CN102534628A - Cadmium-zinc-fluorocarbon composite coating of ship fastener and preparation method of cadmium-zinc-fluorocarbon composite coating - Google Patents
Cadmium-zinc-fluorocarbon composite coating of ship fastener and preparation method of cadmium-zinc-fluorocarbon composite coating Download PDFInfo
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- CN102534628A CN102534628A CN201010611710XA CN201010611710A CN102534628A CN 102534628 A CN102534628 A CN 102534628A CN 201010611710X A CN201010611710X A CN 201010611710XA CN 201010611710 A CN201010611710 A CN 201010611710A CN 102534628 A CN102534628 A CN 102534628A
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Abstract
The invention relates to a cadmium-zinc-fluorocarbon composite coating of a ship fastener and a preparation method of the cadmium-zinc-fluorocarbon composite coating. The outer surface of the fastener is respectively provided with a cadmium plating layer, a zinc plating and a fluorocarbon coating from inside to outside to form a composite protection layer of the fastener. The preparation process of the composite protection layer of the fastener is as follows: a fastener body is subjected to deoiling, washing, electrochemical etching, washing after etching, cadmium plating, zinc plating, passivating, dehydrogenating, fluorocarbon coating spraying and fluorocarbon coating curing in sequence. According to the preparation method disclosed by the invention, the cadmium-zinc-fluorocarbon composite protection layer can be formed on a substrate of the fastener; the substrate can highly resist seawater corrosion due to the matching design of a potential difference between a substrate coating and steel; and therefore the fastener is prevented from being etched by a corrosion source. The fluorocarbon coating as the outer layer has the advantages of high strength, loss resistance and long service life. The fastener with the cadmium-zinc-fluorocarbon composite coating is suitable for fastener surface protection application in the field of shipbuilding and other mechanical manufacturing.
Description
Technical field
The present invention relates to boats and ships fastening piece cadmium-zinc-fluorine carbon compound coating and preparation method.
Background technology
The corrosion of boats and ships fastening piece is often referred to the galvanic corrosion under the stress condition, i.e. stress galvanic corrosion; In the ocean environment, the corrosion of boats and ships fastening piece also belongs to has C1
-The galvanic corrosion that ion exists, under above-mentioned two types of synergetic situation, the corrosion reaction speed of fastening piece is much larger than common natural rust speed.This corrosive failure mode belongs to the intergranular corrosion fracture, normally causes the dominance inducement of great mechanical accident.Therefore, the fastening piece in the ocean environment condition being protected fully is to guarantee safety in production, the essential means of enhancing productivity.
Technologies such as galvanizing at present,, vacuum zinc/aluminium oozes altogether, zinc-plated and Dacroment are boats and ships fastening piece aseptic technics commonly used.But their results of use in actual production process are unsatisfactory, for example; In the fastening piece installation process; Fastening piece receives stronger nip stress and axial extruding or tensile stress, thereby the rustproof layer of its exposed surface is badly damaged, begins to corrode in the shipbuilding n. process subsequently.During deliver the vessel, more serious corrosion has appearred in fastener surface, has the fastening piece at some outboard positions can't normally change, and not only affects adversely man-hour, has also caused a large amount of wastes.The fact shows that the aseptic technic that current boats and ships fastening piece is taked fails effectively to contain that corrosive takes place, and the corrosion prevention problem of boats and ships fastening piece is still severe.
Cause the factor that the fastening piece resist peels off that two aspect factors are arranged: one, the bonding force between coating and the fastener base is not enough; Two, the force of sliding friction of fastener threads inboard is excessive, thereby makes interlayer shear stress greater than the shearing resistance limit between coating and matrix.Solve the disbonding problem and also should start with, not only will guarantee the bonding force of protective coating and matrix, also need take measures to avoid producing excessive shearing force at the inboard frictional coefficient that reduces of screw thread from above-mentioned two aspects.
