CN1687488A - Technique for treating synergism coat of aluminium alloy material and fluorine polymer - Google Patents
Technique for treating synergism coat of aluminium alloy material and fluorine polymer Download PDFInfo
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- CN1687488A CN1687488A CN 200510020551 CN200510020551A CN1687488A CN 1687488 A CN1687488 A CN 1687488A CN 200510020551 CN200510020551 CN 200510020551 CN 200510020551 A CN200510020551 A CN 200510020551A CN 1687488 A CN1687488 A CN 1687488A
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Abstract
The present invention relates to a technique of treating coat the film made of aluminum alloy fluorine-polymer. Material or part of aluminum alloy should be hard anodizing first and introduce fluorine-polymer in the pore or on the surface. We can also expend the pore first and introduce fluorine-polymer on the surface and in the pore later. Fuse fluorine-polymer and anode oxidation coat together by vacuum heat treatment for high temperature. It's suitable for part of optic-electronic equipment. Firstly, it has good extinction, doesn't fade and doesn't break off: secondly, it is rigid and wearable; thirdly, it contains fluorine-polymer, has low friction coefficient, has the capability of self-lubricating, so its wearable and anti-corrosive performance can be improved a lot; fourthly, it has capability of hydrophobicity and can bear litmusless salt spray, so it can sustain most of the corrosion in bad condition and corrodent matter. Fifthly, the surface is self-lubricating, and has the capability of self-lubricating and dustproof.
Description
Technical field
The coating that the present invention relates to aluminum alloy materials is handled particularly a kind of fluoropolymer technique for treating synergism coat that is used for the aluminum alloy spare part of photoelectric instrument.
Background technology
Civilian and the war industry field in the modern times, in order to adapt to high strength, corrosion-resistant and light-weighted requirement, adopted aluminum alloy materials more and more in the equipment and the design of universal machine, in making, aluminum alloy materials occupies an important position in the design of the military equipment and the product for civilian use, in making, and is most important lightweight material; Adopt aluminium alloy in the photoelectron product especially in a large number, many parts of various optical aiming systems, optical ranging system, electronic information instrument, computer etc. are made by aluminum alloy materials such as duralumin, ultralumin, wrought aluminium, corrosion-resisting aluminiums; The method that the surface treatment of aluminum alloy materials or component is adopted at present mainly contains protection by paints and lacquers as being that the workpiece that non-chromium is handled carries out application processing, common anode oxidising dyeing and/or sealing treatment, hard anodizing dyeing and/or sealing treatment through chromic salt oxidation or titanium zirconium, and these methods can satisfy service requirements substantially for common parts or non-wear part; Yet the serious weakness of aluminium alloy is that matter is soft, frictional coefficient is high, wearing and tearing are pulled greatly, easily and is difficult to lubricate, can't meet the demands for wear part and the demanding part of solidity to corrosion, and the one, their hardness is low, not wear-resisting; The 2nd, these protective layers do not have lubricity; The 3rd, the corrosion resisting property deficiency; The 4th, painted the fast light property of shining is poor; Do not have dustproof, moisture-proof function; The result who causes be easily fade in the part use, show money or valuables one carries unintentionally, enamelled coating comes off, matrix corrosion, the key component flexibility of operation is poor.Must research can satisfy high rigidity simultaneously, protection against the tide is damp proof, antiplastering dustproof, corrosion-resistant, light aging resisting and have the special functional protective coating technique of properties of antifriction and wear resistance.
Summary of the invention
The objective of the invention is deficiency for the existing surface protection technique existence that solves aluminum alloy materials, soft as matter, corrosion resisting property is poor, frictional coefficient height, wearing and tearing are pulled greatly, easily and be difficult to lubricate, and a kind of protective capacities that provides is strong, antifriction and the good technique for treating synergism coat of aluminium alloy material and fluorine polymer of wear-resistant self-lubricating performance.
The object of the present invention is achieved like this: a kind of technique for treating synergism coat of aluminium alloy material and fluorine polymer is characterized in that: aluminum alloy materials at first carries out the basement membrane layer of hard anodizing with the preparation synergism coat; In the rete that the hard anodized film layer or the process reaming of preparation are handled, introduce fluoropolymer then; Make fluoropolymer and the fusion of hard anodized film layer be one by vacuum heat-treating method at last, form synergism coat.
