CN101748353A - Method for antiseptic treatment of marine climate resistant engineering component - Google Patents

Method for antiseptic treatment of marine climate resistant engineering component Download PDF

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Publication number
CN101748353A
CN101748353A CN200910262716A CN200910262716A CN101748353A CN 101748353 A CN101748353 A CN 101748353A CN 200910262716 A CN200910262716 A CN 200910262716A CN 200910262716 A CN200910262716 A CN 200910262716A CN 101748353 A CN101748353 A CN 101748353A
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coating
treatment
diffusion layer
carried out
preheating
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CN101748353B (en
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冯立新
张敏燕
缪强
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WUXI LINLONG ALUMINIUM CO Ltd
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WUXI LINLONG ALUMINIUM CO Ltd
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Abstract

The invention relates to a method for antiseptic treatment of marine climate resistant engineering component, comprising: 1. carrying out rust removal treatment on components; 2. carrying out etching treatment to components; 3. carrying out surface activation treatment on the components; 4. putting components into a special atmosphere oven to preheat; 5. dipping the preheated components into plating solution to dip, wherein the components rotate in the dipping process; 6. carrying out diffusion treatment; and 7. adopting coating for seal treatment. Components treated by the method of the invention can endow full corrosion resistance and washing corrosion resistance under the condition of marine climate.

Description

A kind of marine climate resistant engineering component carries out antiseptic method
Technical field
The present invention relates to a kind of marine climate resistant engineering component and carry out antiseptic method.
Background technology
Along with rapid development of science and technology, the engineer equipment that is applied in coastal waters and the ocean is more and more, its service condition press ISO 9225 environmental evaluation standards generally>the C5 level, belong to extreme environment.Described ambient atmosphere is rainy, high temperature, many salt fogs and high wind stream, and exposed part will be subjected to intensive atomospheric corrosion, galvanic corrosion and the comprehensive action of airflow scouring erosive, and the work-ing life of various steel construction is far below general landlocked outdoor environment.As one of the typical project of under the oceanic climate condition, being on active service equipment wind power plant, because wind power generating set is to utilize wind power generation, and in shoreline, offshore ocean, having abundant wind resource, it is that addressing is in inshore or offshore ocean that the construction of wind energy turbine set has significant proportion.Yet, because the external member of unit such as cabin, hood, pylon etc. directly are exposed in the extreme corrosion atmosphere, adopt conventional safeguard procedures, often only several months just produce serious corrosion, this has brought tremendous loss, and according to statistics, the loss of marine corrosion accounts for 1/3 of total corrosion loss, moreover, because the accident that marine corrosion brings especially can't counting loss.As one 5 ton ore Ship for Transporting Module of Japan in 1969, the sinking suddenly because corrosion shortness destroys.Therefore, strengthen corrosion control, reduce the loss of metallic substance, avoid equipment in ocean environment, to suffer too early or unexpected failure, very important strategic importance is arranged.
The fast development of modern surface engineering technology is for the corrosion prevention of steel surface provides multiple solution, as plating, electroless plating, thermospray, vapour deposition etc.Yet, electroplate and the coating of electroless plating too thin, generally have only several microns, and the hardness of coating own too low be difficult to resist contain the particle airflow scouring.Though thermospray has advantages such as coat-thickness is big, easy and simple to handle, the surface shape of guarded part, size control are difficult, are unsuitable for this project goal in research part substantially.And vapour deposition cost height, be difficult to handle the big area part, and the thin thickness of coating own, have pin hole and in salt fog Cl -Erosion under quick corrosion can take place.In addition, the problem of the general character that above-mentioned means also exist is above-mentioned technique means complex process, the production cost height, and even more serious is, adopt coated layer that above-mentioned technique means obtains under environment, stress synergy, be easy to peel off and lose protection effect, therefore, research and develop effective new anticorrosion process, become the active demand of current industry development.
Summary of the invention
At these problems in the prior art, the invention provides a kind of antiseptic method of marine climate resistant engineering component, thereby thoroughly solved the problem that exists in the present technology.
A kind of marine climate resistant engineering component provided by the invention carries out antiseptic method, comprising:
The first step: part is carried out processing of rust removing;
Second step: part is carried out etch handle;
The 3rd step: part is carried out surface activation process;
The 4th step: part is placed on preheating in the atmosphere protection stove;
The 5th step: will immerse submergence in the plating bath through the part of preheating, and in the immersion processes part be imposed rotation;
The 6th step: the part of immersion plating is put into the processing of vacuum oven internal diffusion;
The 7th step: adopt coating to carry out sealing treatment.
