CN1603465A - Treatment process for synergistic fluoropolymer coating on magnesium and its alloy - Google Patents
Treatment process for synergistic fluoropolymer coating on magnesium and its alloy Download PDFInfo
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Abstract
The invention involves a kind of magnesium alloy fluorine polymer harmony coating processing craft, its characteristic lies in: First carries on chemistry nickel plating to the magnesium and the magnesium alloy material to prepare the harmony coating the base first floor, then to chemical plating nickel layer carries on drills out processing, after drills out in the pore and the superficial introduction fluorine polymer, and carries on the heat treatment under the vacuum state to cause the fluorine polymer with chemical plating nickel layer the fusion is a body, forms the harmony coating. Uses this invention to state the craft, the consciousness coating degree of hardness extremely high, the resistance to wear is good; Two is in the coating includes anti-friction the material fluorine polymer, has self lubrication the performance, but large scale increases its wear-resisting performance;Three is in the coating fluorine polymer can resist the majority harmful environment or the corrosive substance archery target erosion, four is the coating for does the membrane self lubrication surface, has does the membrane self lubrication function.
Description
Technical field
The coating that the present invention relates to magnesium and magnesium alloy is handled the fluoropolymer technique for treating synergism coat of particularly a kind of magnesium and magnesium alloy.
Background technology
The chemical property of magnesium is very active.Its standard potential is-2.37V; current potential than other metal is all low; resistance to corrosion is poor; except that stable in alkali lye, dense hydrofluoric acid and kerosene, all very strong with the aqueous solution effect of nearly all acid, salt, at the environment of humidity; particularly in the oceanic climate; very fast corrosion must adopt special safeguard procedures that magnesium alloy materials is carried out surface protection, and Application of Magnesium could large-scale promotion.
In order to improve the antirust ability of magnesium alloy, can in magnesium alloy, increase the metallic element that improves resistance to corrosion, perhaps adopt the rational heat treatment standard; What more generally adopt is to generate compact and complete chemistry or the electro-chemical protection rete of one deck on the magnesium alloy parts surface with chemical oxidation or electrochemical oxidation method; chemical oxidation can obtain the thin film layer of 0.5～3 μ m; electrochemical oxidation can obtain the thick film layers of 10～40 μ m; because chemical oxide film is thin and soft; the membranous crisp and porous of electrochemical oxidation; so the oxidation of magnesium alloy is except that making decoration and middle operation; use seldom separately; need again to spray paint or form extraordinary protective layer, further reach the purpose of protection and finish at film surface.On the other hand, applying of magnesium alloy not only needs to solve the perishable problem that himself has, and will solve defect problems such as its wear resisting property difference, though successfully develop the surface treatment method of many magnesium alloy, seek new functional means of defence and be still a big problem.
In recent years, the scientific worker has carried out extensive studies to the differential of the arc pottery oxidation technology and the chemical plating nickel technology of magnesium alloy; The differential arc oxidation method comes down to a kind of high energy hard anodizing and handles, rely on the introducing of high energy, produce the micro-arc discharge phenomenon on anode (goods) surface, make Mg alloy surface fusing and oxidation, form the ceramic-like coating that one deck contains products such as magnesium oxide and silicon oxide, this coating has certain against corrosion, wear resistance, microhardness can reach 700HV, under the load of 9.8N, thick differential of the arc ceramic conversion layer can stand 1000～3000 times wearing and tearing, after special sealing or japanning, can stand 500 hours or the examination of 5% neutral salt spray test for more time, at automobile, fields such as computer obtain to use, but differential arc oxidation laminar surface roughness is big, the porosity height, easily crisp, have much room for improvement with basal body binding force, be difficult to direct application; Chemical nickel plating equally can be for magnesium alloy provides effective protection, and chemical Ni-plating layer has advantages such as hardness height, wear resistance be good, does not have self-lubricating property etc. and has limited its application but coating is damaged accelerated corrosion problem, the coating of the magnesium alloy substrate at position.And to need in the magnesium alloy component that in ocean environment, uses, the various harsh corrosive environment high anti-corrosion must have the parts of anti-attrition self-lubricating property, unsuitable painted parts, with the contacted magnesium alloy component of other metal; then also there is not ideal to handle guard method; therefore, a kind of not only anti-corrosion but also treatment process attrition resistant fine and close coated layer of research is desired always.