The present invention is with the basement membrane layer of hard anodized film layer as synergism coat, with the protection by paints and lacquers of present employing as being that workpiece that non-chromium is handled carries out application processing, common anode oxidising dyeing and/or sealing treatment, hard anodizing dyeing and/or sealing treatment and compares through chromic salt oxidation or titanium zirconium: 1, the hard anodized film layer is as basement membrane layer, has very high hardness, more much higher than common coating or common anode zone of oxidation hardness, and it and basal body binding force are good, surfacing; 2, the anodic oxidation layer porosity is big, is suitable for follow-up synergism and handles, and the synergism coat of preparation can not satisfy the service requirements of many workpiece yet even do not carry out reaming to handle; 3, the synergism coat that forms through this art breading is that even Dark grey is to black, do not need painted processing, and may command is prepared as even ater coating, be particularly suitable for the processing of photoelectric instrument component, eliminate optical property is good, coating does not fade, does not show money or valuables one carries unintentionally, does not come off, and corrosion resisting property obviously is better than common process for protecting; 4, the component through this art breading have dry film self-lubricating property and dustproof and anti-adhibit property, and wear resistance and antifriction performance are good, component flexible operation, convenience; 5, existing technology is carried out accurate heat treatment process under atmospheric condition, and workpiece is yielding, and the easy carbonization of fluoropolymer is decomposed, and the moisture content in the stratum basale micropore, air or impurity can not thoroughly be got rid of, and is unfavorable to the filling of fluoropolymer in micropore; And this technology is finished under vacuum state, and workpiece is not yielding, and the possibility that the fluoropolymer carbonization is decomposed is much smaller, and the moisture content in the stratum basale micropore, air or impurity are thoroughly got rid of, and are beneficial to the filling of fluoropolymer in micropore.
Specifically, the present invention is such:
1, the hard anodizing of aluminum alloy materials: aluminum alloy materials or component carry out alkaline degreasing and/or alkalescence erosion earlier by well-known method to be washed and goes out optical processing through nitric acid acidwashing, after water cleans, and then carries out hard anodizing and handles.
In above-mentioned steps, the hard anodizing of aluminum alloy materials or component adopts the nitration mixture hard anodizing; Aluminium alloy nitration mixture hard anodizing solution contains sulfuric acid, lactic acid, citric acid, aniline sulfonic acid, aluminum ion; Vitriolic content is 1～10%, the content of lactic acid 0.5～10%, citric acid 0.5～10%, aniline sulfonic acid is 0～5%, aluminum ions content is 0.1～0.5%; Hard anodizing adopts galvanic current; Processing condition are temperature-7～5 ℃, current density 1～5A/dm
2, whole voltage 70～120V, pneumatic blending, oxidization time 30～120min; The gauge control of hard anodized film is at 20～60 μ m.
The hard anodizing of above-mentioned Al-alloy parts adopts vitriolic content in the nitration mixture hard anodizing solution for vitriolic content is 3～8%, the content of lactic acid 2～7%, citric acid 3～8%, aniline sulfonic acid is 0.3～3%, aluminum ions content is 0.3% for good; Processing condition are temperature-5～2 ℃, current density 2～3.5A/dm
2, whole voltage 90～110V, pneumatic blending, oxidization time 50～90min be good; The gauge control of hard anodized film is good at 20～50 μ m.
2, the reaming of aluminium alloy hard anodized film layer is handled: the aluminium alloy hard anodized film has porousness, can directly carry out synergism coat and handle; Also but the antianode oxide film carries out the reaming processing and increases micropore size and porosity, and to increase the infiltration capacity of functional fluoropolymer, reaming is handled and adopted chemical enlargement processing or electrochemistry interchange reaming to handle.
In the above-mentioned steps, chemical enlargement adopts sulfuric acid reaming solution, sulfuric acid content scope 50～300g/l in the reaming solution; The chemical enlargement processing condition are 20～30 ℃ of temperature, time 1～20min; Electrochemistry exchanges reaming and adopts phosphoric acid-oxalic acid reaming solution, and phosphorus acid content scope 50～200g/l, oxalic acid content scope are 10～50g/l in the reaming solution; It is 20～30 ℃ of temperature, voltage 5～30V, time 3～20min that electrochemistry exchanges the chambering process condition.
Sulfuric acid content scope 100～200g/l is good in the above-mentioned chemical enlargement solution; The chemical enlargement processing condition are 20～25 ℃ of temperature, and time 3～10min is good; Phosphorus acid content scope 100～200g/l, oxalic acid content scope 20～30g/l are good in the electrochemistry interchange reaming solution; It is that 20～25 ℃ of temperature, voltage 8～15V, time 5～10min are good that electrochemistry exchanges the chambering process condition.
3, the introducing of fluoropolymer: the hardening oxidation membrane micropore of handling on hardening oxidation membrane micropore and surface thereof and/or through reaming and lubricant is introduced on the surface or encapsulant also is one of committed step of preparation synergism coat, it is many more dark more that fluoropolymer microparticles enters micropore, the over-all properties of final synergism coat is just good more, can use several different methods to introduce lubricants such as fluoropolymer in the aluminum alloy surface stratum basale of preparation.
And technology of the present invention is the difference according to material or component working method, the difference of surface appearance with to the synergism coat performance stress the different of face, the introducing method of fluoropolymer or adopt the emulsion hot dipping method or/and spraying method or/and the re-electrolysis method.
