CN106661708B - The manufacturing method and galvanizing by dipping steel of galvanizing by dipping steel - Google Patents
The manufacturing method and galvanizing by dipping steel of galvanizing by dipping steel Download PDFInfo
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- CN106661708B CN106661708B CN201580041381.0A CN201580041381A CN106661708B CN 106661708 B CN106661708 B CN 106661708B CN 201580041381 A CN201580041381 A CN 201580041381A CN 106661708 B CN106661708 B CN 106661708B
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- steel
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- solder flux
- dipping
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 174
- 239000010959 steel Substances 0.000 title claims abstract description 174
- 238000007598 dipping method Methods 0.000 title claims abstract description 116
- 238000005246 galvanizing Methods 0.000 title claims abstract description 109
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 230000004907 flux Effects 0.000 claims abstract description 137
- 229910000679 solder Inorganic materials 0.000 claims abstract description 129
- 238000007747 plating Methods 0.000 claims abstract description 77
- 239000011701 zinc Substances 0.000 claims abstract description 75
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 68
- 238000012545 processing Methods 0.000 claims abstract description 33
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 15
- 238000005470 impregnation Methods 0.000 claims abstract description 9
- 229910052745 lead Inorganic materials 0.000 claims abstract description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 64
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 60
- 238000001035 drying Methods 0.000 claims description 49
- 239000007788 liquid Substances 0.000 claims description 46
- 235000019270 ammonium chloride Nutrition 0.000 claims description 32
- 239000011592 zinc chloride Substances 0.000 claims description 31
- 235000005074 zinc chloride Nutrition 0.000 claims description 31
- 239000012298 atmosphere Substances 0.000 claims description 25
- 238000005660 chlorination reaction Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 238000000034 method Methods 0.000 description 37
- 230000000694 effects Effects 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 238000005554 pickling Methods 0.000 description 16
- 239000000523 sample Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 10
- 239000011247 coating layer Substances 0.000 description 9
- 239000002893 slag Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910001335 Galvanized steel Inorganic materials 0.000 description 8
- 239000008397 galvanized steel Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 229910000905 alloy phase Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000003287 bathing Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940070259 deflux Drugs 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- -1 that is Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/38—Wires; Tubes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating With Molten Metal (AREA)
Abstract
The manufacturing method and galvanizing by dipping steel of galvanizing by dipping steel good the purpose of the present invention is to provide the wetability to fused zinc and that not plating does not occur.The manufacturing method of the galvanizing by dipping steel, after being plated steel surface progress solder flux processing and being dried, steel will be plated and be impregnated in as at the plating bath progress galvanizing by dipping bath impregnation being grouped as containing Zn:97.5 mass % or more, Fe:1.5 mass % or less, Pb:0.10 mass % or less, Cd:0.01 mass % or less, the Mg:0.001 mass mass of %~0.05 %.
Description
Technical field
The present invention relates to galvanizing by dipping steel (hot dip galvanized steel) and its manufacturing methods.More particularly to
It is limited using RoHS instruction (RoHSdirective, Restriction of Hazardous Substances Directive)
In the range of system, Pb content is 0.10 mass % or less, Cd content is 0.01 mass % galvanizing by dipping bath (hot below
Dip galvanizing bath) when, the manufacturing method and galvanizing by dipping steel of the few galvanizing by dipping steel of plating defect.
Background technique
In recent years, European Union, which has implemented, instructs motor electronics limitation using the RoHS of special harmful substance.It should
The containing ratio of Pb in object product is limited in 0.10 mass % hereinafter, the containing ratio of Cd is limited in 0.01 matter by RoHS instruction
Measure % or less.Although RoHS instruction is the regulation other than Japan, corresponding international regulation can supply inhibition containing to ring
Border harmful substance, necessary is being become to the better product of environment, it is believed that the product containing a large amount of Pb or Cd will be kept away in future
Exempt to be trend.