Metallic surface synergism modified coating technology is the composite modified coating technology of a kind of novel surface, in the research of coat that improves metal and surface treatment properties, the material property feature that the researchist successfully obtains to expect by means of the advantage in conjunction with two or more materials and technological process; The low friction polymer or the lubricant that infiltrate as light metal anode oxide film and control combine, handle by precision again it is carried out modification, finally obtain a kind of accurate Bulk coat and become one of metal parts partly whole, this coating is exactly a synergism coat, its over-all properties surpasses compound coating in general sense, and it has great using value.At present, the main application of this technology is an aluminium alloy, has formed Nituff synergism coat technology on the aluminium by research and development such as U.S. Nimet industrials at first, and similar technology such as Tufram, Polylube, Hardtuf, and has obtained industrial application; Same magnesium alloy also can prepare synergism coat based on similar principles, as the anodic oxidation of magnetism alloy of people such as the Gao Mu exploitation of the magnesium of U.S. General Magnaplate company research and development and magnesium alloy " Magnadize " synergistic fluoropolymer coating technology, Japan and fluoropolymer codeposition coating process etc.; The technique for treating synergism coat of magnesium alloy all prepares on anodised basis, because the defective of anodic oxidation of magnetism alloy film, the synergism coat technology of magnesium alloy does not obtain practical application; The present patent application people once attempted to prepare synergism coat on the micro-arc oxidation films basis, but not success.
Summary of the invention
The objective of the invention is the deficiency that exists for the existing surface protection technique that solves magnesium and magnesium alloy, and a kind of protective capacities that provides is strong, antifriction and good magnesium and the magnesium alloy synergistic fluoropolymer coating treatment process of wear-resistant self-lubricating performance.
The object of the present invention is achieved like this: a kind of magnesium and magnesium alloy synergistic fluoropolymer coating treatment process is characterized in that: at first magnesium and magnesium alloy materials are carried out the stratum basale of chemical nickel plating with the preparation synergism coat; Then chemical Ni-plating layer being carried out reaming handles; Introduce fluoropolymer at micropore and surface after the reaming; And under vacuum state, heat-treat and make the fusion of fluoropolymer and chemical Ni-plating layer be one, form synergism coat.
The present invention is with the stratum basale of chemical Ni-plating layer as synergism coat, with comparing as the stratum basale of synergism coat of present employing with anodic oxide coating, anodic oxide coating is relatively poor with basal body binding force, surface irregularity, hardness is lower, and chemical Ni-plating layer is by the plating of body material autocatalysis, and is good with basal body binding force, surfacing, and hardness height.Existing technology is carried out accurate heat treatment process under atmospheric condition, workpiece is yielding, the easy carbonization of fluoropolymer is decomposed, 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, workpiece is not yielding, 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 chemical nickel plating of magnesium and magnesium alloy: magnesium and magnesium alloy are carried out alkaline degreasing and chromic acid cleanup acid treatment routinely earlier, after water cleans, in hydrofluoric acid solution, carry out activation treatment, generate the fine and close chemical conversion layer of one deck, nickel preplating in the slightly acidic electroless nickel bath subsequently, and then in acid chemical plating nickel is bathed chemical plating nickel-phosphorus alloy.
