CN101487118B - Passivation agent for preventing hot dip galvanizing steel strand surface white rust and coating method - Google Patents
Passivation agent for preventing hot dip galvanizing steel strand surface white rust and coating method Download PDFInfo
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- CN101487118B CN101487118B CN2009100642962A CN200910064296A CN101487118B CN 101487118 B CN101487118 B CN 101487118B CN 2009100642962 A CN2009100642962 A CN 2009100642962A CN 200910064296 A CN200910064296 A CN 200910064296A CN 101487118 B CN101487118 B CN 101487118B
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Abstract
The invention relates to a passivator which is capable of preventing generating white rust on the surface of thermal-galvanizing strand and a coating method thereof; the passivator consists of component A, component B and deioned water by the weight proportion of 1:3-5:16, wherein, the component A consists of aqueous acrylic acid epoxy ester resin and deioned water by the weight proportion of 2-3:1; and the component B consists of 4.0-6.0g/L of chromium chloride, 0.6g/L of sulfuric acid, 2.5ml/L of acetic acid and the balance of water. The coating method is characterized in that the strand continuously passes by a compression roller under the traction force of a supporting roller, enters a trough, dips the passivator, is led out by the supporting roller, subsequently enters a drying box and is subsequently coiled on an I-shaped wheel, thus completing the continuous operation process of the online passivation of the strand. The method has simple process, low cost and strong white rust resistance capability; furthermore, the passivator has no pollution to the environment and human body, can be directly applied to the entwisting and stranding production line of the thermal-galvanizing strand, solves the problem that the white rust is generated on the surface of the thermal-galvanizing strand and has excellent generalization value and social benefits.
Description
One, technical field:
The present invention relates to the hot dip galvanizing coating surface anticorrosive technology in the Steel Wire Products Industry, particularly relate to a kind of hot dip galvanizing steel strand surface that prevents and produce the passivator and the coating method of white rust.
Two, background technology:
Hot dip galvanizing steel strand (Hot-dip galvanized lron wire strands) is a kind of metal products of electric power overhead high voltage transmission line with usefulness such as Aluminium Cable Steel Reinforced, optical cable, tape armored cable, wire communication circuit and mounting article, bolt systems.It is formed by special-purpose stranding machine (closing) system of twisting with the fingers by many hot-dip galvanizing steel wires.Hot dip galvanizing coating is the most effectively one of corrosion protection coating of present steel surface, and generally can reach 15～20 years work-ing life in the atmospheric environment, so be used as the protective coating that prevents the steel product corrosion.But because zinc is very active metal; chemical stability was not high when zinc coating used in atmospheric environment; especially Stranded Galvanized Steel Wire is twisted with the fingers after (closing) system; store, run in the transportation damp atmosphere, sultry environment with the etch that contacts of etchant gas, medium; chemical transformation very easily takes place in its surface; produce white rust and gray corrosion, directly influence the erosion resistance and the outward appearance of its coating, influence the work-ing life of Stranded Galvanized Steel Wire.When hot dip galvanizing steel strand coating surface white rust was serious, the client proposed quality objection, even returned goods, and caused quality problems.
Zinc coating white rust and gray corrosion former appears because: zinc is the very active amphoteric metal of a kind of chemical property, and its metal monomer is met O
2Oxidized at once, its product ZnO belongs to intermediate oxide, generates inclined to one side zincate with alkali reaction, generates zinc salt with acid-respons.Reaction formula is as follows:
Zn+O
2=2ZnO (white)
2Zn+O
2+ 2H
2O=2Zn (OH)
2(white)
ZnO+2NaOH=Na
2ZnO
2+ H
2O (ash is dark-coloured)
ZnO+2HCl=H
2O+ZnCl
2(light green)
ZnO+SO
2=ZnSO
3(canescence)
ZnO+CO
2=ZnCO
3(lead)
Zn+2HCl=ZnCl
2+ H
2(lead)
When the Stranded Galvanized Steel Wire compact winding and place malaria or during etchant gas; owing to there is not fluidizing air freely between Stranded Galvanized Steel Wire; the chemical reaction of above-mentioned corrosion product protective membrane can not take place in the coating local surfaces, but galvanic corrosion takes place, and form white rust.In fact the formation mechanism of white rust be exactly " oxygen concentration corrosion cell " principle.The severity that produces white rust depends on coating surface residual moisture and the time length in environment of living in, if contain in the residual moisture from the muriate in the seawater, from the sulfide of industrial environment, electrical conductivity of water is improved in the capital, thereby increases the effect of oxygen concentration corrosion cell.Galvanic corrosion speed is far above the chemical reaction corrosion speed, and its corrosion product is the zinc salt that does not have protective capability.Therefore, in industrial atmosphere, damp atmosphere and oceanic climate, zinc coating is easy to be corroded.Be in particular in that zinc-plated aspect tarnishes, produce the dimmed zinc rust of one deck.It is a kind of S of containing, C, Cl, O
2Etc. elementary composition, baroque salt compounds.Particularly in the sour gas of humidity, after the ZnO of coating surface layer was dissolved, the Zn of exposure can replace the hydrogen in the acid at a high speed, becomes Zn
+ 2, cause the quick corrosion of Zn layer and to become ash dark-coloured.