Summary of the invention
In order to overcome the not corrosion resistant shortcoming of existing ship fastening piece, the present invention proposes boats and ships fastening piece cadmium-zinc-fluorine carbon compound coating and preparation method.This method solves the anticorrosive problem of boats and ships fastening piece through at fastening piece substrate preparation cadmium, zinc and fluorine carbon composite protection layer.
The technical scheme that the present invention adopts is:
The fastening piece appearance is respectively equipped with cadmium plating layer, zinc coating and fluororine-carbon coating from inside to outside, forms the fastening piece composite protection layer.
The preparation process of fastening piece composite protection layer: the fastening piece body in order through cleaning after the oil removing, cleaning, electrochemical etching, etch, cadmium plating, zinc-plated, passivation, dehydrogenation handle, spraying fluorocarbon coating, fluororine-carbon coating solidification process.
The concrete operations step
1, fastening piece oil removing:, carry out oil removing with 80～90 ℃ of dipping by lye fastening pieces;
2, clean: clean three times with 50～60 ℃ of clear water through the fastening piece after the alkali lye oil removing;
3, electrochemical etching: adopt negative electrode-anode associating etch method, catodic etching and anodic souring time ratio are 3:2;
Catodic etching: with the stereotype is anode, and fastening piece is a negative electrode, and the catodic etching current density is 8A/dm
2, 60 ℃ of etch temperature, the time is 10 minutes;
Anodic souring: with the iron plate is negative electrode, and fastening piece is an anode, and current density is 4A/dm
2, 35 ℃ of etch temperature, the etch time is 6 minutes;
4, clean after the etch oxide debris: clean with the fastening piece of 23 ℃ of cold water after to etch oxide debris;
5, cadmium plating: adopt ammonia carboxylic complex compound cadmium plating technology;
6, zinc-plated: as to adopt alkaline non-cyanogen galvanization technology;
7, passivation: adopt trivalent chromium passivation process;
8, dehydrogenation is handled: 180～190 ℃ of dehydrogenation process temperature scopes are incubated 2.5 hours;
9, spraying fluorocarbon coating: will pass through fastening piece that dehydrogenation handles with hot blast drying after, surface spraying fluorocarbon coating, 10～15 microns of wet-film thickness scopes;
10, fluororine-carbon coating solidifies: the fastening piece that will pass through the spraying fluorocarbon coating places solidification device, under 240 ℃ of temperature condition, solidifies 40 minutes, and the fluorocarbon coating film forming that fastener surface is applied is solidified.
Positively effect adopts method of the present invention to form cadmium-zinc-fluorine carbon composite protection layer at fastener surface, thereby the protection fastening piece does not receive the erosion of source of corrosion.Composite protection layer of the present invention has the advantage of intensity height, wear-resistant, long service life.Suit in the fastener surface security application of shipbuilding and other mechanical manufacturing field.
Description of drawings
Fig. 1 is that boats and ships fastening piece cadmium, zinc and fluorine carbon composite protection layer are provided with state graph.
Among the figure, 1. fastening piece, 1.1. spiral shell tooth, 1.11. cadmium plating layer, 1.12. zinc coating, 1.13. fluororine-carbon coating.
Embodiment
The boats and ships fastening piece comprises bolt, screw rod, nut, and pad, packing ring, pinning and web member are for being used for the device that machine riveting and parts install and fix.
According to shown in Figure 1, be example with the spiral shell tooth position of bolt, on fastening piece 1, be provided with spiral shell tooth 1.1, the spiral shell tooth outside is followed successively by cadmium plating layer 1.11, zinc coating 1.12 and fluororine-carbon coating 1.13.
The preparation process of fastening piece composite protection layer
The fastening piece body in order through cleaning after the oil removing, cleaning, electrochemical etching, etch, cadmium plating, zinc-plated, passivation, dehydrogenation handle, spraying fluorocarbon coating, fluororine-carbon coating solidification process.