In above-mentioned steps, the hydrofluoric acid solution concentration of carrying out activation treatment is 20～200g/l, and processing condition are room temperature, 5～20min; The nickel preplating bath of carrying out the nickel preplating processing contains basic nickel carbonate, hydrofluoric acid, citric acid, ammonium bifluoride, ammoniacal liquor and inferior sodium phosphate, wherein the basic nickel carbonate content range is that 5～30g/l, hydrofluoric acid (40%) content range are that 5～15ml/l, citric acid content scope are that 3～10g/l, ammonium bifluoride content range are that 5～20g/l, ammoniacal liquor (25%) content range are that 20～50ml/l, inferior sodium phosphate content range are 10～30g/l, its pH5.5～7.5, temperature is 70～85 ℃, time 30～120min; Carry out chemical nickel plating or employing rack plating that chemical plating nickel-phosphorus alloy is handled, or employing barrel plating, its nickel-phosphorus alloy plating bath major ingredient comprises nickel salt, hypophosphite, lactic acid, citric acid, oxysuccinic acid, thiocarbamide, nickel salt or be single nickel salt or wherein for nickelous chloride or for nickel acetate etc., hypophosphite can adopt inferior sodium phosphate, the content of single nickel salt is 20-50g/l, the content range of hypophosphite is 15～60g/l, the content range of oxysuccinic acid is 5～30g/l, the content range of lactic acid is 5～20ml/l, the content range of citric acid is 0～5g/l, the content of thiocarbamide is 1mg/l, processing condition are 75～95 ℃ of temperature, time 30～180min.
The hydrofluoric acid solution concentration of above-mentioned activation treatment is good with 60～160g/l; The basic nickel carbonate content range was that 10～15g/l, hydrofluoric acid (40%) content range are that 8～12ml/l, citric acid content scope are that 4～8g/l, ammonium bifluoride content range are that 10～15g/l, ammoniacal liquor (25%) content range are that 25～35ml/l, inferior sodium phosphate content range are 15～25g/l during above-mentioned nickel preplating was bathed, pH6.0～6.5, temperature is 80 ± 2 ℃, and the time is that 60～90min is good; The nickel sulfate content scope of above-mentioned nickel-phosphorus alloy plating bath is that the content range of 25～35g/l, hypophosphite is that the content range of 20～40g/l, oxysuccinic acid is that the content range of 10～20g/l, lactic acid is that the content range of 10～15ml/l, citric acid is that the content of 0.5～2g/l, thiocarbamide is 1mg/l, processing condition are that temperature is 88 ± 2 ℃, and time 60～120min is good.
2, the reaming of chemical Ni-plating layer is handled: the present invention is to guarantee that follow-up fluoropolymer fully combines with it to the purpose that chemical Ni-plating layer carries out reaming, the performance synergy.
Reaming is handled and can be adopted conventional sulphuric acid soln corrosion treatment or similar technology.
Reaming of the present invention is handled, its reaming solution sulfur acid, nickel salt, molysite, wherein the form of nickel salt or employing single nickel salt or nickelous chloride or nickel acetate or nickelous carbonate adds, molysite or the form that adopts ferric sulfate or iron(ic) chloride etc. to be fit to add, the sulfuric acid content scope is 15～50%, the nickel salt content range is 0.01～5g/l, and the molysite content range is 0.01～2g/l; The processing condition of its chemical enlargement are 20～80 ℃ of temperature, time 5～60min; The anode reaming is adopted in its electrochemistry reaming, and processing condition are room temperature, and current density range is 0.5～10A/dm
2, time 1～20min, after the reaming, water cleans up, and dries up surperficial moisture content with cold wind.
Sulfuric acid content scope 25～40% in the above-mentioned reaming solution, nickel salt content range 0.1～3g/l, molysite content range 0.1～1g/l is good.The chemical enlargement processing condition are 30～60 ℃ of temperature, and time 15～35min is good; Current density range 2.0～7A/dm in the electrochemistry chambering process condition
2, time 3～10min is good.
The reaming of chemical Ni-plating layer is handled, and the degree of depth of reaming is the key point of preparation synergism coat, is controlled at 10～60% of chemical nickel plating layer thickness in principle.
It is good that the degree of depth of reaming is controlled at 20～50% of chemical nickel plating layer thickness.
3, the introducing of fluoropolymer: in the chemical nickel plating stratum basale of handling through reaming or lubricant is introduced on its 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 Mg alloy surface stratum basale of preparation.
And technology of the present invention is the difference according to the 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 200～600 ℃, and the treatment time scope is 5～120min, 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 fluoropolymer and chemical nickel plating stratum basale fully fuse the determined treatment time, forms one, with the performance synergy.