However, still have the zinc coat of many galvanizing by dipping products contain have more than RoHS instruct limited value Pb and
Cd.The Pb and Cd is originated from the impurity in the galvanizing by dipping bath as plating raw material.On the other hand, the Pb in galvanizing by dipping bath is produced
Raw improve wants the steel surface (being plated steel surface) of plating to the effect of the wetability of fused zinc.Even if for example making as a result,
The uncleanly situation of steel surface to be plated material in the case where having oxide film thereon (oxide layer), is easily formed
Zinc coat (galvanizing layer).
Therefore, it when carrying out galvanizing by dipping using the extremely low galvanizing by dipping bath of Pb concentration, generates sometimes and does not form zinc coat
Part.This phenomenon that phenomenon be commonly referred to as not plating (unplating), be galvanizing by dipping bath in Pb concentration reduce and it is significant
The undesirable phenomenon occurred.
So-called " batch hot-dip (ど ぶ stain け め っ I) " (batch- that the steel such as steel pipe, steel structure object are carried out
Type hot dip galvanizing) it is different from the galvanizing by dipping processing carried out to sheet metal.The hot dipping that sheet metal is carried out
Zinc-plated processing is that the organic matter of removing surface of steel plate is continuously impregnated in galvanizing by dipping bath in a reducing atmosphere.That is, by making to melt
Zinc is contacted with the surface of very cleaning and the steel plate of active high state, is formed thinly zinc coat in surface of steel plate.Due to
It in reducing atmosphere, also swims certainly in galvanizing by dipping bath almost without zinc oxide etc., to be not easy attachment oxidation in surface of steel plate
Zinc etc. hinders the state of the substance of plating to handle steel plate.In addition, having heating also to control alloy phase (alloy phase)
Growth the case where.In contrast, the galvanizing by dipping processing that steel carry out usually is carried out under atmosphere opening.Therefore, in order to
The oxidation on the surface of steel is prevented, and obtains the removing effect to the dirt on the surface of steel, implements weldering to steel are plated
After agent processing, the dipping in plating bath is carried out.In addition, carrying out the oil etc. on the surface for removing steel before solder flux processing
The pickling processes of dirt carry out ungrease treatment also according to situation before pickling processes.But status be such as steel pipe and steel plate not
Together, complex-shaped, therefore its effect is very insufficient.In addition, alloy phase is formed in galvanizing by dipping bath dipping, from galvanizing by dipping
By the thickness of wiping control dip galvanized after proposing in bath, followed by air is cooling or warm water is cooling.Therefore, feature
It is, the thickness of zinc coat is also from several 10 μm to several 100 μm or more, and compared with the zinc coat of steel plate, thickness is thicker.
In this way, for the batch type plating of the continous way plating of steel plate and steel, technique and resulting zinc coat
Structure is different greatly.That is, the batch type plating of steel is substantially to be easy to happen the undesirable technique of plating, project also with steel plate
Continous way plating it is different.For example, about above-mentioned not plating, even if in the case where using the extremely low galvanizing by dipping bath of Pb concentration,
Problem will not occur in the continous way plating of steel plate, in contrast, be easy to happen not in the batch type plating of steel
The trend of plating.
As the technology improved to the wetability (wetability) of fused zinc, such as patent document 1 can be enumerated.Patent text
It offers and is disclosed in 1 by containing weight %, Al:0.001 of Ni:0.01~0.05~0.01 weight in the zinc bath without containing Pb
% is measured, further containing one or more of the weight of Bi:0.01~0.08 weight of % and In:0.05~0.1 %, to improve zinc
The mobility of bath.In addition, disclosed in patent document 2~6 even if for by Pb content control in 0.1 mass % fused zinc below
Bath contains micro Sn, Bi, Sb etc. in fused zinc bath, can also manufacture few hot-dip galvanized material that not plating occurs.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2006-307316 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2009-221601 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2009-221604 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2009-197328 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2011-26630 bulletin
Patent document 6: Japanese Unexamined Patent Publication 2009-221605 bulletin
Summary of the invention
However, the inventors of the present invention verify patent document 1, as a result, it has been found that if not containing Bi:0.3 weight % with
On, then same wetability when being unable to get with containing Pb.In addition, the micro amount containing element is extremely for patent document 2~6
It is less 0.1 mass %, in order to further obtain effect, the micro content needed when independent containing element greater than 0.1 mass %, or
Person need it is compound containing.Accordingly, there exist cause goods cost to rise due to the element as contain.