The concrete operations step
1, fastening piece oil removing:, carry out oil removing with 80～90 ℃ of dipping by lye fastening pieces;
Alkali lye is formed: in every premium on currency solution, be added with 25 gram sodium hydroxide by quality, 30 gram yellow soda ash, 7 grams, ten phosphate dihydrate sodium, 10 gram water glass, 1.7～2 gram OP emulsifying agents;
2, clean: clean three times with 50～60 ℃ of clear water through the fastening piece after the alkali lye oil removing;
3, electrochemical etching: adopt negative electrode-anode associating etch method, catodic etching and anodic souring time ratio are 3:2, and the fastening piece after cleaning is inserted in the container, add etching solution, through the immersion of etching solution, remove the oxide debris of fastening piece;
Catodic etching: with the stereotype is anode, and fastening piece is a negative electrode, and the catodic etching current density is 8A/dm
2, 60 ℃ of etch temperature, the time is 10 minutes;
Etching solution is formed: in every liter of solution, and by the vitriol oil of quality adding 43 gram proportions 1.84, the hydrochloric acid of 28 gram proportions 1.19,22 gram sodium-chlor, 1～5 gram urotropine;
Anodic souring: with the iron plate is negative electrode, and fastening piece is an anode, and current density is 4A/dm
2, 35 ℃ of etch temperature, the etch time is 6 minutes;
Etching solution is formed: in every liter of solution, and by the vitriol oil of quality adding 12 gram proportions 1.84,230 gram iron vitriols, 50 gram sodium-chlor, 5 gram YLENE thiocarbamides;
4, clean after the etch: clean with the fastening piece of 23 ℃ of cold water after to etch;
5, cadmium plating: adopt ammonia carboxylic complex compound cadmium plating technology;
In every liter of cadmium plating liquid, add 47 gram Cadmium Sulphates by quality, 200 gram ammonium chlorides, 80 gram N (CH
2COOH)
3, 10 milliliters of DE additives, regulating the pH value is 7.0, at ambient temperature, the employing cathode current density is 0.6A/dm
2
6, zinc-plated: as to adopt alkaline non-cyanogen galvanization technology;
In every liter of galvanizing flux, be added with 12 gram zinc oxide by quality, 100 gram sodium hydroxide, 5.5 gram DZ-503 additives, 2.5 gram activity charcoal powders.30 ℃ of electroplating temperatures, cathode current density are 2A/dm
2, the positive and negative pole-face is long-pending than being 2:1, and the fastening piece spacing is more than 200 millimeters;
7, passivation: adopt trivalent chromium passivation process;
Operating process is: the zinc-plated back of fastening piece is cleaned 2 times with cold water, with the polishing of 1.5% dilute nitric acid solution, after passivation, zinc-plated fastening piece is cleaned again, uses centrifugal hot blast drying at last;
Passivating solution is formed: in every liter of passivating solution, be added with 40 gram chromium trichlorides by quality, and 2 gram Neutral ammonium fluorides, 3.5 milliliters of nitric acid, 6 gram Xiao Suangus, regulating the pH value is 2.0,23 ℃ of service temperatures, passivation time of immersion 25 seconds;
8, the zinc coating dehydrogenation is handled: the dehydrogenation process temperature is incubated 2.5 hours at 180～190 ℃.Purpose is in order to reduce owing to cadmium, zinc coating prepare the risk that process produces hydrogen embrittlement;
9, spraying fluorocarbon coating: the fastening piece after will passing through dehydrogenation and handling with hot blast drying after, carry out surface and spray fluorocarbon coating, 10～15 microns of wet-film thickness scopes;
10, fluororine-carbon coating solidifies: the fastening piece that will pass through the spraying fluorocarbon coating places solidification device, under 240 ℃ of temperature condition, solidifies 40 minutes, and the fluorocarbon coating film forming that fastener surface is applied is solidified.