Specifically, hot dipping method technology is as follows: infiltration liquid fluoropolymer microparticles concentration range is 10～100g/l, also can be added with additive increase infiltration effects such as organic fluorine surfactant; The Infiltration Technics condition is 30～100 ℃ of temperature, and the time is 5～60min, and this method is comparatively suitable to complex-shaped part; Spraying method adopts high atomization rate spray gun at model or workpiece surface spraying fluoropolymer, and coating thickness is controlled in the 20 μ m, and spraying is 50～400g/l with the fluoropolymer emulsions concentration range, and this method is applicable to easy spraying part; Re-electrolysis method technology is as follows: adopt anode electrolysis, negative electrode is a stereotype, electrolytic solution fluoropolymer microparticles concentration range is 1～30g/l, also can be added with additive increase infiltration effects such as organic fluorine surfactant, and the electrolysis process condition is that current density range is 10～100mA/dm
2, temperature range is 20～60 ℃, and time range is 1～30min, and this method is suitable for surface smoothness height, the better simply component of profile, the absorption good uniformity.
Infiltration liquid fluoropolymer microparticles concentration range is that 30～70g/l is good in the above-mentioned hot dipping method technology, and the Infiltration Technics condition is that 40～80 ℃ of temperature are good, and the time is that 10～40min is good; Coating thickness is controlled at 5～10 μ m in the spraying method technology, and spraying is that 100～300g/l is good with the fluoropolymer emulsions concentration range; Electrolytic solution fluoropolymer microparticles concentration range is 5～20g/l in the re-electrolysis method, and the electrolysis process condition is that current density range is 20～80mA/dm
2, temperature range is 30～50 ℃, time range is that 5～20min is good.
Above-mentioned fluoropolymer can adopt the water miscible liquid of fluoropolymers such as tetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene copolymer, produces P-202, F-203 polytetrafluoroethyldispersion dispersion and FS-46 fluoroplastics dispersion emulsion etc. as the Teflon of Du Pont emulsion, Shanghai three Ai Fu companies product FR301 ptfe emulsion and FR463 perfluoroethylene-propylene emulsion, Shanghai organic chemistry institute.
4, vacuum heat treatment: after introducing fluoropolymer,, allow fluoropolymer microparticles combine together fully, realize the synergism of the two, could form the coating of performance brilliance with the anodic oxidation micropore by the thermal treatment of precision.
Thermal treatment of the present invention is carried out under vacuum state, and processing condition are that temperature range is 300～450 ℃, and the treatment time scope is 20～120min, and general vacuum degree control is 20～1 * 10
-2The Pa scope.The selected treatment temp of the present invention is relevant with used fluoropolymer, can not cause the carbonization of fluoropolymer microparticles to decompose, but temperature can not be low excessively, otherwise fluoropolymer microparticles is mobile poor, and is unfavorable to forming synergism coat; If the selected vacuum tightness of the present invention is low excessively, synergy is not obvious, and final coating performance is not good, if vacuum tightness is too high, fluoropolymer microparticles is difficult to fill fenestra again, can not be fused in the fenestra equably, thereby cause the smoothness of coating not enough; The present invention must guarantee that the hard anodized film stratum basale of fluoropolymer and hard anodized film or process reaming fully fuses, and forms one, with the performance synergy the determined treatment time.
By the principle that leading portion is stated, the processing condition of above-mentioned vacuum heat treatment are with 300～450 ℃ of temperature ranges; Treatment time scope 30～80min; General vacuum degree control is 5～5 * 10
-2Pa is good.
Thermal treatment of the present invention unlike the prior art be, existing technique for treating synergism coat carries out under atmospheric condition, workpiece may produce distortion, the easy carbonization chain rupture of fluoropolymer, and the present invention carries out under vacuum state, can farthest control the distortion of workpiece, fluoropolymer is difficult for the carbonization chain rupture, the coating performance excellence.
The aluminium alloy synergistic fluoropolymer coating that forms by the present invention shows even ater, thickness 20～60 μ m, microhardness 400～650HV, and 5% neutral salt spray test, 1000～2000h corrosion is rated 7～8 grades, and kinetic friction coefficient is less than 0.15.
Beneficial effect of the present invention: the one, even through the synergism coat color and luster that this art breading forms, and may command is prepared as even ater, is particularly suitable for the processing of photoelectric instrument component, and eliminate optical property is good, and coating does not fade, does not show money or valuables one carries unintentionally, does not come off; The 2nd, coating is the body of combining closely of hard substrate layer and fluoropolymer, and it has become a whole part of metallic matrix, and the coating hardness height reaches 400～650HV, and wear resistance is good; The 3rd, contain the antifriction material fluoropolymer in the coating, kinetic friction coefficient has self-lubricating property less than 0.15, can increase considerably its wear resisting property; The 4th, the fluoropolymer in the coating can improve its anti-corrosion capability greatly, and this coating not only has hydrophobic, oil repellency, also has 1000～2000 hours anti-neutral salt spray test ability, can resist the etch of most of hostile environments or corrosive deposit; The 5th, coating is a dry film self lubricating faade, has dry film self lubricating function; The 6th, coating can have high rigidity, high anti-corrosion and antifriction self-lubricating performance simultaneously, is used for the protection and the self-lubrication treatment of various aluminum alloy materials component.