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 30～60min; 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 magnesium and the magnesium alloy synergistic fluoropolymer coating that form by the present invention show grey to black, and thickness 10～50 μ m, microhardness reach 500～800HV, and 5% neutral salt spray test 500h corrosion is rated 7～8 grades, and kinetic friction coefficient is less than 0.20.
Beneficial effect of the present invention: the one, coating is the body of combining closely of hard substrate layer and fluoropolymer, and it has become a whole part of metallic matrix, and coating hardness is high, reaches 500～800HV, and wear resistance is good; The 2nd, contain the antifriction material fluoropolymer in the coating, kinetic friction coefficient has self-lubricating property less than 0.20, can increase considerably its wear resisting property; The 3rd, the fluoropolymer in the coating can improve its anti-corrosion capability greatly, this coating not only has hydrophobic and lyophobic property, has the anti-neutral salt spray test ability more than 500 hours, can resist the etch of most of hostile environments or corrosive deposit, the anti-corrosion capability of the general protective layer of magnesium alloy can't be compared with it; The 4th, coating is a dry film self lubricating faade, has dry film self lubricating function; The 5th, 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 magnesium alloy materials component; 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 component and action be improved significantly, as in the oceanic climate environment to the high anti-corrosion protection of magnesium alloy, the protective treatment of magnesium alloy web member etc.
Embodiment
Illustrated by following illustration, but these illustrations are not any qualification of technology of the present invention.
Example 1 magnesium alloy materials is the AZ31D pole, and φ 60, and warp is cut into the disk of thick 3mm, is polished to surface roughness Ra 1.6～Ra0.8, and is standby.1. exemplar with alkaline degreasing fluid in 60～75 ℃ of skimming treatment 5～10min; Tap water rinsing 30S, flowing water cleans 15S; Room temperature pickling 2～10min in the chromic acid pickle solution of 200g/l then removes the oxide film of Mg alloy surface; Tap water rinsing 30S, flowing water cleans 30S; 2. room temperature activation treatment 10min in the activating bath of hydrofluoric acid containing 20～200g/l; Tap water rinsing 30S, flowing water cleans 15S; 3. preplating chemical nickel is handled: carry out the processing of preplating chemical nickel by plating bath and processing condition that table 1 is given; Thickness of coating is controlled at 5～10 μ m, takes out with tap water rinsing 30S, and flowing water cleans 30S.
Table 1 magnesium alloy preplating chemical nickel technology
| Preplating chemical nickel plating bath is formed | Preplating chemical nickel processing condition | |
| Material | Content (g/l) | Plating bath pH6.0～6.5,80 ± 2 ℃ of temperature, time 60min. |
| Hydrofluoric acid (40%) | 13 | |
| NiCO 32NiOH4H 2O | 10 | |
| C 6H 8O 7H 2O | 5 | |
| NH 4HF 2 | 10 | |
| CH 4N 2S | 0.001 | |
| NaH 2PO 2 | 20 | |
| NH 3H 2O (25%) | 31 | |
4. chemical nickel plating is handled: carry out the chemical nickel plating processing by plating bath and processing condition that table 2 is given; Thickness of coating is controlled at 15～20 μ m, tap water rinsing 30S, and flowing water cleans 30S.
Table 2 chemical nickel plating process on magnesium alloy
| Chemical nickel-plating solution is formed | The nickel chemical plating technology condition | |
| Material | Content (g/l) | Plating bath pH4.5～5.0,88 ± 2 ℃ of temperature, time 120min. |
| NiSO 47H 2O | 28 | |
| NaH 2PO 2H 2O | 30 | |
| Oxysuccinic acid | 15 | |
| Lactic acid | 10 | |
| Citric acid | 1.0 | |
| Thiocarbamide | 0.001 | |
5. the chemical Ni-plating layer reaming is handled: carry out electrochemistry reaming processing by reaming liquid and processing condition that table 3 is given; Tap water rinsing 30S, flowing water cleans 15S; Dry up standby after the reaming with cold wind.