Avoid corrosion in order to protect hot dip galvanizing coating; need to continue zinc coating is carried out the generation that surface treatment reduces the zinc coating white rust; effective means is to adopt chromating to handle the most at present; behind chromate treating; make the hot dip galvanizing coating surface form the high chromating rete of chemical stability; with the solidity to corrosion and the anti-white rust ability of raising zinc coating, and then the work-ing life of prolongation steel strand.
Though traditional sexavalence chromic acid passivation technology is relatively mature and stable, film forming speed is fast, but sexavalent chrome has high toxicity and carinogenicity, environmental pollution is serious, contact for a long time the toxic effect of human body, strict measure of control have all been formulated in countries in the world, limit its use, and especially some foreign trade pot galvanize product surfaces do not allow sexavalent chrome to exist.But because sea transport and pack surface white rust and gray corrosion phenomenon all can take place causes some foreign trade dispute and financial losses thus.The many non-chromium inactivating techniques of numerous and confused both at home and abroad proposition, however single passive film inorganic or that organic inhibitor obtains is thinner, and anti-corrosion effects can not be satisfactory.Seeking trivalent chromium replaces chromic passivation technology to become the emphasis (trivalent chromium toxicity is lower 100 times than sexavalent chrome toxicity) of paying close attention to and studying.Trivalent chromium has chromic characteristic in many aspects, and trivalent chromium is the basic nutrition element of human body, help lend some impetus to the metabolism of sugar, protein and fat, with compound form exist as Citrate trianion and muriatic trivalent chromium, be the trace element of needed by human.The adaptability that requires and have now factory from ecology is considered, adopts the most possible received suitable alternative techniques of the conventional chromating of trivalent chromium passivation will becoming.
Because the limitation of existing steel-wire galvanizing production technique, directly carry out Passivation Treatment after zinc-plated the pot galvanize in batches unlike steel piece, so still do not have manufacturing enterprise so far both at home and abroad to the online Passivation Treatment of carrying out of steel-wire galvanizing.By literature search, do not retrieve correlation technique and the report that hot dip galvanizing steel strand is prevented the white rust Passivation Treatment.
Three, summary of the invention:
The technical problem to be solved in the present invention: overcome the problem in the background technology, provide a kind of hot dip galvanizing steel strand that prevents to produce the passivator and the coating method of white rust, this passivator formula is reasonable, with low cost, this coating method is to environment friendly and pollution-free, and can continuous production process in twisting hot dip galvanizing steel strand production process.
Technical scheme of the present invention is:
The present invention utilizes chromic salt and metallic zinc reaction to generate the method for colloidal film passivation, in process of production, with the surface is that the steel wire of zinc coating immerses in the passivating solution that compound, film forming catalyst sulfuric acid and the water soluble resin of chromium form and handles, generate the film of the salt compounds composition of one deck densification, indissoluble on the zinc coating surface, zinc coating and extraneous corrosive environment are isolated, improve the erosion resistance of zinc coating with this.
It is generally acknowledged that single chromic acid passivation membrane molecule structure is roughly by CrO
3, Cr
2O
3, CrOOH and ZnCrO
4Form Deng compound.In acid passivating solution, chromic acid generation hydrolysis, most of with Cr
2O
7 2-Form have and and CrO
4 2-There is column balancing down:
2CrO
3+H
2O→H
++HCr
2O
7 -
When zinc coating immerses in the chromate-containing passivating solution, will dissolving, the formation of film and three processes of dissolving of film of zinc take place, its three main processes are almost carried out simultaneously.