Technology of the present invention can be applicable to the protective treatment of many aluminum alloy materials or component, the component or the material that particularly need high anti-corrosion, high abrasion, self-lubricating, the also outstanding properties of desirable its certain aspect, as utilize the antifriction and the self-lubricating property of this coating, can make at a high speed, the stationarity of work-ing life of high frequency motion aluminium matter component and action be improved significantly, as in the oceanic climate environment to the high anti-corrosion protection of aluminium alloy etc.; Because coating cannot not have stickingly anti-dust performance, this technology can prepare even ater coating in addition, and it is good according to property that coating is fast light, has great advantage in the protective treatment of the aluminium matter key components and parts of photoelectric instrument such as sighting instrument, optical ranging system, electronics and IT products, computer etc.
In the present invention, aluminum alloy materials comprises duralumin, ultralumin, wrought aluminium, rust-preventing aluminum alloy or fine aluminium; Above-mentioned photoelectric instrument is meant various optical aiming systems, ranging system, electronic information instrument, computer etc.; The photoelectric instrument aluminum alloy part is meant the parts that various opticinstruments are made of aluminum alloy materials.
Embodiment
Illustrated by following illustration, but these illustrations are not any qualification of technology of the present invention.
Example 1: aluminum alloy materials is the 7A04T6 test plate (panel), and 50mm * 50mm * 3mm is polished to surface roughness Ra 1.6～Ra0.8, and is standby; The photoelectric instrument aluminum alloy spare part exemplar that maybe need handle.1. exemplar with alkaline degreasing fluid in 60～75 ℃ of skimming treatment 5～10min; Tap water rinsing 30S, flowing water cleans 15S; 2～5min is washed in 60～75 ℃ of erosions in the sodium hydroxide solution of 40～50g/l then, removes the oxide film of aluminum alloy surface; Tap water rinsing 30S, flowing water cleans 30S; 2. room temperature cleanup acid treatment 2～10min in 20～30% nitric acid light-emitting solution removes erosion and washes the surperficial dust and the residue of generation; Tap water rinsing 30S, flowing water cleans 15S; 3. hard anodizing is handled: carry out the hard anodizing processing by hard anodizing tank liquor and processing condition that table 1 is given; Thicknesses of layers is controlled at 20～50 μ m, takes out with tap water rinsing 30S, and flowing water cleans 30S.
Table 1 aluminium alloy hard anodizing technology
| The hard anodizing solution composition | The hard anodizing processing condition | |
| Material | Content (%) | Temperature-5～2 ℃, current density 2.5A/dm 2, whole voltage 95～105V, time 70min. |
| Sulfuric acid (98%) | 6.0 | |
| Lactic acid | 5.0 | |
| Citric acid | 3.0 | |
| Aniline sulfonic acid | 1.0 | |
| Wetting agent | 0.02 | |
| Al 3+ | 0.3 | |
In order to reach better wetting effect, added wetting agent nonionogenic tenside TX-10 in this example.
4. hot dipping fluoropolymer and vacuum precision thermal treatment: the hard anodizing exemplar in the ptfe emulsion solution of 60g/l in 60～70 ℃ of hot dipping 20min, after taking-up is dried in air, put into heat treatment furnace, under the vacuum tightness of 1～0.1Pa, handle 40min in 370～380 ℃, close vacuum system after being cooled to the temperature below 150 ℃, take out exemplar and be cooled to room temperature, remove surface residue with naval's pug, be the synergism coat exemplar.
The synergistic fluoropolymer coating outward appearance of preparation be even Dark grey to black coating, feel is lubricated, surperficial hydrophobic, hates oil, anti-dust performance good; Pressing the regulation of GB6462, is 25 μ m with micro-metallographic method test mean thickness; Pressing the regulation of GB9790, is 500HV with micro-metallographic method tested for hardness; Press the regulation of ASTM B117, behind 1000 hours 5% neutral salt spray tests, press ASTM D1654 evaluation, corrosion be rated 7 grades qualified.
Example 2: by the given prepared hard anodizing exemplar of example 1; Carry out electrochemistry by the given reaming liquid of table 2 with processing condition and exchange the reaming processing; Tap water rinsing 30S, flowing water cleans 15S; Dry up standby after the reaming with cold wind.
