CN106756876B - Magnesium alloy parent/super-hydrophobic controllable composite membrane in region preparation method - Google Patents

Magnesium alloy parent/super-hydrophobic controllable composite membrane in region preparation method Download PDF

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CN106756876B
CN106756876B CN201611181820.0A CN201611181820A CN106756876B CN 106756876 B CN106756876 B CN 106756876B CN 201611181820 A CN201611181820 A CN 201611181820A CN 106756876 B CN106756876 B CN 106756876B
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magnesium alloy
layer
super
hydrophobic
region
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CN106756876A (en
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赵明
王宇
王学良
陈睿
赵全亮
何广平
铁军
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Taihu County Market Supervision And Inspection Institute Taihu County Functional Membrane Testing Institute
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North China University of Technology
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    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/02—Electrolytic coating other than with metals with organic materials

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Abstract

The present invention provides a kind of preparation methods of magnesium alloy parent/super-hydrophobic controllable composite membrane in region, it is prepared for one layer of overall leveling ferric phosphate zinc calcium/manganese salt layer for being uniformly distributed fine cracks in Mg alloy surface first, the Si of different zones deposition micro-nano-scale in this phosphatization layer surface3N4Partial layer grows super-hydrophobic layer in other region surfaces of phosphate coating on this basis.The Si of ferric phosphate zinc calcium/manganese salt layer and its surface of the invention3N4Invigoration effect is played to super-hydrophobic film layer as skeleton in region, the controllable compound conversion film layer in prepared parent/super-hydrophobic region, it may be implemented the operation such as to transmit microlayer model, separate, stablize, select, collect, sort and fix, and it can be very good a magnesium alloy and external environment isolation, play the role of anticorrosive, expands the application field of magnesium alloy.

Description

Magnesium alloy parent/super-hydrophobic controllable composite membrane in region preparation method
Technical field
The present invention relates to technical field of magnesium alloy surface treatment, especially a kind of magnesium alloy parent/super-hydrophobic region is controllably multiple Close the preparation method of film.
Background technique
Magnesium alloy due to have it is light take into account many advantages, such as being easily recycled, becoming steel, aluminium alloy, engineering plastics A kind of important alternative materials.And magnesium rich reserves in the earth's crust, it is only second to aluminium, iron, belongs to light metal, density 1.74g/ cm3, about aluminium 2/3, steel 1/5, have a very wide range of applications prospect as structural material.
Magnesium has very high chemical activity, and equilibrium potential is very low, contacts Shi Yifa with the higher metal of equilibrium potential Raw galvanic corrosion, and serve as anode.Magnesium elements and oxygen element have very big affinity, it is easy to it reacts with oxygen, shape At loose porous MgO, the intrusion of oxygen in air not only cannot be effectively obstructed, also will form primary battery, aggravates the corruption of magnesium alloy Erosion.
The corrosion resistance for improving magnesium alloy mainly has two approach, first is that impurity content is reduced by addition alloying element, into The methods of row heat treatment appropriate improves the corrosion resistance of alloy material itself, second is that carrying out at surface appropriate to magnesium alloy product Reason realizes the isolation with external environment, hinders the generation of corrosion.
In existing surface treatment method of Mg alloy, one layer of phosphorization membrane or super thin usually is prepared in Mg alloy surface Water film can isolate contact of the magnesium alloy with environment, but there are a large amount of crackles for phosphate coating, and it is anti-corrosion largely to influence its Performance, super-hydrophobic film common intensity is not high, and existing surface treatment method is all based on magnesium alloy matrix surface, in magnesium alloy Film surface further progress is surface-treated and obtains splendid corrosion proof processing method and yet there are no relevant report.