Table 3 chemical Ni-plating layer electrochemistry chambering process
| Electrochemistry reaming solution composition | The chambering process condition | |
| Material | Content (%) | The electrochemistry reaming: workpiece is an anode, and negative electrode is a stereotype, room temperature, current density 3A/dm 2, time 4min. |
| Sulfuric acid | 40 | |
| Ni 2+ | 0.1 | |
| Fe 3+ | 0.03 | |
Nickel salt in the table 3 can adopt single nickel salt or nickelous chloride or nickel acetate or nickelous carbonate; Molysite adopts ferric sulfate.
The reaming rear surface show even brown to black, do not play ash, do not fall film, matrix does not have corrosion, in air, place 24h and do not play rust,, marshalling even, clear through scanning electron microscope microanalysis surface pore.
6. hot dipping fluoropolymer and vacuum precision thermal treatment: chemical nickel plating reaming 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 is the grey black uniform coating, and feel profit, is hated oil at surperficial hydrophobic; Pressing the regulation of GB6462, is 25 μ m with micro-metallographic method test mean thickness; Pressing the regulation of GB9790, is 650HV with micro-metallographic method tested for hardness; Press the regulation of ASTM B117, behind 500 hours 5% neutral salt spray tests, press ASTM D1654 evaluation, corrosion be rated 7 grades qualified.
Example 2 is by the given prepared chemical nickel plating exemplar of example 1.Carry out the chemical enlargement processing by reaming liquid and processing condition that table 4 is given; Tap water rinsing 30S, flowing water cleans 15S; Dry up standby after the reaming with cold wind.
Table 4 chemical Ni-plating layer chemical enlargement technology
| Electrochemistry reaming solution composition | The chambering process condition | |
| Material | Content (%) | Chemical enlargement: 40 ℃ of temperature, time 15min. |
| Sulfuric acid | 40 | |
| Ni 2+ | 0.1 | |
| Fe 3+ | 0.03 | |
What nickel salt was selected for use in the table is single nickel salt, and what molysite was selected for use is iron(ic) chloride.
The reaming rear surface shows even brown, does not play ash, does not fall film, matrix does not have corrosion, places 24h and do not play rust,, marshalling even, clear through scanning electron microscope microanalysis surface pore in air.
Chemical nickel plating reaming exemplar in the ptfe emulsion solution of 60g/l in 60～70 ℃ of hot dipping 30min, after taking-up is dried in air, put into heat treatment furnace, under the vacuum tightness of 1～0.1Pa, 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 grey black uniform coating, and feel profit, is hated oil at surperficial hydrophobic; Pressing the regulation of GB6462, is 24 μ m with micro-metallographic method test mean thickness; Pressing the regulation of GB9790, is 650HV with micro-metallographic method tested for hardness; Press the regulation of ASTM B117, behind 500 hours 5% neutral salt spray tests, press ASTM D1654 evaluation, corrosion be rated 7 grades qualified.
The reaming simultaneous test of example 3 chemical Ni-plating layers.By the given prepared chemical nickel plating exemplar of example 1.As everyone knows, chemical Ni-plating layer can turn black with nitric acid, is applied to the processing of solar panels etc., and this process in fact also is a kind of corrosion coarsening process; In order to verify whether this technology can be used for the reaming processing of chemical Ni-plating layer, adopts comparatively typical process such as U.S. Pat 4233107 disclosed technologies, press table 5 processing condition checking reaming effect.
Table 5 nitric acid pickling process chambering process
| The reaming solution composition | Processing condition | The reaming effect | ||
| Material | Content (%) | Temperature | Time | |
| Nickelous nitrate 2%+ nitric acid (68%) | ????16 | ?25～30 ?℃ | 1min | Grey black, surface play ash, fall film; |
| ????32 | ?25～30 ?℃ | 1min | Grey black, surface are played ash, are fallen film; | |
| ????48 | ?25～30 ?℃ | 0.5min | Black, surface are played ash, are fallen film, matrix corrosion; | |
| ????60 | ?25～30 ?℃ | 0.5min | Black, surface are played ash, are fallen film, matrix corrosion; | |
Through verification experimental verification, exist coating easily to wipe, the phenomenon of matrix corrosion is arranged, surface hardness declines to a great extent; And the blackout time is too short, and there is the macro-corrosion crackle in uppity shortcoming through scanning electron microscope microanalysis surface; Single angle from blackout, effect is all right, but from the reaming effect, can not satisfy the preparation requirement of synergism coat fully.