Preferably, wherein processing of rust removing described in the first step is first with after part cleaning, the oil removing, carries out processing of rust removing by pickling again.
Preferably, wherein etch processing described in second step is the part behind the degreasing and rust removal to be placed in hydrochloric acid and the hydrofluoric acid mixing solutions room temperature etch 1~3 minute, rinsed with deionized water again; Wherein said hydrochloric acid and hydrofluoric acid mixing solutions by volume are calculated hydrochloric acid HCl and are accounted for 94%~96%, and hydrofluoric acid HF accounts for 4%~6%.
Preferably, wherein the treatment temp of surface activation process is 40~60 ℃ described in the 3rd step, and the time is 30~40min, and the prescription of the activation solution of described surface activation process is:
Ethylene glycol C 2H 6O 2600~900ml/L
Acid ammonium fluoride NH 4HF 225~45g/L
Nickelous chloride NiCl 2-6H 2O 10~30g/L
Boric acid H 3BO 320~60g/L
Lactic acid C 3H 6O 310~35ml/L
Acetic acid C 2H 4O 270~230ml/L.
Preferably, wherein in the 4th step described part is placed in the atmosphere protection stove through 500~650 ℃ of preheatings 10~20 minutes.
Preferably, wherein will immerse through the part of preheating in the plating bath in the 5th step, submergence 1~5 minute, wherein said plating bath mainly is made up of Zn, Al, Si, RE, microalloy element and nano-oxide particles toughener, and described nano-oxide particles toughener is selected from TiO 2, CeO 2In one or both, described microalloy element is selected from a kind of or several arbitrarily among Mg, Ti, the Ni, and each composition accounts for plating bath total mass per-cent: Zn:35~58%, Si:0.3~4.0%, RE:0.02~1.0%, the content that the nano-oxide particles toughener is total: 0.01~1.0%, the content that microalloy element is total: 0.01~6.0%, Al: surplus.
Preferred, the median size of wherein said nano-oxide particles toughener is 15~60nm, and the concrete add-on of described each composition of microalloy element accounts for total mass per-cent and is: Mg:0.1~5.0%, Ti:0.01~0.5%, Ni:0.1~3.0%.
Preferably, wherein will be in the 6th step the part of immersion plating put into vacuum oven, 800~950 ℃ of insulations after 1~3 hour progressively cooling take out, thereby make atomic diffusion at the interface and on matrix, form the metallurgical binding of diffusion layer realization and coating and matrix, described thickness of diffusion layer is 10~30 μ m.
Preferably, wherein in the 7th step coating adopt silane, Resins, epoxy or polyurethane.
On the other hand, the present invention also provides the component of the antiseptic marine climate resistant of a kind of process, the coat-thickness of described component surface is 200~300 μ m, also comprise the diffusion layer that makes atomic diffusion at the interface and on matrix, form in the described coating, realize the metallurgical binding of coating and matrix by described diffusion layer, the thickness of described diffusion layer is 10~30 μ m, and wherein said diffusion layer forms through following technological process:
The first step: part is carried out processing of rust removing;
Second step: part is carried out etch handle;
The 3rd step: part is carried out surface activation process;
The 4th step: part is placed on preheating in the atmosphere protection stove;
The 5th step: will immerse submergence in the plating bath through the part of preheating, and in the immersion processes part be imposed rotation;
The 6th step: DIFFUSION TREATMENT;
The 7th step: adopt coating to carry out sealing treatment.
Adopt activation solution of the present invention before immersion plating, part to be carried out surface activation process, basically eliminate activation solution part is produced the corrosive risk, and owing to substituted the use of fluoroboric acid in the prior art or hydrofluoric acid, environmental pollution is little, thereby environmental protection more, energy-conservation.
The present invention puts into the atmosphere protection stove with the parts of immersion plating before immersion plating, the preheated one-section time, thus reduced mechanical property mismatch between coating and the body material, even coating is not also peeled off under the effect of contact fine motion load.
On the other hand, the coating that adopts plating bath of the present invention to form, opposing atomospheric corrosion, galvanic corrosion and airflow scouring erosional competency significantly improve, and the intensity of coating, hardness, and scour resistance is also all significantly improved.
Moreover, the present invention has also increased the step of DIFFUSION TREATMENT after immersion plating, impel atomic diffusion at the interface and form diffusion layer and the metallurgical binding of realization and coating and matrix at the base material place, make coating and matrix bond firm, even coated layer is under environment, stress synergy, also be not easy to peel off, thereby played good protection effect, be applicable to exceedingly odious environment such as ocean fully.