The present invention is to carry out in order to solve the above problems, and its purpose is to provide the manufacturing methods of galvanizing by dipping steel
With galvanizing by dipping steel, Pb the and Cd concentration that the manufacturing method of the galvanizing by dipping steel contains in galvanizing by dipping bath is extremely low
In the case of, or without in the case where Pb and Cd, it is also excellent to the wetability of fused zinc, therefore can be in the feelings that not plating does not occur
The good coating layer of quality is formed under condition.
The inventors of the present invention are conceived to the solder flux treatment process in galvanizing by dipping processing, at drying to reach the above subject
Science and engineering sequence and galvanizing by dipping bathe impregnation process.Solder flux processing is for being cleaned in galvanizing by dipping is handled by pickling
Steel surface protected in order to avoid being reoxidized, and remove the process of remaining oxide, dirt in plating.Solder flux is dry
Process is to keep the solder flux liquid for being attached to steel surface dry, and in the process of the fixed solder flux of steel surface, plating process is by steel
It is impregnated in the process that fused zinc bath carries out plating to steel surface.It should be noted that the galvanizing by dipping processing in the present invention refers to pair
So-called " the batch hot-dip " that the steel of steel pipe, steel structure object etc. carry out is handled with the galvanizing by dipping carried out to sheet metal
It is different.
In solder flux processing, the solder flux used in the past is the double salt (double salt) or mixture of zinc chloride and ammonium chloride.
It is right when using the solder flux being made of previous two kinds of chlorides in distilled zinc (distilled zinc) plating bath containing Pb
The wetability of fused zinc sufficiently improves.However, for electrolytic zinc (electrolytic zinc) plating bath for being free of Pb, wetting
Property is very poor.Therefore, in the present invention, in order to improve wetability, probe has been carried out to the galvanizing by dipping situation of actual steel
Research.
It should be noted that distilled zinc mentioned here refers to distillation a kind of (JIS of zinc ingot metal specified in JIS H2107 (1999)
Class 1distilled zinc ingot), the Pb of 0.3~1.3 mass %, the Cd of 0.1~0.4 mass % are usually contained, electricity
Solution zinc refers to most pure zinc ingot (special high grade zinc ingot) as defined in JIS H2107 (1999), is usual Pb
It is 0.002 mass % electrolytic zinc below for 0.003 mass % or less, Cd.In addition, as shown in JIS H8641 (2007), to each
Plating bath is managed in the mode for maintaining the purity of the zinc in coating operations to be 97.5 mass % or more.
The inventors of the present invention study wetability, as a result, it has been found that, the generation for not plating, it is important that attached in solder flux
Whether good and few in the solder flux adhesion amount region of wetability in the few region of amount, by containing in galvanizing by dipping is bathed
Mg, Ti, V can be improved the wetability for being plated steel to fused zinc.In addition discovery steel are from solder flux processing via drying process
During being impregnated in galvanizing by dipping bath, the solder flux for facilitating wetability is gradually degraded, and has found the degradation inhibiting minimum
The manufacturing condition of limit.
It is established especially in the case where being bathed using the poor fused zinc of Pb, can not be sent out according to the above research
The manufacturing method of the raw not galvanizing by dipping steel of the excellent surface quality of plating.
The present invention is further to be studied and completed based on the above opinion.Its purport is as follows.