1) zinc layer dissolving: 3Zn+Cr
2O
7 2-+ 14H
+=3Zn
2++ 2Cr
3++ 7H
2O (1)
3Zn+2CrO
4 2-+16H
+＝3Zn
2++2Cr
3++8H
2O (2)
Zn+2H
+＝Zn
2++H
2↑ (3)
2) formation of passive film:
Cr
3++ OH
-+ CrO
4 2-=Cr (OH) CrO
4(alkali formula chromic salt) (4)
2Cr
3++ 6OH
-=Cr
2O
33H
2O (chromium sesquioxide) (5)
2Zn
2++ 2OH
-+ CrO
4 2-=Zn
2(OH)
2CrO
4(alkali formula chromic salt) (6)
Zn
2++ 2Cr
3++ 8OH
-=Zn (CrO
2)
24H
2O (chromous acid zinc) (7)
The composition more complicated of passive film, its chemical formula roughly is:
Cr(OH)CrO
4·Cr
2(CrO
4)
3·ZnSO
4·Zn
2(OH)
2CrO
4·Zn(CrO
2)·xH
2O
3) dissolution process of passive film: when passive film is formed into to a certain degree, if continue galvanized workpiece is placed in the passivator, because ionic diffusion, hydrogen ion concentration in the passive film near surface solution can raise again, the pH value reduces, and passive film can dissolve, so passivation time is oversize, not only passive film can be not thick, on the contrary can attenuation.
Above-mentioned resultant of reaction has been identified by method of electron diffraction and has been obtained confirmation.Trivalent chromium in the chromic acid passivation film is insoluble in water, and the chemical property torpescence can not descend because of the dissolving of making moist makes bonding strength in environment, so formed skeleton, plays skeleton function; Wherein sexavalent chrome is soluble in water, Cr (OH)
3Be colloidal, by absorption Cr
3+And alkali formula chromic salt composition conversion film, the resistance of oxidation of assurance zinc coating, therefore in certain limit, passive film can prevent the direct etch zinc of some etchant gases layer, and the zinc layer is shielded.
The hot galvanized layer that prevents of the present invention is given birth to the coating method of white rust, be according to chromic acid passivation mechanism, do not contain toxic sexavalent chrome in the passivator for making, adopt the reaction of trivalent chromium and zinc layer to generate the zinc chrome oxide compound, in rete, play skeleton function, employing forms colloidal solution add some water soluble acrylic acid epoxy ester resins in passivating solution after, generates colloid to substitute the reaction of sexavalent chrome and zinc coating, reaches to substitute chromic purpose; Water soluble acrylic acid epoxy ester resin itself also has certain buffer action simultaneously, can prevent that outside moisture and corrosive gases from penetrating into the zinc coating surface, brings into play certain corrosion-resisting function.
The passivator that prevents the hot dip galvanizing steel strand white rust of the present invention is to mix by A, B component and 1: 3～5: 16 weight ratio of deionized water to form; Described A component is pressed the weight ratio of water soluble acrylic acid epoxy ester resin and deionized water 2～3: 1 and is formed; Described B component is made up of chromium chloride 4.0～6.0g/L, sulfuric acid 0.6g/L, acetic acid 2.5ml/L and surplus deionized water.
During preparation passivator, according to (Wt%) 1: 3～5: 16 ratio, thorough mixing stirs the back and uses with A component, B component and deionized water.During configuration, earlier water is put into container, add A component and B component while stirring successively, stir after finishing, must not be earlier with A, the water dilution is converted in the two mixing of B again.
Apply the method for hot dip galvanizing steel strand with passivator of the present invention, its step comprises: add passivator in the passivator groove earlier, hot dip galvanizing steel strand is continuous in having the Wirewinding roller of arc groove under the tractive force effect by carrying roller, enter dipping passivator in the passivator groove, hot dip galvanizing steel strand is drawn through carrying roller then, enter the drying baker oven dry, hot dip galvanizing steel strand on H-wheel, is finished the continuous production process process of the online anti-white rust passivation of hot dip galvanizing steel strand by rolling subsequently.