Table 2 hard anodizing horizon electrochemistry of the present invention chambering process
| Electrochemistry reaming solution composition | The chambering process condition | |
| Material | Content (g/l) | The electrochemistry reaming: workpiece is an anode, and negative electrode is a stereotype, 20～25 ℃ of temperature, voltage 8～15V, time 5min; |
| Phosphoric acid (85%) | ????150 | |
| Oxalic acid | ????20 | |
The reaming rear surface show even brown to black, do not play ash, do not fall film, matrix does not have corrosion, through even, clear, the marshalling in scanning electron microscope microanalysis surface pore.
Hot dipping fluoropolymer and vacuum precision thermal treatment: hard anodizing reaming exemplar in the ptfe emulsion solution of 50g/l in 45～55 ℃ of hot dipping 30min, after taking-up is dried in air, put into heat treatment furnace, under the vacuum tightness of 5～1Pa, handle 50min in 370～380 ℃, close vacuum system after being cooled to the temperature below 150 ℃, take out exemplar and be cooled to room temperature, remove surface residue with naval's pug, be the synergism coat exemplar.
The synergistic fluoropolymer coating outward appearance of preparation be even Dark grey to black coating, feel is lubricated, surperficial hydrophobic, hates oil, anti-dust performance good; Pressing the regulation of GB6462, is 25 μ m with micro-metallographic method test mean thickness; Pressing the regulation of GB9790, is 400HV with micro-metallographic method tested for hardness; Press the regulation of ASTM B117, behind 1000 hours 5% neutral salt spray tests, press ASTM D1654 evaluation, corrosion be rated 8 grades qualified.
Example 3: by the given prepared hard anodizing exemplar of example 1; Sulfuric acid reaming liquid at 100g/l carries out the chemical enlargement processing, and processing condition are 20～25 ℃ of temperature, 5min; Tap water rinsing 30S, flowing water cleans 15S; Dry up standby after the reaming with cold wind.
The reaming rear surface show even brown to black, do not play ash, do not fall film, matrix does not have corrosion, through even, clear, the marshalling in scanning electron microscope microanalysis surface pore.
Hot dipping fluoropolymer and vacuum precision thermal treatment: hard anodizing reaming exemplar in the ptfe emulsion solution of 70g/l in 80～90 ℃ of hot dipping 15min, after taking-up is dried in air, put into heat treatment furnace, under the vacuum tightness of 0.5～0.05Pa, handle 60min in 370～380 ℃, close vacuum system after being cooled to the temperature below 150 ℃, take out exemplar and be cooled to room temperature, remove surface residue with naval's pug, be the synergism coat exemplar.
The synergistic fluoropolymer coating outward appearance of preparation be even Dark grey to black coating, feel is lubricated, surperficial hydrophobic, hates oil, anti-dust performance good; Pressing the regulation of GB6462, is 25 μ m with micro-metallographic method test mean thickness; Pressing the regulation of GB9790, is 400HV with micro-metallographic method tested for hardness; Press the regulation of ASTM B117, behind 1000 hours 5% neutral salt spray tests, press ASTM D1654 evaluation, corrosion be rated 8 grades qualified.
Example 4: the hard anodizing exemplar of pressing the given prepared of table 3.
Table 3 aluminium alloy hard anodizing technology
| The hard anodizing solution composition | The hard anodizing processing condition | |
| Material | Content (%) | Temperature-5～2 ℃, current density 2.5A/dm2, whole voltage 95～105V, time 90min. |
| Sulfuric acid (98%) | 5.0 | |
| Lactic acid | 4.0 | |
| Citric acid | 5.0 | |
| Aniline sulfonic acid | 2.0 | |
| Al3+ | 0.3 | |
Exemplar in the ptfe emulsion solution of 40g/l in 50～60 ℃ of hot dipping 10min, spraying concentration is the perfluoroethylene-propylene emulsion of 200g/l, gauge control after drying, is put into heat treatment furnace at 10～15 μ m in air, under the vacuum tightness of 5～1Pa, handle 30min in 350～370 ℃, close vacuum system after being cooled to the temperature below 150 ℃, take out exemplar and be cooled to room temperature, remove surface residue with naval's pug, be the synergistic fluoropolymer coating exemplar.
The synergistic fluoropolymer coating outward appearance of preparation is even black coating, and feel is lubricated, surperficial hydrophobic, hates oil, anti-dust performance good; Pressing the regulation of GB6462, is 30 μ m with micro-metallographic method test mean thickness; Pressing the regulation of GB9790, is 400HV with micro-metallographic method tested for hardness; Press the regulation of ASTM B117, behind 2000 hours 5% neutral salt spray tests, press ASTM D1654 evaluation, corrosion be rated 7 grades qualified.
Example 5: the hard anodizing exemplar of pressing the given prepared of table 3.Spray the ptfe emulsion that concentration is 280g/l subsequently, gauge control is at 10～15 μ m, after in air, drying, put into heat treatment furnace, under the vacuum tightness of 1～0.1Pa, handle 30min in 390～410 ℃, close vacuum system after being cooled to the temperature below 150 ℃, take out exemplar and be cooled to room temperature, remove surface residue, be the synergistic fluoropolymer coating exemplar with naval's pug.