Example 4 is by the chemical nickel plating reaming exemplar of the given prepared of example 1, and wherein the chemical nickel plating time is 90min, and all the other processing condition are identical.Chemical nickel plating reaming 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 1～0.1Pa, 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 the grey black uniform coating, and feel profit, is hated oil at surperficial hydrophobic; Pressing the regulation of GB6462, is 21 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 800 hours 5% neutral salt spray tests, press ASTM D1654 evaluation, corrosion be rated 7 grades qualified;
Example 5 is by the chemical nickel plating reaming exemplar of the given prepared of example 1, and wherein the chemical nickel plating time is 90min, and all the other processing condition are identical.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 the grey black uniform coating, and feel profit, is hated oil at surperficial hydrophobic; Pressing the regulation of GB6462, is 20 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 500 hours 5% neutral salt spray tests, press ASTM D1654 evaluation, corrosion be rated 7 grades qualified.
Example 6 magnesium alloy materials are casting magnesium AZ91D blank, and warp is cut into the test plate (panel) of 50 * 50 * 3mm, is polished to surface roughness Ra 1.6～Ra0.8, and is standby.By the chemical nickel plating reaming exemplar of the given prepared of example 1, wherein the chemical nickel plating time is 90min, and 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 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, be the synergistic fluoropolymer coating exemplar with naval's pug.
The synergistic fluoropolymer coating outward appearance of preparation is the grey black uniform coating, and feel profit, is hated oil at surperficial hydrophobic; Pressing the regulation of GB6462, is 20 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 500 hours 5% neutral salt spray tests, press ASTM D1654 evaluation, corrosion be rated 7 grades qualified.
Example 7 is by the chemical nickel plating reaming exemplar of the given prepared of example 1, and wherein the chemical nickel plating time is 90min, and all the other processing condition are identical.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 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, spraying concentration again is the perfluoroethylene-propylene emulsion of 200g/l, gauge control after drying, is put into heat treatment furnace at 10～15 μ m, under the vacuum tightness of 1～0.1Pa, handle 40min 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 profit, is hated oil at surperficial hydrophobic; Pressing the regulation of GB6462, is 21 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 800 hours 5% neutral salt spray tests, press ASTM D1654 evaluation, corrosion be rated 7 grades qualified.
Example 8 magnesium alloy materials are the AZ31D pole, and φ 65, and warp is cut into the disk of thick 10mm, are dimensioned to annulus by the GB12444.1 regulation, are polished to anchor ring roughness Ra0.4, and are standby.By the chemical nickel plating reaming exemplar of the given prepared of example 1, wherein the chemical nickel plating time is 90min, and all the other processing condition are identical.Chemical nickel plating reaming exemplar in the ptfe emulsion solution of 60g/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 5～0.1Pa, 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 grey black uniform coating, and feel is lubricated, surperficial hydrophobic, hates oil, press the regulation of GB12444.1 and tests kinetic friction coefficient, and friction co-efficient value is 0.08～0.12, shows that coating has tangible antifriction performance.
Claims (14)
1, a kind of magnesium and magnesium alloy synergistic fluoropolymer coating treatment process is characterized in that: at first magnesium and magnesium alloy materials are carried out the stratum basale of chemical nickel plating with the preparation synergism coat; Then chemical Ni-plating layer being carried out reaming handles; Introduce fluoropolymer at micropore and surface after the reaming, and under vacuum state, heat-treat and make fluoropolymer and chemical Ni-plating layer fusion be one, the formation synergism coat.