The temperature of passivator, passivation time are very obvious to the influence of the formation of passive film and thickness.Consideration according to production efficiency and comprehensive various factors requires the use temperature of passivator to remain between 35～37 ℃, and passivation time is 3～5s.
The pH value is also fairly obvious to the influence of film forming speed and thicknesses of layers, and the high film forming speed of pH value is slow, and rete is discontinuous; The pH value is crossed when hanging down, along with the prolongation of time will be the gluey film dissolving that has formed, and consumption effective constituent, and make the hot dip galvanizing coating surface staining, require the pH value of passivator between 2.0～2.8, to be advisable.
The hot galvanized layer that prevents that the present invention adopts is given birth to the device of white rust, comprises passivation device and drying unit two portions.Wherein the passivation device partly is the passivator cell body, and it is of a size of long 1500 * wide by 1000 * high by 500 (mm), and the cell body material is that PPH (polypropylene) plate of acid corrosion-resistant is welded; In the centre diameter being installed is the Wirewinding roller that 400mm has arc groove; On top, cell body two ends the holder line roller that has circular arc on two circumference is installed, plays supporting role, and can regulate the distance between two rollers, guarantee that hot dip galvanizing steel strand dipping time in anti-white rust passivating solution is 3～5 seconds hot dip galvanizing steel strand.
The oven dry part adopts drying baker, drying baker to be of a size of long 1000 * wide by 1000 * high by 300 (mm); Heating can adopt electricity or other modes to heat.When adopting resistive heating, it is the electric heating panel of 300KW that heating source can adopt power.The bake out temperature of hot dip galvanizing steel strand is controlled at 100～120 ℃.
After passivator of the present invention uses for some time, can contain the contamination precipitations such as muriate of zinc in the passivator, available filter periodic filtering passivator is to guarantee the purity of passivating solution.
Positive beneficial effect of the present invention:
(1) hot galvanized layer that prevents of the present invention is given birth to the passivator of white rust, it is reasonable, with low cost to fill a prescription, and does not contain hexavalent chromium compound in the composition, and the working space does not have the volatile matter of insoluble chromic salt,, environmentally safe harmless to human body when therefore passivator uses meets requirements of green environmental protection.
(2) method of hot dip galvanizing steel strand surface white rust that prevents of the present invention is compared with prior art, technology is simple, low production cost, anti-white rust anti-corrosion capability is strong, can make the Stranded Galvanized Steel Wire coating surface obtain continuous, the fine and close gluey film that contains trivalent chromium zincate and Resins, epoxy composition, after drying is solidified, can significantly improve the erosion resistance ability of pot galvanize product, its rete is conventional single sexavalent chrome passivator or trivalent chromium, sulfuric acid, the formed chromate passivation film of the nitric acid mixing passivator corrosive power of anti-neutral salt spray the 15～25 times.
(3) passivator coating method of the present invention can directly utilization on hot dip galvanizing steel strand twisting, plying production line, and can be to the online Passivation Treatment of carrying out of steel-wire galvanizing, but continuous production process in twisting Stranded Galvanized Steel Wire production process.Therefore, this method passivation efficiency height, effective has solved the problem of the living white rust of hot dip galvanizing steel strand coating surface for a long time, and environmentally safe, has certain advanced level and economic implications.Therefore, this technology will have excellent generalization values and social benefit.
Four, description of drawings:
The anti-white rust of Fig. 1 Stranded Galvanized Steel Wire applies the synoptic diagram of passivator method.
Five, embodiment:
The invention will be further described below in conjunction with embodiment.
Embodiment one: the passivator and the coating method that prevent hot dip galvanizing steel strand surface white rust, referring to Fig. 1, utilize existing many galvanized steel wires to twist with the fingers the hot dip galvanizing steel strand that (closing) system forms through special-purpose stranding machine, cabling operation under the effect of H-wheel spooler pulling force, under the pressure effect of the arc groove Wirewinding roller of steel strand in the passivator groove, the passivator that dipping prepares in advance by regulating the distance between the cell body pop-up line roller, is regulated passivation time.Stranded Galvanized Steel Wire enters in the electrically heated drying baker subsequently, passivator oven dry with steel strand zinc coating surface adhesion, form the anti-white rust of one deck, corrosion resistant film, Stranded Galvanized Steel Wire rolling is subsequently finished the whole process of the online anti-white rust passivation continuous production process of steel strand on H-wheel.