Nowadays, by bionic principle, various micro-structure surfaces is constantly prepared and is used to realization pair The operation such as transmission, separation, stabilization, selection, collection, sequence and fixation of fine droplet is repelled super-hydrophobic including a variety of pairs of water Surface there is the parent-of capacity gauge to dredge blending surface water, can be to the hydrophily distribution gradient that hydrophily is identified Surface also may be implemented to titrate the surface etc. of position in micro-scaled structures and mesostructure upper liquid of receiving, and how in magnesium alloy Surface forms such micro-structure surface, especially realize to the transmission of fine droplet, separation, stabilization, selection, collection, sequence and The corrosion resistance that Mg alloy surface is also ensured while the operation such as fixed, becomes current this field researcher key to be solved One of problem.If Mg alloy surface has both the above-mentioned specific function to fine droplet and corrosion resistance is good, will certainly be to magnesium alloy Application field exert far reaching influence.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of magnesium alloy parent/super-hydrophobic controllable composite membranes in region Preparation method, first Mg alloy surface be prepared for one layer be uniformly distributed fine cracks overall leveling ferric phosphate zinc calcium/ Manganese salt layer prepares local hydrophilic Si in smooth ferric phosphate zinc calcium/manganese salt layer surface3N4Layer and super-hydrophobic layer, realizing magnesium alloy can Control region surface such as is transmitted to microlayer model, is separated, is stablized, is selected, is collected, sorted and is fixed at the operation, and is also further mentioned The high corrosion resisting property of magnesium alloy, and then it is greatly improved the application field and application effect of magnesium alloy.
The technical solution adopted by the present invention to solve the technical problems is: a kind of magnesium alloy parent/super-hydrophobic region is controllably multiple The preparation method for closing film, includes the following steps:
S1: Mg alloy surface is subjected to phosphate conversion processing, obtains anti-corrosion conversion coating；
S2: the Si of one layer of micro-nano-scale is deposited on the anti-corrosion conversion coating3N4Layer；
S3: to the Si3N4The partial region of layer performs etching, so that (not being etched) is Si in design section3N4Layer, Design section outer (being etched) is anti-corrosion conversion coating；
S4: the anti-corrosion conversion layer surface outside the design section prepares one layer of super-hydrophobic film layer.
Embodiment as a further preference, step S1 specifically comprise the following steps:
(1) Mg alloy surface is pre-processed；
(2) pretreated magnesium alloy is placed in by phosphate, potassium permanganate, citrate, sodium alginate, phosphoric acid, gone Conversion processing is carried out in the conversion treating solution of ionized water composition, conversion treating solution water-bath maintains the temperature at 30-45 DEG C, handles the time It is 15-20 minutes, control gentle agitation is carried out using multifunction constant temperature magnetic stirring apparatus in conversion processing process.
Embodiment as a further preference, it is described that Mg alloy surface is subjected to pretreated concrete operation step such as Under:
(1) magnesium alloy is first processed into 20 × 20 × 1mm3Square sheet metal specimens；
(2) successively two square surfaces of sample are roughly ground with the water-proof abrasive paper of 400 mesh, 800 mesh；
(3) fine grinding successively is carried out to specimen surface with the water-proof abrasive paper of 1000 mesh, 1500 mesh and 2000 mesh；
(4) sample is polished with diamond paste；
(5) respectively with acetone and analytically pure alcohol successively to magnesium alloy sample ultrasonic cleaning 10 minutes, sample is removed The grease stain and other impurities on surface, then cool breeze dries up.
Embodiment as a further preference, the phosphatic concentration are 90-150g/L, are 1.2 by mass ratio: The FeHPO of 1:0.84、Zn3(PO4)2And Ca3(PO4)2It mixes；The concentration of the potassium permanganate is 20-60g/L；The lemon Lemon hydrochlorate is potassium citrate or sodium citrate, and concentration is 0.2~0.35g/L；The concentration of the sodium alginate be 0.5~ 1.2g/L；The pH value of conversion fluid is adjusted between 6.0-6.5 using the phosphoric acid.
Embodiment as a further preference, step S2 specifically:
Using chemical vapor deposition method, chemical vapor deposition machine is evacuated to 3 × 10-4-4×10-4After Pa, it is passed through Ammonia and H2And SiH4Mixed gas, wherein H2And SiH4Volume ratio be 4:1, the flow of ammonia is 110mL/min, H2With SiH4Mixed gas flow be 105mL/min, temperature is set as 280-300 DEG C, the Si of deposition3N4Layer is with a thickness of 3000-5000 Angstrom.
