxidation efficiency and uniformity, processing time 0.5min, obtains 25nm thickness water white transparency aluminium oxide by air agitation Film layer, cleans film using room temperature pure water, until electrolyte noresidue, using being wound after 50 DEG C of hot-air seasonings, winds With unreeling speed 20m/min；
The porosity of aluminum oxide film layer made from the present embodiment is 60%, and aperture is 0.6 μm；
(3) processing of titanium oxide film layer
Method using smooth vacuum GRJR series roll and vacuum plated film machines by magnetron sputtering plating, in aluminum oxide film layer Surface depositing Ti O2Film, concrete technology sequence are：TiO is used using shielding power supply2Film radio-frequency power supply, target are empty using DETECH Between plane magnetic control TiO2Sputtering target, target purity 99.6%, technique and condition are：Vacuum 2 × 10-4Pa, radio-frequency power 150W, Rf frequency 25MHz, magnetic field intensity 120G, argon flow amount 20ml/min, operating air pressure 0.1Pa, range 60mm, TiO2Film Deposition is 5nm/min, rolling speed 3m/min, 10 DEG C of target cooler-water temperature, flow 20L/min.
Embodiment 3
The preparation of titanium dioxide plastic film
Titanium dioxide plastic film includes macromolecule plastic film, is covered in the fine aluminium on the macromolecule plastic film surface Film layer, pass through the aluminum oxide film layer for the loose structure that oxidation processes generate by the surface of the fine aluminium film layer and be deposited on institute The titanium oxide film layer of pellumina layer surface is stated, its preparation method comprises the following steps：
(1) processing of fine aluminium film layer
80 μm of thickness, the BOPP plastic films of width 1000mm are selected, platinum profit JBL-1000K sided corona treatments are praised using Nanjing Machine carries out sided corona treatment, and treatment process uses AC220V (± 20%) constant voltage dc source, 6 tip electrodes, electrode gap 1mm, right Film carries out continuous single side sided corona treatment, handles voltage 20000V, the output power 13000VA of corona treatment, output frequency 25kHz, processing speed 80m/min, processing rear film surface tension can reach more than 42mN/m；
BOPP film after sided corona treatment is placed in sincere CCZK-RC vacuum roll coaters of speeding, using vacuum evaporation work Skill, aluminizes BOPP film corona surface, and vacuum chamber first is evacuated to vacuum 1.3 × 10-5Pa, evaporator temperature control exist 1400 DEG C, diameter 2mm, the aluminium wire that purity is 99.99% are continuously sent to evaporation boat, aluminium wire cooling with the wire feed rate of 1m/min - 10 DEG C of system operating temperatures, control process speed 200m/min, make aluminium wire continuously melt, evaporate on evaporation boat, in film Surface forms a layer thickness 500nm fine aluminium film layers；
(2) processing of aluminum oxide film layer
Metallized film is sent into the aqueous sulfuric acid groove of concentration 230g/L, passes to 20V direct currents, control control electrolyte 20 DEG C of solution temperature, Al3+Ion concentration 15g/L, anodic current density 1.5A/dm2, and compressed air is passed through in a cell, Oxidation efficiency and uniformity are promoted by air agitation, processing time 2min, obtains 500nm thickness water white transparency pelluminas Layer；Film is cleaned using room temperature pure water, until electrolyte noresidue, using being wound after 50 DEG C of hot-air seasonings, winding with Unreel speed 20m/min；
The porosity of aluminum oxide film layer made from the present embodiment is 65%, and aperture is 0.25 μm；
(3) processing of titanium oxide film layer
Method using smooth vacuum GRJR series roll and vacuum plated film machines by magnetron sputtering plating, in aluminum oxide film layer Surface depositing Ti O2Film, concrete technology sequence are：TiO is used using shielding power supply2Film radio-frequency power supply, target are empty using DETECH Between plane magnetic control TiO2Sputtering target, target purity 99.9%, technique and condition are：Vacuum 2 × 10-5Pa, radio-frequency power 400W, Rf frequency 35MHz, magnetic field intensity 120G, argon flow amount 60ml/min, operating air pressure 0.2Pa, range 90mm, TiO2Film Deposition is 10nm/min, rolling speed 3m/min, 10 DEG C of target cooler-water temperature, flow 20L/min.
Embodiment 4
The performance test of titanium dioxide plastic film
Carry out adhesive force test and pliability test, attachment respectively to titanium dioxide plastic film made from embodiment 1 to 3 Force test method is with reference to GB/T 1720-1979 paint film adhesion determination methods；Pliability test method is with reference to GB/T 1731-1993 Paint film flexibility determination method.The result is shown in table 2 below.
Table 2
It can be seen that, it can be seen that titanium dioxide plastic film adhesive force produced by the present invention and pliability tool are preferable.
The present invention prepares TiO2The nanoscale loose structure that plating layer film has, TiO2Nanoscale coating macromolecule is thin Film can become strong oxidizer under action of ultraviolet light, pass through TiO2Photocatalysis, decomposing organic pollutant, while ultraviolet Under line effect, its porous surface can obtain long-acting super-hydrophilic property, when dirt is in contact with it, TiO2Trickle dirt is decomposed into Carbon dioxide and water, because of primary surface Superhydrophilic, can make the moisture of attachment thereon form moisture film and pour in dirt and TiO2Interface, Make the reduction of dirt, peeled off when by water shower.
At the same time because its super hydrophilicity can regain after being irradiated by ultraviolet, its ultra-hydrophilic surface property has length Effect property, can use as antifog film, applied to auto mirror, vehicle window pad pasting, by the way that such a hyaline membrane is attached to glass surface Make its not fogging, bear water drop, keep what comes into a driver's clear.Agriculturally, using its hydrophilic feature with for agricultural greenhouse film, on ceiling Droplet along canopy face toward flow down, without falling down, can reduce causes crops since the water polo of plastic greenhouse ceiling falls down Infringement.With for building glass, exterior wall film pasting when, equally with anti-fogging, self-cleaning effect.In terms of traffic, for anti- Mirror, dial plate are penetrated when pad pasting, can antifog, automatically cleaning.In terms of household electrical appliances, composite material is made as with for household electrical appliances face with steel plate Panel can be made to obtain easy to clean or self-cleaning characteristic during plate.Application, marine surface paste hydrophilic film in terms of movement under water After can reduce frictional resistance, some researches show that water-wetted surface can reducing friction resistance 85%-90%.
It should be understood that example as described herein and embodiment are not intended to limit the invention, this area only for explanation Technical staff can make various modifications or change according to it, within the spirit and principles of the invention, any modification for being made, Equivalent substitution, improvement etc., should all be included in the protection scope of the present invention.