[1] a kind of manufacturing method of galvanizing by dipping steel carries out solder flux processing and drying process to steel surface is plated
Afterwards, steel will be plated and be impregnated in plating bath (galvanizing bath) progress galvanizing by dipping bath impregnation, the plating bath
As at being grouped as, contain Zn:97.5 mass % or more, Fe:1.5 mass % or less, Pb:0.10 mass % or less, Cd:0.01
Quality % or less, the Mg:0.001 mass mass of %~0.05 %.
[2] according to the manufacturing method for the galvanizing by dipping steel recorded in [1], wherein in above-mentioned plating bath at being grouped as
In, further containing a kind in Ti:0.001 mass mass %, the V:0.001 mass mass of %~0.05 of %~0.05 %
Or 2 kinds.
[3] manufacturing method for the galvanizing by dipping steel recorded according to [1] or [2], wherein in above-mentioned plating bath at grouping
Cheng Zhong further contains Al:0.001 mass %~0.02 mass %, further satisfaction ([Mg]+[Ti]+[V])/2 >=[Al]
(wherein, [Mg], [Ti], [V], the content that [Al] is each element.).
[4] manufacturing method for the galvanizing by dipping steel recorded according to any one of [1]~[3], wherein at above-mentioned solder flux
In reason, the molar ratio of the zinc chloride and ammonium chloride that contain in solder flux liquid is 1:1~1:4, the above-mentioned zinc chloride contained in solder flux liquid
Total molar concentration with above-mentioned ammonium chloride is 3~10mol/L, and above-mentioned chlorination zinc concentration is 600g/L hereinafter, on and
The temperature for stating solder flux liquid is 40 DEG C~85 DEG C.
[5] manufacturing method for the galvanizing by dipping steel recorded according to any one of [1]~[4], wherein at above-mentioned solder flux
When being dried after reason, meet following formula (1).
FE=9.6 × exp (- 2500/T) × RH × t0.5≤0.85…(1)
In above-mentioned formula (1),
T: solder flux treated be plated steel after flux bath comes out until entering drying oven the atmosphere be detained
Environment temperature (K)
RH: solder flux treated be plated steel after flux bath comes out until entering drying oven the atmosphere be detained
Envionmental humidity (%)
T: solder flux treated be plated steel from flux bath come out after to enter drying oven until residence time (point
Clock).
[6] manufacturing method for the galvanizing by dipping steel recorded according to any one of [1]~[5], wherein at above-mentioned drying
In reason, the temperature of dry furnace atmosphere is 180 DEG C hereinafter, the dew-point temperature of dry furnace atmosphere is (into the steel of drying oven
Surface temperature -10) DEG C hereinafter, the maximum temperature reached of steel surface when dry is the drying of 80 DEG C~140 DEG C and steel
The residence time is 600 seconds or less in furnace.
[7] a kind of galvanizing by dipping steel are the manufacturing methods for the galvanizing by dipping steel recorded by any one of [1]~[6]
It is fabricated.
According to the present invention, it even if in the case that the Pb concentration contained in galvanizing by dipping bath is extremely low, is also capable of providing and does not send out
The manufacturing method and galvanizing by dipping steel of the raw not galvanizing by dipping steel of plating.
Detailed description of the invention
Fig. 1 is the figure for indicating the relationship of mole fraction and contact angle of ammonium chloride.
Specific embodiment
In general, being handled by pickling processes, solder flux " batch hot-dip " processing based on fused zinc that steel carry out, being dry
Processing, the sequence progress of galvanizing by dipping bath dipping.Also there is the case where ungrease treatment is carried out before pickling processes.In addition, also having
After ungrease treatment, pickling processes, as needed the case where progress washing step.Here, solder flux processing refers to for being covered with solder flux
Steel surface after lid pickling inhibits oxidation, and by the solder flux decomposition when galvanizing by dipping is bathed and impregnated that steel surface is clear
Clean promotes the processing of the formation of zinc coat.In order to make solder flux be attached to steel surface, production makes solder flux be dissolved in the water-soluble of water
Liquid, that is, solder flux liquid, is impregnated in steel in solder flux liquid, or solder flux liquid is directly applied to steel surface.Hot-dip of the invention
The manufacturing method of zinc steel is as principle also in compliance with the process content and sequence.Moreover, in galvanizing by dipping steel of the invention
Technical feature described below is further added in manufacturing method.