Embodiment as a further preference, step S3 specifically comprise the following steps:
(1) first in Si3N4Layer surface smear a layer photoresist, wherein photoresist classification be AZ4620, spin coating photoresist, Revolving speed is 100-150r/s, and drying 2-4 minutes is carried out on baking-glue machine, is aligned with mask plate to photoresist on exposure machine Exposure, is finally developed using developer solution, has just obtained the photoetching compound protective layer in designed region；
(2) magnesium alloy handled through previous step is fixed on the platform inside plasma etching machine, by plasma Body etching machine vacuumizes, and is passed through the CF that volume ratio is 1:1:14、C4F8And SF6Gas performs etching, time 45min-1h, it It washes remaining photoresist in acetone afterwards, has just obtained in design section as Si3N4It is anti-corrosion conversion outside layer, design section The magnesium alloy of layer.
Embodiment as a further preference, super-hydrophobic film layer described in step S4 are prepared using electrodeposition process, specifically Are as follows: will through step S3, treated that magnesium alloy is placed in electrodeposit liquid, using this magnesium alloy as cathode, platinum electrode as anode, Electro-deposition is carried out under 10~30V voltage, 20-30 DEG C is maintained the temperature in electrodeposition process, electrodeposition time is 15-30 points Clock.Constant temperature and stir process are carried out using constant temperature blender with magnetic force in electrodeposition process.
Embodiment as a further preference, the electrodeposit liquid are formed sediment by fatty acid, cerium salt, ethylamine hydrochloride, straight chain Powder and dehydrated alcohol composition, wherein the concentration of fatty acid is 20-40g/L, and the concentration of cerium salt is 15-25g/L, ethylamine hydrochloride Concentration is 1.2-1.5g/L, and the concentration of amylose is 0.6-0.8g/L.
Embodiment as a further preference, the fatty acid be mass ratio be 1:1.2:1.1:1 straight chain stearic acid, The mixture that eicosenoic acid, linoleic acid, antiform oleic acid form, the cerium salt is the Ce (NH that mass ratio is 0.8:14)2(NO3)6 With Ce (SO4)2·4H2The mixture of O.
The positive effect of the present invention: in the present invention, since magnesium alloy sample is polished and after the pretreatment that polishes, reach Required roughness is prepared for apparent distribution uniform ground after phosphate conversion processing, locally there is the ferric phosphate of fine cracks Zinc calcium/manganese salt base.Then plasma-deposited is utilized, after vacuumizing, reaction gas is passed through, makes it in phosphatization substrate surface It nearby ionizes, phosphatization substrate surface generates cathodic sputtering, improves surface-active, thus completes on magnesium alloy sample surface Thermal chemical reaction and plasma chemical reaction form the Si of micro-nano-scale in phosphatization substrate surface3N4Layer.Recycle light Lithography deposited Si3N4The surface of film layer forms one layer of uniform photoresist film layer by spin coating-drying, uses exposure Ray machine and mask plate are formed using positive lithography in Mg alloy surface with phosphatization base and Si3N4Film layer is substrate, particular design shape The film layer of the photoresist overlay of shape.Binding plasma lithographic method etches away the Si not being covered by photoresist3N4Film layer passes through Developing technique, and the photoresist of specific region is washed with acetone, it is formed using ferric phosphate zinc calcium/manganese salt as substrate, regional area Cover Si3N4The magnesium alloy of film layer (regional area is controllable).Due to Si3N4Insulating properties is very good, and the region being entirely covered is caused to exist Hereafter hardly exchange electronics with the external world in electrodeposition process, so and being not involved in the process of electro-deposition, therefore holding Si3N4 The original water-wet behavior in region.During electro-deposition, the surface of phosphate coating be initially formed the micron of one layer of fatty acid cerium salt/ Nano combined Multi-scale model, while fatty acid has carried out moditied processing to the structure on this basis, reduce its surface can, two Kind effect, which intersects, to be carried out and finally forms one layer of super-hydrophobic film layer in the ferric phosphate zinc calcium/manganese salt conversion base.This is super thin Water film is filled in the gap of phosphating coat base first, finally covers phosphate coating not by the Si of micro-nano-scale3N4The table of protection Face, this results in two benefits: 1, the shortcomings that compensating for phosphatization layer surface discrepitate；2, super-hydrophobic film layer is with ferric phosphate zinc Calcium/manganese salt layer and have micro-nano-scale Si3N4Layer is " skeleton ", increases self-strength.