2, magnesium as claimed in claim 1 and magnesium alloy synergistic fluoropolymer coating treatment process, it is characterized in that: the chemical nickel plating of described magnesium and magnesium alloy is meant and carries out alkaline degreasing and chromic acid cleanup acid treatment earlier, after water cleans, in hydrofluoric acid solution, carry out activation treatment, generate the fine and close chemical conversion layer of one deck, nickel preplating in the slightly acidic electroless nickel bath subsequently, and then in acid chemical plating nickel is bathed chemical plating nickel-phosphorus alloy.
3, magnesium as claimed in claim 2 and magnesium alloy synergistic fluoropolymer coating treatment process is characterized in that: in described electroless nickel step, the hydrofluoric acid solution concentration of carrying out activation treatment is 20～200g/l, and processing condition are room temperature, 5～20min; The nickel preplating bath of carrying out the nickel preplating processing contains basic nickel carbonate, hydrofluoric acid, citric acid, ammonium bifluoride, ammoniacal liquor and inferior sodium phosphate, wherein the basic nickel carbonate content range is that 5～30g/l, hydrofluoric acid (40%) content range are that 5～15ml/l, citric acid content scope are that 3～10g/l, ammonium bifluoride content range are that 5～20g/l, ammoniacal liquor (25%) content range are that 20～50ml/l, inferior sodium phosphate content range are 10～30g/l, its pH5.5～7.5, temperature is 70～85 ℃, time 30～120min; Carry out chemical nickel plating or employing rack plating that chemical plating nickel-phosphorus alloy is handled, or employing barrel plating, its nickel-phosphorus alloy plating bath major ingredient comprises nickel salt, hypophosphite, lactic acid, citric acid, oxysuccinic acid, thiocarbamide, nickel salt or be single nickel salt or wherein for nickelous chloride or for nickel acetate, hypophosphite can adopt inferior sodium phosphate, the content of single nickel salt is 20-50g/l, the content range of hypophosphite is 15～60g/l, the content range of oxysuccinic acid is 5～30g/l, the content range of lactic acid is 5～20ml/l, the content range of citric acid is 0～5g/l, the content of thiocarbamide is 1mg/l, processing condition are 75～95 ℃ of temperature, time 30～180min.
4, magnesium as claimed in claim 3 and magnesium alloy synergistic fluoropolymer coating treatment process, it is characterized in that: the hydrofluoric acid solution concentration of described activation treatment is 60～160g/l; The basic nickel carbonate content range was that 10～15g/l, hydrofluoric acid (40%) content range are that 8～12ml/l, citric acid content scope are that 4～8g/l, ammonium bifluoride content range are that 10～15g/l, ammoniacal liquor (25%) content range are that 25～35ml/l, inferior sodium phosphate content range are 15～25g/l during described nickel preplating was bathed, pH6.0～6.5, temperature is 80 ± 2 ℃, and the time is 60～90min; The nickel sulfate content scope of described nickel-phosphorus alloy plating bath is that the content range of 25～35g/l, hypophosphite is that the content range of 20～40g/l, oxysuccinic acid is that the content range of 10～20g/l, lactic acid is that the content range of 10～15ml/l, citric acid is that the content of 0.5～2g/l, thiocarbamide is 1mg/l, processing condition are that temperature is 88 ± 2 ℃, time 60～120min.
5, magnesium as claimed in claim 1 and magnesium alloy synergistic fluoropolymer coating treatment process is characterized in that: described reaming is handled or is adopted chemical enlargement or adopts the electrochemistry reaming.
6, magnesium as claimed in claim 5 and magnesium alloy synergistic fluoropolymer coating treatment process, it is characterized in that: reaming solution sulfur acid, nickel salt, molysite that described reaming is handled, nickel salt or adopt single nickel salt or nickelous chloride or nickel acetate or nickelous carbonate wherein, molysite or employing ferric sulfate or iron(ic) chloride, the sulfuric acid content scope is 15～50%, the nickel salt content range is 0.01～5g/l, and the molysite content range is 0.01～2g/l; The processing condition of its chemical enlargement are 20～80 ℃ of temperature, time 5～60mi; The anode reaming is adopted in its electrochemistry reaming, and processing condition are room temperature, and current density range is 0.5～10A/dm
2, time 1～20min, after the reaming, water cleans up, and dries up surperficial moisture content with cold wind.