In sum, the technology of the present invention compared with prior art, production technique is simplified, not only cost is low, and environmental protection, energy-conservation.Owing to need not adopt chemical plating fluid, so carrying capacity of environment is also very little.Hot dip process is easy and simple to handle, lower cost for material, the thickness of coating adjustable range is wide, coating and matrix bond are firm, and coating anti-corrosion, wear resistance good, be fit to the processing of various size part, the part that the technology of the present invention was handled can be given its abundant corrosion resistance nature and antiscour erosion performance under the oceanic climate condition.
Embodiment
Marine climate resistant engineering component provided by the invention carries out antiseptic method, comprising:
The first step: part is carried out processing of rust removing;
Second step: part is carried out etch handle;
The 3rd step: part is carried out surface activation process;
The 4th step: part is placed on preheating in the atmosphere protection stove;
The 5th step: will immerse submergence in the plating bath through the part of preheating, and in the immersion processes part be imposed rotation;
The 6th step: the part of immersion plating is put into the processing of vacuum oven internal diffusion;
The 7th step: adopt coating to carry out sealing treatment.
Below, provide some preferred specific embodiments that adopt method of the present invention to prepare the marine climate resistant corrosion protection coating at the steel construction piece surface, but need to prove, the condition that provides in the following specific embodiment is described as essential features, to those skilled in the art, can on the basis of the listed numerical value of embodiment, rationally summarize and derive fully.
Embodiment 1
(1) with after part cleaning, the oil removing, handles rinsed with deionized water by acid pickling and rust removing.
(2) with the part behind the degreasing and rust removal in hydrochloric acid HCl 94% (volume fraction)+hydrofluoric acid HF6% (volume fraction) mixing solutions, room temperature etch 1 minute, rinsed with deionized water.
(3) at ethylene glycol, acid ammonium fluoride, nickelous chloride, boric acid, lactic acid, activation treatment in the mixing solutions of acetic acid, 40 ℃ of temperature, time 40min, rinsed with deionized water, drying.
(4) part that will handle through (1)~(3) be put into the atmosphere protection stove, 500 ℃ of preheatings 20 minutes.
(5) in the atmosphere protection smelting furnace, will immerse in the plating bath through the steel part of preheating, submergence 1 minute imposes rotation to part in the immersion processes.
(6) parts of immersion plating are put into vacuum oven, 800 ℃ of insulation progressively cooling taking-ups after 3 hours make to form diffusion layer under its coating, through above-mentioned technological process, form the protection plating at piece surface and ooze composite bed.
(7) adopt conventional coating process and coating such as silane, Resins, epoxy or polyurethane to carry out sealing treatment.
Embodiment 2
(1) with after part cleaning, the oil removing, handles rinsed with deionized water by acid pickling and rust removing.
(2) with the part behind the degreasing and rust removal in hydrochloric acid HCl 95% (volume fraction)+hydrofluoric acid HF5% (volume fraction) mixing solutions, room temperature etch 2 minutes, rinsed with deionized water.
(3) at ethylene glycol, acid ammonium fluoride, nickelous chloride, boric acid, lactic acid, activation treatment in the mixing solutions of acetic acid, 50 ℃ of temperature, time 35min, rinsed with deionized water, drying.
(4) part that will handle through (1)~(3) be put into the atmosphere protection stove, 600 ℃ of preheatings 15 minutes.
(5) in the atmosphere protection smelting furnace, will immerse in the plating bath through the steel part of preheating, submergence 3 minutes imposes rotation to part in the immersion processes.
(6) parts of immersion plating are put into vacuum oven, 880 ℃ of insulation progressively cooling taking-ups after 2 hours make to form diffusion layer under its coating, through above-mentioned technological process, form the protection plating at piece surface and ooze composite bed.
(7) adopt conventional coating process and coating such as silane, Resins, epoxy or polyurethane to carry out sealing treatment.
Embodiment 3
(1) with after part cleaning, the oil removing, handles rinsed with deionized water by acid pickling and rust removing.
(2) with the part behind the degreasing and rust removal in hydrochloric acid HCl 96% (volume fraction)+hydrofluoric acid HF4% (volume fraction) mixing solutions, room temperature etch 3 minutes, rinsed with deionized water.
(3) at ethylene glycol, acid ammonium fluoride, nickelous chloride, boric acid, lactic acid, activation treatment in the mixing solutions of acetic acid, 60 ℃ of temperature, time 30min, rinsed with deionized water, drying.