Detailed description of the invention
Fig. 1 is magnesium alloy parent/super-hydrophobic controllable composite membrane in region preparation flow figure.
Fig. 2 is magnesium alloy parent/super-hydrophobic controllable composite film surface in region SEM photograph.
Fig. 3 is magnesium alloy parent/super-hydrophobic controllable composite film surface in region EDS Surface scan figure.
Fig. 4 is magnesium alloy parent/super-hydrophobic controllable composite film surface in region contact angle picture.
Specific embodiment
With reference to the accompanying drawing to a preferred embodiment of the present invention will be described in detail.
Implement to select AZ91D magnesium alloy, A refers to that Al, Z refer to Zn, specific ingredient and the following table of content:
Title Mg Al Zn Mn Si Cu Ni Fe
AZ91D Surplus 8.5-9.5 0.45-0.9 0.17-0.4 ≤0.05 ≤0.025 ≤0.001 ≤0.004
Embodiment 1
Referring to Fig.1, the preferred embodiment of the present invention 1 provides a kind of preparation of magnesium alloy parent/super-hydrophobic controllable composite membrane in region Method includes the following steps:
1) 20 × 20 × 1mm is used3Magnesium alloy sample, which is performed the following operation: 1. by magnesium on polishing machine The water-proof abrasive paper of two facings of alloy sample, 400 mesh to 800 mesh is roughly ground；2. successively by the facing of magnesium alloy sample With 1000 mesh, the water-proof abrasive paper fine grinding of 1500 mesh and 2000 mesh；3. being arrived using diamond paste to magnesium alloy sample fine grinding The facing of 2000 mesh is polished；4. successively super to polished magnesium alloy sample with acetone and analytically pure alcohol respectively Sound wave cleans 10 minutes, washes away the impurity such as the greasy dirt on surface, is then dried up with cool breeze, obtains magnesium alloy to be processed.
2) in the solution being made of ferric phosphate zinc calcium salt, manganese salt, citrate, sodium alginate, phosphoric acid, deionized water into The processing of row phosphate conversion.First configuration phosphate concn be 150g/L, the conversion treating solution that manganese salt concentration is 40g/L, wherein Phosphate is the FeHPO that mass ratio is 1.2:1:0.84、Zn3(PO4)2And Ca3(PO4)2Mixture, manganese salt is KMnO4；It is described Citrate is potassium citrate, concentration 0.3g/L；The concentration of the sodium alginate is 0.6g/L；Into conversion treating solution by It gradually instills phosphoric acid and adjusts its pH value, its pH value is made to reach 6.5.Magnesium alloy to be processed is placed in conversion treating solution, conversion processing Process is using multifunction constant temperature magnetic stirrer and keeps 45 DEG C of constant temperature, and the conversion processing time is 16 minutes.
3) PECVD is used, is sunk on the magnesium alloy sample after phosphorating treatment using plasma activated chemical vapour deposition platform One layer of Si of product3N4Film layer.Concrete operations are as follows: chemical vapor deposition platform is evacuated to 3.5 × 10-4Pa-4×10-4Pa is passed through ammonia Gas and H2And SiH4Mixed gas, wherein H2And SiH4Volume ratio be 4:1, the flow of ammonia is 110mL/min, H2With SiH4Mixed gas flow be 105mL/min, temperature is set as 280-300 DEG C, and deposition thickness is 4500 angstroms.
4) to the Si3N4The partial region of layer performs etching, so that (not being etched) is Si in design section3N4Layer, if Counting outside region (being etched) is anti-corrosion conversion coating, specifically: first in Si3N4Layer surface smears a layer photoresist, wherein photoresist Classification is AZ4620, spin coating photoresist, revolving speed 150r/s, and drying 2 minutes is carried out on baking-glue machine, mask is used on exposure machine Plate carries out alignment exposure to photoresist, is finally developed using developer solution, has just obtained the photoresist protection in designed region Layer.
It is fixed on the platform inside plasma etching machine, plasma etching machine is vacuumized, being passed through volume ratio is The CF of 1:1:14、C4F8And SF6Gas performs etching, and time 1h washes remaining photoresist in acetone later, must It has arrived in design section as Si3N4It is the magnesium alloy of anti-corrosion conversion coating outside layer, design section.