7, magnesium as claimed in claim 6 and magnesium alloy synergistic fluoropolymer coating treatment process is characterized in that: sulfuric acid content scope 25～40% in the described reaming solution, nickel salt content range 0.1～3g/l, molysite content range 0.1～1g/l; The chemical enlargement processing condition are 30～60 ℃ of temperature, time 15～35min; Current density range 2.0～7A/dm in the electrochemistry chambering process condition
2, time 3～10min.
8, magnesium as claimed in claim 5 and magnesium alloy synergistic fluoropolymer coating treatment process is characterized in that: the reaming of chemical Ni-plating layer is handled, and the degree of depth of reaming is controlled at 10～60% of chemical nickel plating layer thickness.
9, magnesium as claimed in claim 8 and magnesium alloy synergistic fluoropolymer coating treatment process, it is characterized in that: the degree of depth of reaming is controlled at 20～50% of chemical nickel plating layer thickness.
10, magnesium as claimed in claim 1 and magnesium alloy synergistic fluoropolymer coating treatment process 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.
11, magnesium as claimed in claim 10 and magnesium alloy synergistic fluoropolymer coating treatment process, it is characterized in that: described hot dipping method technology is meant that infiltration liquid fluoropolymer microparticles concentration range is 10～100g/l, also can be 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, 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.
12, magnesium as claimed in claim 11 and magnesium alloy synergistic fluoropolymer coating treatment process, it 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, 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.
13, magnesium as claimed in claim 1 and magnesium alloy synergistic fluoropolymer coating treatment process, it is characterized in that: described thermal treatment is carried out under vacuum state, processing condition are that temperature range is 200～600 ℃, and the treatment time scope is 5～120min, and vacuum degree control is 20～1 * 10
-2The Pa scope.
14, magnesium as claimed in claim 13 and magnesium alloy synergistic fluoropolymer coating treatment process is characterized in that: 300～450 ℃ of the technological temperature scopes of described vacuum heat treatment, treatment time scope 30～60min; Vacuum degree control is 5～5 * 10
-2Pa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100413996C (en) * | 2005-12-15 | 2008-08-27 | 周婉秋 | Method of nickel sulfate solution system chemical nickel plating on magnesium alloy |
| CN103774125A (en) * | 2014-02-10 | 2014-05-07 | 杭州广荣科技有限公司 | Thermal treatment method of chemical nickel-phosphate plating alloy layer of aluminium alloy |
| CN109234779A (en) * | 2017-07-10 | 2019-01-18 | 中国兵器工业第五九研究所 | Aluminium alloy high temperature antiplastering synergistic fluoropolymer coating processing method |
| CN112247097A (en) * | 2020-10-22 | 2021-01-22 | 重庆建谊祥科技有限公司 | Semi-solid die-casting and double-fluorination combined manufacturing method for magnesium alloy building template |
-
2004
- 2004-08-31 CN CN 200410040591 patent/CN1603465A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100413996C (en) * | 2005-12-15 | 2008-08-27 | 周婉秋 | Method of nickel sulfate solution system chemical nickel plating on magnesium alloy |
| CN103774125A (en) * | 2014-02-10 | 2014-05-07 | 杭州广荣科技有限公司 | Thermal treatment method of chemical nickel-phosphate plating alloy layer of aluminium alloy |
| CN109234779A (en) * | 2017-07-10 | 2019-01-18 | 中国兵器工业第五九研究所 | Aluminium alloy high temperature antiplastering synergistic fluoropolymer coating processing method |
| CN109234779B (en) * | 2017-07-10 | 2020-07-21 | 中国兵器工业第五九研究所 | Method for treating aluminum alloy high-temperature anti-adhesion fluoropolymer synergistic coating |
| CN112247097A (en) * | 2020-10-22 | 2021-01-22 | 重庆建谊祥科技有限公司 | Semi-solid die-casting and double-fluorination combined manufacturing method for magnesium alloy building template |
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