Advantage of the present invention
The present invention includes the fluorocarbon coating sealer coat of fastening piece appearance and cadmium plating, zinc coating two portions of fastening piece substrate.Fastening piece appearance fluororine-carbon coating can reduce shear-stress, avoids the coating shedding in the installation process, guarantees the integrity of fastener surface coating greatly; In addition, fluororine-carbon coating has extremely strong chemical-resistant, and complete fluororine-carbon coating can play the electrolytical effect of shielding, avoids corrosive medium to contact with metallographic phase.Damaged when fluororine-carbon coating, behind the solution and metal layer contacting of chloride ion-containing, substrate cadmium plating, zinc-plated coating can be brought into play long lasting sacrificial anode effect.Substrate coating adopts the dual compound pattern of cadmium/zinc film forming, in cl ions solution and the coupling of the potential difference between ferrous materials appropriate, avoided single coating electrochemistry to consume too fast problem, can guarantee that fastening piece is in capacity all the time and effectively among the protection.
Present method has systematically solved the corrosion failure problem of fastening piece from ionogen shielding and electro-chemical protection two aspects.To the problem of fastening piece coating damage in the installation process, adopt electrochemical method to compensate, reasonably design the potential difference between cadmium, zinc coating and fastening piece base metal, form long-term sacrificial anode effect, in order to solve the etching problem of fastening piece.
Claims (2)
1. boats and ships fastening piece cadmium-zinc-fluorine carbon compound coating is characterized in that: on fastening piece (1), be provided with spiral shell tooth (1.1), be followed successively by cadmium plating layer (1.11), zinc coating (1.12) and fluororine-carbon coating (1.13) outside the spiral shell tooth from inside to outside.
2. boats and ships fastening piece cadmium-zinc-fluorine carbon preparation method of composite coating is characterized in that: the fastening piece body in order through cleaning after oil removing, cleaning, electrochemical etching, the etch, cadmium plating, zinc-plated, passivation, dehydrogenation handle, spraying fluorocarbon coating, fluororine-carbon coating solidification process;
The concrete operations step
(1) fastening piece oil removing:, carry out oil removing with 80～90 ℃ of dipping by lye fastening pieces;
Alkali lye is formed: in every premium on currency solution, be added with 25 gram sodium hydroxide by quality, 30 gram yellow soda ash, 7 grams, ten phosphate dihydrate sodium, 10 gram water glass, 1.7～2 gram OP emulsifying agents;
(2) clean: clean three times with 50～60 ℃ of clear water through the fastening piece after the alkali lye oil removing;
(3) electrochemical etching: adopt negative electrode-anode associating etch method; Catodic etching and anodic souring time ratio are 3:2, and the fastening piece after oil removing is cleaned is inserted in the container, add the etch liquid that descales; Through the descale immersion of liquid of etch, the oxide debris of removing fastening piece;
Catodic etching: with the stereotype is anode, and fastening piece is a negative electrode, and the catodic etching current density is 8A/dm
2, 60 ℃ of etch temperature, the time is 10 minutes;
Etching solution is formed: in every liter of solution, and by the vitriol oil of quality adding 43 gram proportions 1.84, the hydrochloric acid of 28 gram proportions 1.19,22 gram sodium-chlor, the urotropine of 1～5 gram;
Anodic souring: with the iron plate is negative electrode, and fastening piece is an anode, and current density is 4A/dm
2, 35 ℃ of etch temperature, the etch time is 6 minutes;
Etching solution is formed: in every liter of solution, and by the vitriol oil of quality adding 12 gram proportions 1.84,230 gram iron vitriols, 50 gram sodium-chlor, 5 gram YLENE thiocarbamides;
(4) clean after the etch: clean with the fastening piece of 23 ℃ of cold water after to etch;