Be impregnated in it is a feature of the present invention that steel will be plated as at being grouped as, containing Zn:97.5 mass % with
Upper, Fe:1.5 mass % or less, Pb:0.10 mass % or less, Cd:0.01 mass % or less, Mg:0.001 mass %~0.05
The plating bath of quality % carries out galvanizing by dipping and bathes impregnation.Hereinafter, limitation of the invention reason is illustrated.It should say
It is bright, hereinafter, quality % is also abbreviated as %.
Pb:0.10 mass % or less, Cd:0.01 mass % or less
Ingredient for the plating bath in the present invention, as the galvanizing by dipping bath for being plated steel that dipping is handled through solder flux
Composition, Pb and Cd limited for RoHS instruction in the range of, contain Pb:0.10 mass % or less, Cd:0.01 mass % with
Under.Wherein, as described above, when using most pure zinc ingot specified in JIS H2107 (1999), usual Pb be 0.003 mass % with
Under, Cd be 0.002 mass % hereinafter, even if for such low concentration or detection limit hereinafter, absolutely not influence.
The Mg:0.001 mass mass of %~0.05 %
It is a feature of the present invention that containing Mg in plating bath.The inventors of the present invention are first to the steel pair for being attached with solder flux
The wetability of galvanizing by dipping bath is investigated.Specifically, assembling is also used for the Wilhelmy method of the wettability evaluation of solder
The experimental provision of (flat band method) is tested with aftermentioned method.Wilhelmy method is to be impregnated the sample of plate by measuring
Weight (quality) when liquid certain depth can acquire its contact under the situation known to the density of liquid, surface tension
One of the method at angle.It tests as follows: as the sample for evaluating to the wetability of fused zinc, with resistance weld pipe (electric
Resistance welded tube) raw sheet processes smooth surface and sheet metal (50 × 20mm with a thickness of 0.5mm.Hereinafter,
The also referred to as sample in the explanation of wetting sex investigation), carry out degreasing, pickling, after washing, be impregnated in change concentration by chlorination
In the solder flux liquid that zinc and ammonium chloride are constituted, lifts and dry.Thereafter, sample is hung on to the state of electronic balance, it will be away from sample
Product lower end 10mm is impregnated into galvanizing bath 20 seconds, records weight therebetween.The weight during impregnating 20 seconds of a certain amount of sample
Amount changes (sample surfaces in bath face are oxidized and form iron oxide, therefore are difficult to soak gradually), therefore by showing most
The maximum weight value soaked greatly calculates minimal contact angle (specifically, acquiring according to γ × L × cos θ=F+S × h × ρ × g.
Here, γ: surface tension, L: the perimeter of solid sample, θ: contact angle, F: measurement power (power for acting on sample), F=(measurement
Weight-sample weight) × g, S: the sectional area of sample, h: the dipping distance of sample, ρ: the density of liquid (fused zinc), g: gravity
Acceleration).When usual contact angle is 90 degree or less, for the state of wetting, it is believed that wetability is good.It should be noted that distilled zinc and
Electrolytic zinc uses electrolytic zinc A and distilled zinc shown in table 1 respectively.