5) it is obtaining using ferric phosphate zinc calcium/manganese salt layer as base, design section covers Si3N4The magnesium alloy sample table of layer Face carries out electro-deposition.Required electrodeposit liquid is prepared first, prepared electrodeposit liquid in this embodiment are as follows: 12g mass ratio is The straight chain stearic acid of 1:1.2:1.1:1, the mixture that eicosenoic acid, linoleic acid, antiform oleic acid form, 7g mass ratio is 0.8: 1 Ce (NH4)2(NO3)6With Ce (SO4)2·4H2The mixture of O composition, 0.4g ethylamine hydrochloride, 0.2g amylose, and 300mL dehydrated alcohol.The sample is connected on the cathode of electrolytic cell, is put into electrodeposit liquid and carries out electro-deposition.Supply voltage is 15V makees anode with platinum electrode.Electrodeposition temperature is maintained at 25 DEG C, and electrodeposition time is 15 minutes.Magnesium alloy is taken out after 15 minutes Sample is dried up with washes of absolute alcohol and with cool breeze, and magnesium alloy parent/super-hydrophobic region controllably compound conversion film can be obtained.
The SEM experimental result of the prepared controllable compound conversion film surface in magnesium alloy parent/super-hydrophobic region as shown in Fig. 2, It can be seen that Mg alloy surface significantly separates two regions, wherein round 201 regions are that deposited Si3N4The region of layer, also It is hydrophilic region, is elsewhere super-hydrophobic region.Fig. 3 show magnesium alloy parent/super-hydrophobic region controllably compound conversion film EDS Surface scan picture, thus figure it can be seen that Mg alloy surface deposited Si3N4In the region of layer, characteristic element silicon is at rule Circular distribution, this region and the process for being not involved in electro-deposition, thus the characteristic element carbon of super-hydrophobic film this area distribution very It is few.The region surface shows hydrophilic characteristic, and other regions then show super-hydrophobic characteristic.Fig. 4 is controllably multiple in region It closes conversion film surface and places the effect picture that water droplet obtains, it can be seen that Mg alloy surface is performance parent/superhydrophobic characteristic, This is realization in actual production to the control lay a good foundation of microlayer model.
Embodiment 2
The preferred embodiment of the present invention 2 provides a kind of preparation method of magnesium alloy parent/super-hydrophobic controllable composite membrane in region, including Following steps:
1) 20 × 20 × 1mm is used3Magnesium alloy sample, which is performed the following operation: 1. by magnesium on polishing machine The water-proof abrasive paper of two facings of alloy sample, 400 mesh to 800 mesh is roughly ground；2. successively by the facing of magnesium alloy sample With 1000 mesh, the water-proof abrasive paper fine grinding of 1500 mesh and 2000 mesh；3. being arrived using diamond paste to magnesium alloy sample fine grinding The facing of 2000 mesh is polished；4. successively super to polished magnesium alloy sample with acetone and analytically pure alcohol respectively Sound wave cleans 10 minutes, washes away the impurity such as the greasy dirt on surface, is then dried up with cool breeze, obtains magnesium alloy to be processed.
2) in the solution being made of ferric phosphate zinc calcium salt, manganese salt, citrate, sodium alginate, phosphoric acid, deionized water into The processing of row phosphate conversion.First configuration phosphate concn be 130g/L, the conversion treating solution that manganese salt concentration is 30g/L, wherein Phosphate is the FeHPO that mass ratio is 1.2:1:0.84、Zn3(PO4)2And Ca3(PO4)2Mixture, manganese salt is KMnO4；；It is described Citrate is sodium citrate, concentration 0.35g/L；The concentration of the sodium alginate is 1g/L；Into conversion treating solution by It gradually instills phosphoric acid and adjusts its pH value, its pH value is made to reach 6.2.Magnesium alloy to be processed is placed in conversion treating solution, conversion processing Process is using multifunction constant temperature magnetic stirrer and keeps 40 DEG C of constant temperature, and the conversion processing time is 15 minutes.