The synergistic fluoropolymer coating outward appearance of preparation is even black coating, and feel is lubricated, surperficial hydrophobic, hates oil, anti-dust performance good; Pressing the regulation of GB6462, is 30 μ m with micro-metallographic method test mean thickness; Pressing the regulation of GB9790, is 550HV with micro-metallographic method tested for hardness; Press the regulation of ASTM B117, behind 1000 hours 5% neutral salt spray tests, press ASTM D1654 evaluation, corrosion be rated 7 grades qualified.
Example 6: corrosion-resisting aluminium LF5 presses the hard anodizing exemplar of the given prepared of table 4.
Table 4 aluminium alloy hard anodizing technology
| The hard anodizing solution composition | The hard anodizing processing condition | |
| Material | Content (%) | Temperature-5～2 ℃, current density 2.5A/dm2, whole voltage 95～105V, time 90min. |
| Sulfuric acid (98%) | 8.0 | |
| Lactic acid | 3.0 | |
| Citric acid | 6.0 | |
| Aniline sulfonic acid | 2.0 | |
| Al3+ | 0.3 | |
Owing to heat-treat under suitable temperature, anode oxide film will produce phase transformation, can increase film hardness.Therefore this example places vacuum oven to handle 30min under 500 ℃, the vacuum tightness of 1～0.1Pa the anodic oxidation exemplar, spray the ptfe emulsion that concentration is 300g/l subsequently, gauge control is at 10～15 μ m, after in air, drying, put into heat treatment furnace, under the vacuum tightness of 1～0.1Pa, handle 80min in 390～410 ℃, close vacuum system after being cooled to the temperature below 150 ℃, take out exemplar and be cooled to room temperature, remove surface residue with naval's pug, be the synergistic fluoropolymer coating exemplar.
The synergistic fluoropolymer coating outward appearance of preparation is even black coating, and feel is lubricated, surperficial hydrophobic, hates oil, anti-dust performance good; Pressing the regulation of GB6462, is 25 μ m with micro-metallographic method test mean thickness; Pressing the regulation of GB9790, is 630HV with micro-metallographic method tested for hardness; Press the regulation of ASTM B117, behind 1000 hours 5% neutral salt spray tests, press ASTM D1654 evaluation, corrosion be rated 7 grades qualified.
Example 7: press the hard anodizing exemplar of the given prepared of table 1,90min during hardening oxidation wherein, all the other processing condition are identical.Fluoropolymer is introduced in re-electrolysis subsequently: exemplar is an anode, and stereotype is a negative electrode; Tetrafluoroethylene thing particulate loading is 10g/l, FC-5 perfluorocarboxylic acid salt fluorine surfactant 0.2g/l in the electrolytic solution; The electrolysis process condition is anodic current density 40mA/dm2,30 ℃ of electrolyte temperatures, time 5min; After taking-up is dried in air, put into heat treatment furnace, under the vacuum tightness of 1～0.1Pa, handle 70min in 355～375 ℃, close vacuum system after being cooled to the temperature below 150 ℃, take out exemplar and be cooled to room temperature, remove surface residue, be the synergistic fluoropolymer coating exemplar with naval's pug.
The synergistic fluoropolymer coating outward appearance of preparation is even black coating, and feel is lubricated, surperficial hydrophobic, hates oil, anti-dust performance good; Pressing the regulation of GB6462, is 30 μ m with micro-metallographic method test mean thickness; Pressing the regulation of GB9790, is 500HV with micro-metallographic method tested for hardness; Press the regulation of ASTM B117, behind 1500 hours 5% neutral salt spray tests, press ASTM D1654 evaluation, corrosion be rated 7 grades qualified.
Example 8: the hard anodizing exemplar of pressing the given prepared of table 4.At first carry out re-electrolysis subsequently and introduce fluoropolymer: exemplar is an anode, and stereotype is a negative electrode; Tetrafluoroethylene thing particulate loading is 20g/l, FC-5 perfluorocarboxylic acid salt fluorine surfactant 0.3g/l in the electrolytic solution; The electrolysis process condition is anodic current density 60mA/dm2,40 ℃ of electrolyte temperatures, time 10min; After taking-up is dried in air, spraying concentration again is the perfluoroethylene-propylene emulsion of 100g/l, gauge control after drying, is put into heat treatment furnace at 8～10 μ m, under the vacuum tightness of 1～0.1Pa, handle 80min in 355～375 ℃, close vacuum system after being cooled to the temperature below 150 ℃, take out exemplar and be cooled to room temperature, remove surface residue with naval's pug, be the synergistic fluoropolymer coating exemplar.