Claims (8)

1. a kind of titanium dioxide plastic film, it is characterised in that including macromolecule plastic film, be covered in the high molecule plastic The fine aluminium film layer of film surface, the pellumina by loose structure of the surface of the fine aluminium film layer by oxidation processes generation Layer and the titanium oxide film layer for being deposited on the pellumina layer surface.
2. titanium dioxide plastic film as claimed in claim 1, it is characterised in that the porosity of the aluminum oxide film layer is 60 ~65%, aperture is 0.25~0.6 μm.
3. titanium dioxide plastic film as claimed in claim 1 or 2, it is characterised in that the thickness of the macromolecule plastic film Spend for 10~80 μm, the thickness of the fine aluminium film layer is 25~500nm, and the thickness of the aluminum oxide film layer is 25~500nm.
4. the processing method of titanium dioxide plastic film as claimed any one in claims 1 to 3, it is characterised in that including Following steps：
(1) processing of fine aluminium film layer
For the macromolecule plastic film of polarity, directly fine aluminium film layer is coated on the surface of macromolecule plastic film；
For nonpolar macromolecule plastic film, sided corona treatment first is carried out to the surface of macromolecule plastic film, then in high score The surface of sub- plastic film coats fine aluminium film layer；
(2) processing of aluminum oxide film layer
Using fine aluminium film layer as anode, it is placed in aqueous sulfuric acid, passes to direct current, anodized is carried out to fine aluminium film layer, Make the surface oxidation of fine aluminium film layer by electrolysis, generate the aluminum oxide film layer of loose structure；
(3) processing of titanium oxide film layer
In the surface deposition of titanium oxide of aluminum oxide film layer, titanium oxide film layer is made.
5. the processing method of titanium dioxide plastic film as claimed in claim 4, it is characterised in that the work of anodized Skill condition is：Decomposition voltage AC18~25V, aqueous sulfuric acid 180~230g/L of concentration, 10~20 DEG C of electrolyte solution temperature, 0.8~1.5A/dm of anodic current density2, aluminium ion concentration Al3+<20g/L。
6. the processing method of titanium dioxide plastic film as described in claim 4 or 5, it is characterised in that the work of sided corona treatment Skill condition is：AC220V (± 20%) stabilized power source, 1~2mm of electrode gap, 10000~20000V of voltage range, sided corona treatment 1000~13000VA of output power range of machine, 10~25kHz of frequency-tuning range of corona treatment.
7. the processing method of titanium dioxide plastic film as described in claim 4 or 5, it is characterised in that coat pure aluminium film Layer uses vacuum evaporation process, and the process conditions of vacuum evaporation are：Vacuum 1.3 × 10-2~1.3 × 10-5Pa, evaporation boat temperature 1300~1400 DEG C of degree.
8. the processing method of titanium dioxide plastic film as described in claim 4 or 5, it is characterised in that make titanium dioxide Film layer uses magnetron sputtering technique, and the process conditions of magnetron sputtering are：60~90mm of range, vacuum 2 × 10-4~2 × 10- 5Pa, 150~400W of radio-frequency power, 25~35MHz of frequency, is passed through argon gas, 20~60mL/min of argon flow amount.
CN201711349122.1A 2017-12-15 2017-12-15 A kind of titanium dioxide plastic film and its processing method Pending CN107916400A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711349122.1A CN107916400A (en) 2017-12-15 2017-12-15 A kind of titanium dioxide plastic film and its processing method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711349122.1A CN107916400A (en) 2017-12-15 2017-12-15 A kind of titanium dioxide plastic film and its processing method