3) PECVD is used, is sunk on the magnesium alloy sample after phosphorating treatment using plasma activated chemical vapour deposition platform One layer of Si of product3N4Film layer.Concrete operations are as follows: chemical vapor deposition platform is evacuated to 3.5 × 10-4Pa-4×10-4Pa is passed through ammonia Gas and H2And SiH4Mixed gas, wherein H2And SiH4Volume ratio be 4:1, the flow of ammonia is 110mL/min, H2With SiH4Mixed gas flow be 105mL/min, temperature is set as 280-300 DEG C, and deposition thickness is 4000 angstroms.
4) to the Si3N4The partial region of layer performs etching, so that (not being etched) is Si in design section3N4Layer, if Counting outside region (being etched) is anti-corrosion conversion coating, specifically: first in Si3N4Layer surface smears a layer photoresist, wherein photoresist Classification is AZ4620, spin coating photoresist, revolving speed 100r/s, and drying 2 minutes is carried out on baking-glue machine, mask is used on exposure machine Plate carries out alignment exposure to photoresist, is finally developed using developer solution, has just obtained the photoresist protection in designed region Layer.
It is fixed on the platform inside plasma etching machine, plasma etching machine is vacuumized, being passed through volume ratio is The CF of 1:1:14、C4F8And SF6Gas performs etching, and time 45min washes remaining photoresist, just in acetone later It has obtained in design section as Si3N4It is the magnesium alloy of anti-corrosion conversion coating outside layer, design section.
5) it is obtaining using ferric phosphate zinc calcium/manganese salt layer as base, design section covers Si3N4The magnesium alloy sample table of layer Face carries out electro-deposition.Required electrodeposit liquid is prepared first, prepared electrodeposit liquid in this embodiment are as follows: 8g mass ratio is 1: The mixture that straight chain stearic acid, eicosenoic acid, linoleic acid, the antiform oleic acid of 1.2:1.1:1 forms, 6g mass ratio are 0.8:1 Ce (NH4)2(NO3)6With Ce (SO4)2·4H2The mixture of O composition, 0.42g ethylamine hydrochloride, 0.25g amylose, and 300mL dehydrated alcohol.The sample is connected on the cathode of electrolytic cell, is put into electrodeposit liquid and carries out electro-deposition.Supply voltage is 20V makees anode with platinum electrode.Electrodeposition temperature is maintained at 25 DEG C, and electrodeposition time is to take out magnesium alloy after 12 minutes, 12 minutes Sample is dried up with washes of absolute alcohol and with cool breeze, and magnesium alloy parent/super-hydrophobic region controllably compound conversion film can be obtained.
It is above-described to be merely a preferred embodiment of the present invention, it should be understood that the explanation of above embodiments is only used In facilitating the understanding of the method and its core concept of the invention, it is not intended to limit the scope of protection of the present invention, it is all of the invention Any modification for being made within thought and principle, equivalent replacement etc., should all be included in the protection scope of the present invention.

Claims (7)

1. a kind of preparation method of magnesium alloy parent/super-hydrophobic controllable composite membrane in region, which comprises the steps of:
S1: Mg alloy surface is subjected to phosphate conversion processing, obtains anti-corrosion conversion coating；
S2: the Si of one layer of micro-nano-scale is deposited on the anti-corrosion conversion coating3N4Layer；
S3: to the Si3N4The partial region of layer performs etching, so that (not being etched) is Si in design section3N4Layer designs area Overseas (being etched) is anti-corrosion conversion coating；
S4: the anti-corrosion conversion layer surface outside the design section prepares one layer of super-hydrophobic film layer；
Wherein step S2 specifically:
Using chemical vapor deposition method, chemical vapor deposition machine is evacuated to 3 × 10-4-4×10-4After Pa, be passed through ammonia with And H2And SiH4Mixed gas, wherein H2And SiH4Volume ratio be 4:1, the flow of ammonia is 110mL/min, H2And SiH4's Mixed gas flow is 105mL/min, and temperature is set as 280-300 DEG C, the Si of deposition3N4Layer is with a thickness of 3000-5000 angstroms；
Step S3 specifically comprises the following steps:
(1) first in Si3N4Layer surface smears a layer photoresist, and wherein photoresist classification is AZ4620, spin coating photoresist, revolving speed For 100-150r/s, drying 2-4 minutes is carried out on baking-glue machine, alignment exposure is carried out to photoresist with mask plate on exposure machine Light is finally developed using developer solution, and the photoetching compound protective layer in designed region has just been obtained；
(2) magnesium alloy handled through previous step is fixed on the platform inside plasma etching machine, plasma is carved Erosion machine vacuumizes, and is passed through the CF that volume ratio is 1:1:14、C4F8And SF6Gas performs etching, time 45min-1h, Zhi Hou Remaining photoresist is washed in acetone, has just been obtained in design section as Si3N4It is anti-corrosion conversion coating outside layer, design section Magnesium alloy.