The synergistic fluoropolymer coating outward appearance of preparation is the grey black uniform coating, and feel is lubricated, surperficial hydrophobic, hates oil, anti-dust performance good; Pressing the regulation of GB6462, is 30 μ m with micro-metallographic method test mean thickness; Pressing the regulation of GB9790, is 400HV with micro-metallographic method tested for hardness; Press the regulation of ASTM B117, behind 1500 hours 5% neutral salt spray tests, press ASTM D1654 evaluation, corrosion be rated 8 grades qualified.
Example 9: aluminum alloy materials 7A04T6 pole, φ 65, and warp is cut into the disk of thick 10mm, is dimensioned to annulus by the GB12444.1 regulation, is polished to anchor ring roughness Ra0.4, and is standby.Press the given prepared hard anodizing exemplar of table 1,90min during hardening oxidation wherein, all the other processing condition are identical.Exemplar in the ptfe emulsion solution of 70g/l in 80～90 ℃ of hot dipping 30min, after taking-up is dried in air, put into heat treatment furnace, under the vacuum tightness of 5～1Pa, handle 40min in 380～390 ℃, close vacuum system after being cooled to the temperature below 150 ℃, take out exemplar and be cooled to room temperature, remove surface residue with naval's pug, be the synergistic fluoropolymer coating exemplar.
The synergistic fluoropolymer coating outward appearance of preparation is the black even coating, feel is lubricated, surperficial hydrophobic, hates oil, anti-dust performance good, press the regulation of GB12444.1 and tests kinetic friction coefficient, friction co-efficient value is 0.10～0.15, shows that coating has tangible antifriction performance.
Example 10: opticinstrument or electronic information instrument aluminum alloy spare part are handled.As aluminium base eyepiece stalk, pedestal, objective tube, graduation panel seat, reticle trim ring, the guide pin bushing of sighting instrument, or distance mearuring equipment aluminum part, the aluminium base housing of electronic information instrument etc.; Carry out synergism coat by example 1 given technology and handle, wherein the hard anodizing time is 80～100min, and all the other processing condition are identical.
The synergistic fluoropolymer coating outward appearance of preparation is even ater coating, and feel is lubricated, surperficial hydrophobic, hates oil, anti-dust performance good; Through sampling observation, the regulation of pressing GB6462 is 25～30 μ m with micro-metallographic method test thickness; Pressing the regulation of GB9790, is 500～550HV with micro-metallographic method tested for hardness; Press the regulation of ASTM B117, behind 1000 hours 5% neutral salt spray tests, press ASTM D1654 evaluation, corrosion be rated 7 grades qualified; Oilness is good, can satisfy the service requirements of corresponding product fully.
Claims (19)
1, a kind of technique for treating synergism coat of aluminium alloy material and fluorine polymer, it is characterized in that: aluminum alloy materials at first carries out hard anodizing, introduce fluoropolymer at the hard anodized film layer or through the rete that reaming is handled then, make fluoropolymer and hard anodizing horizon fusion be one by vacuum heat-treating method at last, form synergism coat.
2, technique for treating synergism coat of aluminium alloy material and fluorine polymer as claimed in claim 1, it is characterized in that: the hard anodizing of described aluminum alloy materials is meant that carrying out alkaline degreasing and/or alkalescence erosion earlier washes and go out optical processing through nitric acid acidwashing, after water cleans, and then carry out hard anodizing and handle.
3, technique for treating synergism coat of aluminium alloy material and fluorine polymer as claimed in claim 1 or 2 is characterized in that: described hard anodizing adopts the nitration mixture hard anodizing.
4, technique for treating synergism coat of aluminium alloy material and fluorine polymer as claimed in claim 3 is characterized in that: the mixed acid solution of described nitration mixture hard anodizing contains sulfuric acid, lactic acid, citric acid, aniline sulfonic acid, aluminum ion.
5, technique for treating synergism coat of aluminium alloy material and fluorine polymer as claimed in claim 4 is characterized in that: vitriolic content is 1～10% in the described mixed acid solution, the content of lactic acid 0.5～10%, citric acid 0.5～10%, aniline sulfonic acid is 0～5%, aluminum ions content is 0.1～0.5%.
6, technique for treating synergism coat of aluminium alloy material and fluorine polymer as claimed in claim 5 is characterized in that: vitriolic content is 3～8% in the described mixed acid solution, the content of lactic acid 2～7%, citric acid 3～8%, aniline sulfonic acid is 0.3～3%, aluminum ions content is 0.3%.
7, technique for treating synergism coat of aluminium alloy material and fluorine polymer as claimed in claim 1 or 2 is characterized in that: described hard anodizing adopts galvanic current; Processing condition are temperature-7～5 ℃, current density 1～5A/dm
2, whole voltage 70～120V, pneumatic blending, oxidization time 30～120min.
8, technique for treating synergism coat of aluminium alloy material and fluorine polymer as claimed in claim 7 is characterized in that: the processing condition of hard anodizing are temperature-5～2 ℃, current density 2～3.5A/dm
2, whole voltage 90～110V, pneumatic blending, oxidization time 50～90min.