1, prevents the device of the living white rust of hot galvanized layer, comprise passivation device and drying unit two portions.
The passivation device: be made into the cell body that is of a size of long 1500mm * wide 1000mm * high 500mm with the PPH plate, on cell body diameter being installed is the Wirewinding roller that 400mm has arc groove, and two holder line rollers are installed at the cell body two ends, and distance can be adjusted between the two holder line rollers;
Drying unit: adopt drying baker, be of a size of long 1000 * wide by 1000 * high by 300 (mm); Heating can adopt electricity or other modes to heat.When adopting resistive heating, it is the electric heating panel of 300KW that heating source can adopt power.
2, the preparation of passivator: get A, B component and deionized water, in (Wt%) A: B: deionized water is 1: 3～5: 16 ratio preparation, fully stirs the back and uses.
A component wherein: the weight ratio of water soluble acrylic acid epoxy ester resin and deionized water is 2.5: 1;
The B component: chromium chloride 5.0g/L, sulfuric acid 0.6g/L, acetic acid 2.5ml/L and surplus deionized water, B component pH value is 1.5～2.0;
Wherein used water soluble acrylic acid epoxy ester resin is the YD-600A type, and outward appearance is oil-in-water type milk sap, wherein self-emulsification solid part (.%) 40 ± 1, viscosity (being coated with-4 glasss) .S 〉=20, and its main component is epoxy and acrylic resin; Used sulfuric acid is the vitriol oil of massfraction 98.3%; Used acetic acid is common acetate, contains pure acetate 36% approximately, density 1.0492g/cm
3
Compound method: earlier deionized water is put into container, add A component and B component while stirring successively.For example, prepare 200kg passivator, add the 160kg deionized water in proportion earlier in container, add 10kg A component and 30kg B component while stirring successively, stir after finishing; Require passivator pH value between 2.0～2.8;
3, technological process:
Among Fig. 1, hot dip galvanizing steel strand 1 behind the twisting plying is continuous in having the Wirewinding roller 3 of arc groove under the tractive force effect by carrying roller 2, enter dipping passivator 4 in the passivator groove 6, hot dip galvanizing steel strand 1 is drawn through carrying roller 5 then, enter drying baker 7 oven dry, hot dip galvanizing steel strand 1 on H-wheel, is finished the continuous production process process of the online anti-white rust passivation of hot dip galvanizing steel strand by rolling subsequently.
Adopt JHL circulating filtration machine equipment in the production, periodic filtering is removed the impurity in the passivator solution.
Other processing parameters: the use temperature of passivator remains on 35～37 ℃; The steel strand cabling is through in the anti-white rust passivator groove process, and keeping passivator pH value is 2.0～2.8, passivation time 3～5s; The bake out temperature of hot dip galvanizing steel strand is controlled between 100～120 ℃.
Embodiment two, no longer repeat with embodiment one something in common, difference is:
Passivator formula: A, B and deionized water are 1: 3: 16;
A component wherein: the weight ratio of water soluble acrylic acid epoxy ester resin and deionized water is 2: 1, the B component: chromium chloride 4.0g/L, sulfuric acid 0.6g/L, acetic acid 2.5ml/L and surplus deionized water.
Embodiment three, no longer repeat with embodiment one something in common, difference is:
Passivator formula: A, B and deionized water are 1: 3: 16;
A component wherein: the weight ratio of water soluble acrylic acid epoxy ester resin and deionized water is 2.5: 1, and the B component is made up of chromium chloride 5.0g/L, sulfuric acid 0.6g/L, acetic acid 2.5ml/L and surplus deionized water.
Embodiment four, no longer repeat with embodiment one something in common, difference is:
The prescription of passivator: A, B and deionized water are 1: 3: 16;
A component wherein: the weight ratio of water soluble acrylic acid epoxy ester resin and deionized water is 3: 1, and the B component is made up of chromium chloride 6.0g/L, sulfuric acid 0.6g/L, acetic acid 2.5ml/L and surplus deionized water.