As a result, think that solder flux is sufficiently adhering to the state of steel, specifically solder flux concentration used in solder flux processing,
That is, when total molar concentration of zinc chloride contained in solder flux liquid and ammonium chloride is 3mol/L or more, the electrolytic zinc without Pb
Bath, the distilled zinc bath containing Pb show sufficient wetability.On the other hand, it is believed that solder flux is not sufficiently adhering to steel, weldering
When total molar concentration of zinc chloride contained in agent liquid and ammonium chloride is 1mol/L or less, in electrolytic zinc bath and distilled zinc bath
In its behavior it is different, wetability sharply deteriorates in electrolytic zinc bath.The difference of wetability when suggesting solder flux adhesion amount less causes
Plating does not have a difference in electrolytic zinc bath and distilled zinc bath in actually manufacture.Therefore, to from fluxless processing to weldering
Total molar concentration 1mol/L of the zinc chloride and ammonium chloride that contain in agent liquid, sample that solder flux does not adhere to sufficiently are to hot dipping
The wetability of zinc-plated bath makes further research, and wetability is improved when as a result containing Mg in plating bath.In turn, by containing
There are aftermentioned Ti, V also to improve wetability.
In the present invention, Mg is element easy to oxidize compared with Zn, FeI, by covering melting with relatively thin oxide film thereon
Zinc bath surface, thus show inhibit Zn oxide generate barriering effect, and may also suppress steel plate be impregnated in zinc bath when
Surface of steel plate oxidation, it is ensured that wetability.When the content of Mg is less than 0.001 mass %, specific effect can't see, even if containing
Have and is also saturated more than 0.05 mass % effect.Therefore, Mg is defined in the range of 0.001 mass of mass %~0.05 %.
In the present invention, for the purpose for improving wetability, in can further containing in being grouped as above-mentioned plating bath
1 kind in Ti or V or 2 kinds.
The Ti:0.001 mass mass of %~0.05 %
Ti improves the wetability for being plated steel and bathing to galvanizing by dipping that solder flux does not adhere to sufficiently.Ti is compared with Zn, Fe
Element easy to oxidize, the oxidation of surface of steel plate when steel plate being inhibited to be impregnated in galvanizing by dipping bath, it is ensured that wetability.But such as
Fruit individually contains in galvanizing by dipping bath, then forms oxide film thereon (oxide layer) on galvanizing by dipping bath surface, the oxidation quilt
Film is with time continued growth.Therefore, the present invention in show barriering effect Mg it is compound containing.The content of Ti is less than 0.001
When quality %, specific effect can't see, even if containing 0.05 mass % is greater than, effect is also saturated.Therefore, preferably 0.001 Ti
The range of the mass of quality %~0.05 %.
The V:0.001 mass mass of %~0.05 %
V improves the wetability for being plated steel and bathing to galvanizing by dipping that solder flux does not adhere to sufficiently.V is to hold compared with Zn, Fe
Oxidizable element, the oxidation of surface of steel plate when steel plate being inhibited to be impregnated in galvanizing by dipping bath, it is ensured that wetability.But if
Individually contain in galvanizing by dipping bath, then forms oxide film thereon on galvanizing by dipping bath surface, which continues with the time
Growth.Therefore, the present invention in display barriering effect Mg it is compound containing.It can't see when the content of V is less than 0.001 mass % bright
True effect, even if containing 0.05 mass % is greater than, effect is also saturated.Therefore, V preferably 0.001 mass of mass %~0.05 %
Range.
In the present invention, for the purpose for improving plating appearance, it can further contain Al in above-mentioned plating bath composition.
The Al:0.001 mass mass % of %~0.02, and meet ([Mg]+[Ti]+[V])/2 >=[Al] (wherein, [Mg],
[Ti], [V] are the content of each element.)
Although Al does not improve the effect for being plated the wetability that steel bathe galvanizing by dipping that solder flux does not adhere to sufficiently,
Al assigns gloss to the surface of coating layer, therefore is improved the effect for having glossiness plating appearance.In addition, Al and Zn, Fe phase
Than being element easy to oxidize, by covering the surface of galvanizing by dipping bath with thin oxide film thereon, display inhibits the oxide of Zn
The barriering effect of generation.But Al is the element strong with Fe associativity, it is a large amount of containing hindering the alloys of Fe and Zn mutually to grow sometimes and
The reason of as not plating.It can't see specific gloss when the content of Al is less than 0.001 mass % and assign effect, even if containing big
In 0.02 mass %, effect is also saturated.When in turn, containing the half of total content for having more than Mg, Ti and V, it may hinder
Wetability improvement.According to the above, being set as the range of 0.001 mass of mass %~0.02 %, and meet when containing Al
([Mg]+[Ti]+[V])/2 >=[Al] (wherein, [Mg], [Ti], [V], the content that [Al] is each element.).It should be noted that being free of
When having Ti, calculated as [Ti]=0.When without containing V and Al, [V] and [Al] is similarly operated.