2. a kind of preparation method of magnesium alloy parent/super-hydrophobic controllable composite membrane in region according to claim 1, feature exist In step S1 specifically comprises the following steps:
(1) Mg alloy surface is pre-processed；
(2) pretreated magnesium alloy is placed in by phosphate, potassium permanganate, citrate, sodium alginate, phosphoric acid, deionization Conversion processing is carried out in the conversion treating solution of water composition, and conversion treating solution water-bath maintains the temperature at 30-45 DEG C, and the processing time is 15-20 minutes, control gentle agitation is carried out using multifunction constant temperature magnetic stirring apparatus in conversion processing process.
3. a kind of preparation method of magnesium alloy parent/super-hydrophobic controllable composite membrane in region according to claim 2, feature exist In, it is described by Mg alloy surface carry out it is pretreated specific steps are as follows:
(1) magnesium alloy is first processed into 20 × 20 × 1mm3Square sheet metal specimens；
(2) successively two square surfaces of sample are roughly ground with the water-proof abrasive paper of 400 mesh, 800 mesh；
(3) fine grinding successively is carried out to specimen surface with the water-proof abrasive paper of 1000 mesh, 1500 mesh and 2000 mesh；
(4) sample is polished with diamond paste；
(5) respectively with acetone and analytically pure alcohol successively to magnesium alloy sample ultrasonic cleaning 10 minutes, specimen surface is removed Grease stain and other impurities, then cool breeze dry up.
4. a kind of preparation method of magnesium alloy parent/super-hydrophobic controllable composite membrane in region according to claim 2, feature exist In: the phosphatic concentration is 90-150g/L, the FeHPO for being 1:1:1 by mass ratio4、Zn3(PO4)2And Ca3(PO4)2It is mixed It closes；The concentration of the potassium permanganate is 20-60g/L；The citrate is potassium citrate or sodium citrate, and concentration is 0.2~0.35g/L；The concentration of the sodium alginate is 0.5~1.2g/L；The pH value of conversion fluid is adjusted to using the phosphoric acid Between 6.0-6.5.
5. a kind of preparation method of magnesium alloy parent/super-hydrophobic controllable composite membrane in region according to claim 1, feature exist It is prepared in: super-hydrophobic film layer described in step S4 using electrodeposition process, specifically: it will treated that magnesium alloy is placed in through step S3 In electrodeposit liquid, using this magnesium alloy as cathode, platinum electrode carries out electro-deposition, electro-deposition as anode under 10~30V voltage 20-30 DEG C is maintained the temperature in the process, and electrodeposition time is 15-30 minutes, and constant temperature blender with magnetic force is used in electrodeposition process Carry out constant temperature and stir process.
6. a kind of preparation method of magnesium alloy parent/super-hydrophobic controllable composite membrane in region according to claim 5, feature exist In: the electrodeposit liquid is made of fatty acid, cerium salt, ethylamine hydrochloride, amylose and dehydrated alcohol, and wherein fatty acid is dense Degree is 20-40g/L, and the concentration of cerium salt is 15-25g/L, and the concentration of ethylamine hydrochloride is 1.2-1.5g/L, the concentration of amylose For 0.6-0.8g/L.
7. a kind of preparation method of magnesium alloy parent/super-hydrophobic controllable composite membrane in region according to claim 6, feature exist In, the fatty acid be mass ratio be 1:1.2:1.1:1 straight chain stearic acid, eicosenoic acid, linoleic acid, antiform oleic acid composition Mixture, the cerium salt is the Ce (NH that mass ratio is 0.8:14)2(NO3)6With Ce (SO4)2·4H2The mixture of O.
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CN104711572A (en) * 2015-01-26 2015-06-17 北方工业大学 Production method of magnesium alloy phosphate/fatty acid salt composite super-hydrophobic corrosion resistant membrane

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