Publications (1)

Publication Number Publication Date
CN107916400A true CN107916400A (en) 2018-04-17

Family

ID=61893545

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711349122.1A Pending CN107916400A (en) 2017-12-15 2017-12-15 A kind of titanium dioxide plastic film and its processing method

Country Status (1)

Country Link
CN (1) CN107916400A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101591745A (en) * 2008-05-30 2009-12-02 鸿富锦精密工业（深圳）有限公司 Aluminum products and preparation method thereof
CN101700703A (en) * 2009-10-30 2010-05-05 湖州金泰科技股份有限公司 Chromium-plated plastic product

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101591745A (en) * 2008-05-30 2009-12-02 鸿富锦精密工业（深圳）有限公司 Aluminum products and preparation method thereof
CN101700703A (en) * 2009-10-30 2010-05-05 湖州金泰科技股份有限公司 Chromium-plated plastic product

Similar Documents

Publication Publication Date Title
Fu et al. A review on the electrochemically self-organized titania nanotube arrays: synthesis, modifications, and biomedical applications
Jiang et al. Preparation, corrosion resistance and hemocompatibility of the superhydrophobic TiO2 coatings on biomedical Ti-6Al-4V alloys
JP6061202B2 (en) Non-metal coating and production method thereof
Yousefpour Electrodeposition of TiO2–RuO2–IrO2 coating on titanium substrate
Yangi et al. Effects of current density on microstructure of titania coatings by micro-arc oxidation
Nakajima et al. Fabrication of a novel aluminum surface covered by numerous high-aspect-ratio anodic alumina nanofibers
Sun et al. Effect of heat treatment on surface hydrophilicity-retaining ability of titanium dioxide nanotubes
Solovyev et al. Application of PVD methods to solid oxide fuel cells
JP5995906B2 (en) Manufacturing method of diaphragm and manufacturing method of metal coating
CN106555188A (en) For the preparation method of the Ag/ Graphenes/titania nanotube composite film photo-anode of photoproduction cathodic protection
US20120279853A1 (en) Cathode, electrolytic cell for electrolysis of alkali metal chloride, and method for producing negative electrode
Park et al. Formation of ZnO nanowires during short durations of potentiostatic and galvanostatic anodization
CN104726834A (en) Hydrophilic and hydrophobic-reversible switching titanium dioxide nanometer film material and preparation method thereof
Szkoda et al. Semi-transparent ordered TiO2 nanostructures prepared by anodization of titanium thin films deposited onto the FTO substrate
Li et al. Fabrication and corrosion behavior of TiO2 nanotubes on AZ91D magnesium alloy
Khosravani et al. The effect of various oxidation temperatures on structure of Ag-TiO2 thin film
CN103695981B (en) A kind of method of micro-arc oxidation of aluminum alloy surface film functionalized design
US10782014B2 (en) Plasmonic energy conversion device for vapor generation
CN101261901B (en) A dye sensitized solar battery anode and its making method
CN104451955B (en) Metal or metal oxide with hierarchical structure and preparation method of metal or metal oxide
CN107916400A (en) A kind of titanium dioxide plastic film and its processing method
Yi et al. Photocatalytic performance and microstructure of thermal-sprayed nanostructured TiO2 coatings
Karaman et al. Chemical and physical modification of surfaces
Ismail et al. Segmented nanoporous WO 3 prepared via anodization and their photocatalytic properties
Xiaohong et al. TiO2 ceramic films prepared by micro-plasma oxidation method for photodegradation of rhodamine B

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20180417

RJ01 Rejection of invention patent application after publication