(5) cadmium plating: adopt ammonia carboxylic complex compound cadmium plating technology;
In every liter of cadmium plating liquid, add 47 gram Cadmium Sulphates by quality, 200 gram ammonium chlorides, 80 gram N (CH
2COOH)
3, 10 milliliters of DE additives, regulating the pH value is 7.0, at ambient temperature, the employing cathode current density is 0.6A/dm
2
(6) zinc-plated: as to adopt alkaline non-cyanogen galvanization technology;
In every liter of galvanizing flux, be added with 12 gram zinc oxide by quality, 100 gram sodium hydroxide, 5.5 gram DZ-503 additives, 2.5 gram activity charcoal powders, 30 ℃ of electroplating temperatures, cathode current density is 2A/dm
2, the positive and negative pole-face is long-pending than being 2:1, and the fastening piece spacing is more than 200 millimeters;
(7) passivation: adopt trivalent chromium passivation process;
Operating process is: the zinc-plated back of fastening piece is cleaned 2 times with cold water, with the polishing of 1.5% dilute nitric acid solution, after passivation, zinc-plated fastening piece is cleaned again, uses hot blast drying at last;
Passivating solution is formed: in every liter of passivating solution, be added with 40 gram chromium trichlorides by quality, and 2 gram Neutral ammonium fluorides, 3.5 milliliters of nitric acid, 6 gram Xiao Suangus, regulating the pH value is 2.0,23 ℃ of service temperatures, passivation time of immersion 25 seconds;
(8) dehydrogenation is handled: the dehydrogenation process temperature is incubated 2.5 hours at 180～190 ℃;
(9) spraying fluorocarbon coating: the fastening piece after will passing through dehydrogenation and handling with hot blast drying after, carry out surface and spray fluorocarbon coating, coating wet-film thickness scope is at 10～15 microns;
(10) fluororine-carbon coating solidifies: the fastening piece that will pass through the spraying fluorocarbon coating places solidification device, under 240 ℃ of temperature condition, solidifies 40 minutes, and the fluorocarbon coating film forming that fastener surface is applied is solidified.
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| CN 201010611710 CN102534628B (en) | 2010-12-29 | 2010-12-29 | Method for preparing cadmium-zinc-fluorocarbon composite coating of ship fastener |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974519A (en) * | 2012-11-15 | 2013-03-20 | 宝鸡森特瑞石油机械科技有限公司 | Anticorrosive technology used for marine environment fastener |
| CN106191938A (en) * | 2016-08-31 | 2016-12-07 | 贵州红林机械有限公司 | A kind of non-cyanide plating cadmium tank liquor, its compound method and purposes |
| TWI735302B (en) * | 2020-07-31 | 2021-08-01 | 林憲良 | Multi-color electro-galvanization and its alloy coating structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3765944A (en) * | 1971-11-26 | 1973-10-16 | Dow Chemical Co | Battery having a molten alkali metal polysulfide catholyte and carbon coated metallic electrode for use therein |
| CN1931571A (en) * | 2005-09-15 | 2007-03-21 | 李富春 | Double layer anticorrosive plastic-steel metal member and its production process |
| CN101270404A (en) * | 2008-04-17 | 2008-09-24 | 葛海泉 | Method for producing special fastener |
-
2010
- 2010-12-29 CN CN 201010611710 patent/CN102534628B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3765944A (en) * | 1971-11-26 | 1973-10-16 | Dow Chemical Co | Battery having a molten alkali metal polysulfide catholyte and carbon coated metallic electrode for use therein |
| CN1931571A (en) * | 2005-09-15 | 2007-03-21 | 李富春 | Double layer anticorrosive plastic-steel metal member and its production process |
| CN101270404A (en) * | 2008-04-17 | 2008-09-24 | 葛海泉 | Method for producing special fastener |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974519A (en) * | 2012-11-15 | 2013-03-20 | 宝鸡森特瑞石油机械科技有限公司 | Anticorrosive technology used for marine environment fastener |
| CN106191938A (en) * | 2016-08-31 | 2016-12-07 | 贵州红林机械有限公司 | A kind of non-cyanide plating cadmium tank liquor, its compound method and purposes |
| TWI735302B (en) * | 2020-07-31 | 2021-08-01 | 林憲良 | Multi-color electro-galvanization and its alloy coating structure |
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