Embodiment five, no longer repeat with embodiment one something in common, difference is:
The prescription of passivator: A, B and deionized water are 1: 4: 16;
A component wherein: the weight ratio of water soluble acrylic acid epoxy ester resin and deionized water is 2.5: 1, and the B component is made up of chromium chloride 5.0g/L, sulfuric acid 0.6g/L, acetic acid 2.5ml/L and surplus deionized water.
Embodiment six, no longer repeat with embodiment one something in common, difference is:
The prescription of passivator: A, B and deionized water are 1: 4: 16;
A component wherein: the weight ratio of water soluble acrylic acid epoxy ester resin and deionized water is 2.2: 1, and the B component is made up of chromium chloride 5.0g/L, sulfuric acid 0.6g/L, acetic acid 2.5ml/L and surplus deionized water.
Embodiment seven, no longer repeat with embodiment one something in common, difference is:
The prescription of passivator: A, B and deionized water are 1: 5: 16;
A component wherein: the weight ratio of water soluble acrylic acid epoxy ester resin and deionized water is 2.7: 1, and the B component is made up of chromium chloride 4.5g/L, sulfuric acid 0.6g/L, acetic acid 2.5ml/L and surplus deionized water.
Embodiment eight, no longer repeat with embodiment one something in common, difference is:
The prescription of passivator: A, B and deionized water are 1: 5: 16;
A component wherein: the weight ratio of water soluble acrylic acid epoxy ester resin and deionized water is 3: 1, and the B component is made up of chromium chloride 5.0g/L, sulfuric acid 0.6g/L, acetic acid 2.5ml/L and surplus deionized water.
Claims (9)
1. passivator that prevents the hot dip galvanizing steel strand white rust is characterized in that: this passivator is pressed A, B component and 1: 3～5: 16 weight ratio of deionized water and is mixed and form; Described A component is pressed the weight ratio of water soluble acrylic acid epoxy ester resin and deionized water 2～3: 1 and is formed; Described B component is made up of chromium chloride 4.0～6.0g/L, sulfuric acid 0.6g/L, acetic acid 2.5ml/L and surplus deionized water.
2. passivator according to claim 1 is characterized in that: described passivator pH value is 2.0～2.8.
3. passivator according to claim 2 is characterized in that: described B component pH value is 1.5～2.0.
4. method that applies hot dip galvanizing steel strand with the described passivator of claim 1, it is characterized in that: add passivator (4) in the passivator groove (6) earlier, hot dip galvanizing steel strand (1) is continuous in having the Wirewinding roller (3) of arc groove under the tractive force effect by carrying roller (2), enter dipping passivator (4) in the passivator groove (6), hot dip galvanizing steel strand (1) is drawn through carrying roller (5) then, enter drying baker (7) oven dry, hot dip galvanizing steel strand (1) on H-wheel, is finished the continuous production process process of the online anti-white rust passivation of hot dip galvanizing steel strand by rolling subsequently.
5. passivator according to claim 4 applies the method for hot dip galvanizing steel strand, and it is characterized in that: the dipping time of described steel strand (1) in passivator (4) is 3～5 seconds, and described bake out temperature is 100～120 ℃.
6. passivator according to claim 5 applies the method for hot dip galvanizing steel strand, it is characterized in that: described passivator groove (6) is made for the acid corrosion-resistant material, and cell body is of a size of long 1500mm * wide 1000mm * high 500mm; Described Wirewinding roller (3) diameter is 400mm.
7. passivator according to claim 4 applies the method for hot dip galvanizing steel strand, and it is characterized in that: described drying baker (7) is of a size of long 1000mm * wide 1000mm * high 300mm, and the power of heat source of drying baker (7) is the electric heating panel of 300KW.
8. passivator according to claim 4 applies the method for hot dip galvanizing steel strand, and it is characterized in that: described B component pH value is 1.5～2.0.
9. apply the method for hot dip galvanizing steel strand according to each described passivator of claim 4-8, it is characterized in that: described passivator temperature is 35～37 ℃, and passivator pH value is 2.0～2.8.
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|---|---|---|---|
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|---|---|---|---|
| CN2009100642962A CN101487118B (en) | 2009-02-27 | 2009-02-27 | Passivation agent for preventing hot dip galvanizing steel strand surface white rust and coating method |
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| CN108796584B (en) * | 2017-04-28 | 2020-08-25 | 宝山钢铁股份有限公司 | Flexible control method for surface passivation film structure of tinned product |
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