9, technique for treating synergism coat of aluminium alloy material and fluorine polymer as claimed in claim 7 is characterized in that: the gauge control of hard anodized film is at 20～60 μ m.
10, technique for treating synergism coat of aluminium alloy material and fluorine polymer as claimed in claim 9 is characterized in that: the gauge control of hard anodized film is at 20～50 μ m.
11, technique for treating synergism coat of aluminium alloy material and fluorine polymer as claimed in claim 1 is characterized in that: the reaming of described hard anodized film is handled and is adopted chemical enlargement to handle or electrochemistry interchange reaming processing.
12, technique for treating synergism coat of aluminium alloy material and fluorine polymer as claimed in claim 11 is characterized in that: described chemical enlargement adopts sulfuric acid reaming solution, sulfuric acid content scope 50～300g/l in the reaming solution; The chemical enlargement processing condition are 20～30 ℃ of temperature, time 1～20min; Described electrochemistry exchanges reaming and adopts phosphoric acid-oxalic acid reaming solution, and phosphorus acid content scope 50～200g/l, oxalic acid content scope are 10～50g/l in the reaming solution; It is 20～30 ℃ of temperature, voltage 5～30V, time 3～20min that electrochemistry exchanges the chambering process condition.
13, as claim 11 or 12 described technique for treating synergism coat of aluminium alloy material and fluorine polymer, it is characterized in that: described chemical enlargement adopts sulfuric acid content scope 100～200g/l in the sulfuric acid reaming solution; The chemical enlargement processing condition are 20～25 ℃ of temperature, time 3～10min; Electrochemistry exchanges phosphorus acid content scope 100～200g/l, the oxalic acid content scope 20～30g/l in reaming employing phosphoric acid-oxalic acid reaming solution; It is 20～25 ℃ of temperature, voltage 8～15V, time 5～10min that electrochemistry exchanges the chambering process condition.
14, technique for treating synergism coat of aluminium alloy material and fluorine polymer as claimed in claim 1 is characterized in that: the introducing of described fluoropolymer or adopt hot dipping method or/and spraying method or/and the re-electrolysis method; Described fluoropolymer or employing tetrafluoroethylene or the water miscible liquid of tetrafluoroethylene/hexafluoropropylene copolymer fluoropolymer or the water-dispersion emulsion of similar fluoropolymer.
15, technique for treating synergism coat of aluminium alloy material and fluorine polymer as claimed in claim 14, it is characterized in that: described hot dipping method technology is meant that infiltration liquid fluoropolymer microparticles concentration range is 10～100g/l or also is added with organic fluorine surfactant, 30～100 ℃ of infiltration temperatures, the time is 5～60min; Described spraying method adopts high atomization rate spray gun at model or workpiece surface spraying fluoropolymer, and coating thickness is controlled in 3～20 μ m, and spraying is 50～400g/l with the fluoropolymer emulsions concentration range; Described re-electrolysis method is meant the employing anode electrolysis, and negative electrode is a stereotype, and electrolytic solution fluoropolymer microparticles concentration range is 1～30g/l, or also can be added with organic fluorine surfactant, and electrolytic current density range is 10～100mA/dm
2, temperature range is 20～60 ℃, time range is 1～30min.
16, technique for treating synergism coat of aluminium alloy material and fluorine polymer as claimed in claim 15 is characterized in that: infiltration liquid fluoropolymer microparticles concentration range is 30～70g/l in the described hot dipping method technology, 40～80 ℃ of infiltration temperatures, and the time is 10～40min; Coating thickness is controlled at 5～10 μ m in the described spraying method technology, and spraying is 100～300g/l with the fluoropolymer emulsions concentration range; Electrolytic solution fluoropolymer microparticles concentration range is 5～20g/l in the described re-electrolysis method, and electrolytic current density range is 20～80mA/dm
2, temperature range is 30～50 ℃, time range is 5～20min.
17, technique for treating synergism coat of aluminium alloy material and fluorine polymer as claimed in claim 1, it is characterized in that: described thermal treatment is carried out under vacuum state, processing condition are that temperature range is 300～450 ℃, and the treatment time scope is 20～120min, and vacuum degree control is 20～1 * 10
-2The Pa scope.
18, technique for treating synergism coat of aluminium alloy material and fluorine polymer as claimed in claim 17 is characterized in that: 300～450 ℃ of the technological temperature scopes of described vacuum heat treatment, treatment time scope 30～80min; Vacuum degree control is 5～5 * 10
-2Pa.
19, technique for treating synergism coat of aluminium alloy material and fluorine polymer as claimed in claim 1 is characterized in that: described aluminum alloy materials is duralumin, ultralumin, wrought aluminium, rust-preventing aluminum alloy or fine aluminium.
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