(4) part that will handle through (1)~(3) be put into the atmosphere protection stove, 650 ℃ of preheatings 10 minutes.
(5) in the atmosphere protection smelting furnace, will immerse in the plating bath through the steel part of preheating, submergence 5 minutes imposes rotation to part in the immersion processes.
(6) parts of immersion plating are put into vacuum oven, 950 ℃ of insulation progressively cooling taking-ups after 1 hour make to form diffusion layer under its coating, through above-mentioned technological process, form the protection plating at piece surface and ooze composite bed.
(7) adopt conventional coating process and coating such as silane, Resins, epoxy or polyurethane to carry out sealing treatment.
Wherein, the composition of the activation solution of surface activation process and content are as shown in table 1 below among the embodiment 1-3, and of particular note, only be to provide the composition of activation solution of the present invention and some preferred embodiments of content in the table 1, but the composition of activation solution of the present invention and content are not limited to listed numerical value in this table, for a person skilled in the art, fully can be in table rationally summarize and reasoning on the basis of listed numerical range, therefore, following examples all are as preferred condition, and are described as prerequisite of the present invention.
Table 1: the activation solution prescription, the composition of per 1 liter (L) and content, surplus is a water.
Figure G2009102627168D00071
Wherein, the composition of plating bath and content are as shown in table 2 below among the embodiment 1-3, and of particular note, only some preferred embodiments that provide plating bath of the present invention in the table 2, although the microalloy element of table 2 comprises Mg, Ti, three kinds of elements of Ni simultaneously, but these are described as essential features, microalloy element of the present invention can be selected among Mg, Ti, the Ni any, two or three, similarly, be Ti0 although list described nano-oxide particles toughener in the table 2 2, but nano-oxide particles toughener of the present invention can also be selected from CeO 2Or two kinds of uses simultaneously.
Table 2: each composition accounts for the mass percentage content (%) of gross weight
Figure G2009102627168D00081
On the other hand, the present invention also provides the component of the antiseptic marine climate resistant of a kind of process, the coat-thickness of described component surface is 200~300 μ m, also comprise the diffusion layer that makes atomic diffusion at the interface and on matrix, form in the described coating, realize the metallurgical binding of coating and matrix by described diffusion layer, the thickness of described diffusion layer is 10~30 μ m, and wherein said diffusion layer forms through following technological process:
The first step: part is carried out processing of rust removing;
Second step: part is carried out etch handle;
The 3rd step: part is carried out surface activation process;
The 4th step: part is placed on preheating in the atmosphere protection stove;
The 5th step: will immerse submergence in the plating bath through the part of preheating, and in the immersion processes part be imposed rotation;
The 6th step: DIFFUSION TREATMENT;
The 7th step: adopt coating to carry out sealing treatment.
Provide below the coating through DIFFUSION TREATMENT of the present invention some preferred embodiment, as following table 3:
Table 3: thickness unit (μ m)
Sequence number Coat-thickness Thickness of diffusion layer Binding force of cladding material Solidity to corrosion
??1 ??200 ??10 1 grade Very
??2 ??210 ??11 1 grade Very
??3 ??220 ??13 1 grade Excellent
??4 ??235 ??16 1 grade Excellent
??5 ??250 ??19 1 grade Excellent
??6 ??260 ??21 1 grade Excellent
??7 ??270 ??25 1 grade Excellent
??8 ??290 ??28 2 grades Excellent
??9 ??300 ??30 2 grades Excellent
Annotate: the binding force of cladding material testing method is carried out with reference to GB1720-79
In sum, although above enumerated the present invention some preferred embodiment, inventive concept of the present invention is not limited thereto, and is on this basis all, and the present invention is carried out the change of unsubstantiality, all should fall within protection scope of the present invention.

Claims (10)

1. a marine climate resistant engineering component carries out antiseptic method, comprising:
The first step: part is carried out processing of rust removing;
Second step: part is carried out etch handle;
The 3rd step: part is carried out surface activation process;
The 4th step: part is placed on preheating in the atmosphere protection stove;
The 5th step: will immerse submergence in the plating bath through the part of preheating, and in the immersion processes part be imposed rotation;
The 6th step: the part of immersion plating is put into the processing of vacuum oven internal diffusion;
The 7th step: adopt coating to carry out sealing treatment.
2. method according to claim 1, wherein processing of rust removing described in the first step is first with after part cleaning, the oil removing, carries out processing of rust removing by pickling again.
3. method according to claim 1, wherein the etch processing is the part behind the degreasing and rust removal to be placed in hydrochloric acid and the hydrofluoric acid mixing solutions room temperature etch 1~3 minute, rinsed with deionized water again described in second step; Wherein said hydrochloric acid and hydrofluoric acid mixing solutions by volume are calculated hydrochloric acid HCl and are accounted for 94%~96%, and hydrofluoric acid HF accounts for 4%~6%.
4. method according to claim 1, wherein the treatment temp of surface activation process is 40~60 ℃ described in the 3rd step, and the time is 30~40min, and the prescription of the activation solution of described surface activation process is:
Ethylene glycol C 2H 6O 2600~900ml/L
Acid ammonium fluoride NH 4HF 225~45g/L
Nickelous chloride NiCl 2-6H 2O 10~30g/L
Boric acid H 3BO 320~60g/L
Lactic acid C 3H 6O 310~35ml/L
Acetic acid C 2H 4O 270~230ml/L.
5. method according to claim 1 wherein in the 4th step is placed in the atmosphere protection stove described part through 500~650 ℃ of preheatings 10~20 minutes.
6. method according to claim 1, wherein will immerse through the part of preheating in the plating bath in the 5th step, submergence 1~5 minute, wherein said plating bath mainly are made up of Zn, Al, Si, RE, microalloy element and nano-oxide particles toughener, and described nano-oxide particles toughener is selected from TiO 2, CeO 2In one or both, described microalloy element is selected from a kind of or several arbitrarily among Mg, Ti, the Ni, and each composition accounts for plating bath total mass per-cent: Zn:35~58%, Si:0.3~4.0%, RE:0.02~1.0%, the content that the nano-oxide particles toughener is total: 0.01~1.0%, the content that microalloy element is total: 0.01~6.0%, Al: surplus.
7. method as claimed in claim 5, the median size of wherein said nano-oxide particles toughener is 15~60nm, the concrete add-on of described each composition of microalloy element accounts for total mass per-cent: Mg:0.1~5.0%, Ti:0.01~0.5%, Ni:0.1~3.0%.
8. method according to claim 1, wherein will be in the 6th step the part of immersion plating put into vacuum oven, 800~950 ℃ of insulation progressively cooling taking-ups after 1~3 hour, thereby make atomic diffusion at the interface and form the metallurgical binding of diffusion layer realization and coating and matrix on matrix, described thickness of diffusion layer is 10~30 μ m.
9. method according to claim 1, wherein coating adopts silane, Resins, epoxy or polyurethane in the 7th step.
10. the component of the antiseptic marine climate resistant of process, the coat-thickness of described component surface is 200~300 μ m, also comprise the diffusion layer that makes atomic diffusion at the interface and on matrix, form in the described coating, realize the metallurgical binding of coating and matrix by described diffusion layer, the thickness of described diffusion layer is 10~30 μ m, and wherein said diffusion layer forms through following technological process:
The first step: part is carried out processing of rust removing;
Second step: part is carried out etch handle;
The 3rd step: part is carried out surface activation process;
The 4th step: part is placed on preheating in the atmosphere protection stove;
The 5th step: will immerse submergence in the plating bath through the part of preheating, and in the immersion processes part be imposed rotation;
The 6th step: DIFFUSION TREATMENT;
The 7th step: adopt coating to carry out sealing treatment.
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CN103361588A (en) * 2012-03-30 2013-10-23 鞍钢股份有限公司 Production method of low-aluminum low-magnesium zinc-aluminum-magnesium coated steel plate and coated steel plate thereof
CN103361588B (en) * 2012-03-30 2016-04-06 鞍钢股份有限公司 Production method of low-aluminum low-magnesium zinc-aluminum-magnesium coated steel plate and coated steel plate thereof
CN107488818A (en) * 2017-06-27 2017-12-19 马鞍山市鑫龙特钢有限公司 A kind of weathering steel being used under marine environment
CN107488818B (en) * 2017-06-27 2020-04-10 马鞍山市鑫龙特钢有限公司 Weather-resistant steel used in marine environment
CN110643932A (en) * 2019-09-25 2020-01-03 马鞍山市三川机械制造有限公司 Treatment process for improving corrosion resistance of steel structure
CN116550577A (en) * 2023-04-14 2023-08-08 烟台大学 Coating treatment process for marine climate resistant engineering part surface coating
CN116550577B (en) * 2023-04-14 2024-02-13 烟台大学 Coating treatment process for marine climate resistant engineering part surface coating

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