In plating bath, as galvanizing by dipping bath at being grouped as, in addition to it is above-mentioned containing element other than, contain JIS defined
Zn:97.5 mass % or more, Fe:1.5 mass % or less and inevitable impurity.About Fe, by the plating for continuing steel
It covers, the Fe amount being dissolved in galvanizing by dipping bath increases.Fe amount more than 0.1 mass % means Fe-Zn alloy (so-called bottom
Slag) swim, preferably by Fe amount control below 0.1 mass %.
In the present invention, as long as being the plating bath of above-mentioned composition, it can obtain not plating not containing other elements
The good galvanizing by dipping steel covered.It should be noted that for the purpose for obtaining ensuring the characteristic other than wetability, it can be according to need
To contain one kind or two or more in Sb, Bi, Sn, Ni, Cu, Si etc..
In the present invention, galvanizing by dipping bath impregnation is carried out using the galvanizing by dipping bath formed with mentioned component.
Each condition of galvanizing by dipping bath impregnation other than plating bath can carry out by known method.In turn, this hair
It, being capable of plating most pure zinc ingot below using Pb:0.003 mass % or less, Cd:0.002 mass % in bright.
From the viewpoint of stablizing manufacture and quality, the temperature of plating bath is preferably 440~470 DEG C.This is because being less than
At 440 DEG C, because plating bath caused by temperature variation solidification a possibility that get higher；In addition, then iron-zinc closes if it exceeds 470 DEG C
The growth of metallographic becomes faster, and coating layer becomes fragile, and plated thickness becomes difficult to control.
It, can be to being plated steel in addition, when will be plated steel after plating bath dipping and lift from plating bath, or after lifting
Material blows the adjustment plating adhesion amount such as attached air or steam.As long as carrying out cooling by the way that warm water cooling or air are cooling thereafter.
Next, to galvanizing by dipping treatment process, (pickling processes solder flux processing, are dried, at galvanizing by dipping bath dipping
Reason) in above-mentioned galvanizing by dipping bath impregnation other than each condition be illustrated.
Pickling processes
As pickling processes, the known method of the pickling processes as steel can be used.Contain for example, can be impregnated in
There is the method to fall off etc. in the aqueous hydrochloric acid solution of inhibitor until confirming the oxide skin of steel surface by visual observation.At pickling
The preceding process of reason can according to need and carry out degreasing process and washing step.
Solder flux processing
In the present invention, the molar ratio of the zinc chloride and ammonium chloride that preferably contain in solder flux liquid is 1:1~1:4, in solder flux liquid
The total of the molal quantity of the above-mentioned zinc chloride and above-mentioned ammonium chloride that contain is calculated as 3mol/L~10mol/L with molar concentration, above-mentioned
Chlorination zinc concentration be 600g/L hereinafter, and the temperature of above-mentioned solder flux liquid is 40 DEG C~85 DEG C, carry out solder flux processing.
Galvanizing by dipping is the double salt or mixture of zinc chloride and ammonium chloride with solder flux.Zinc chloride mitigate in actual operation by
The decomposition of thermally-induced ammonium chloride disappears, and extends the effective time of solder flux.In addition, ammonium chloride is cleaning more to steel surface
Effective substance.Therefore, when the substance of either one is few, it is likely to make the effect that cleans of steel surface to be significantly damaged.
The inventors of the present invention in solder flux liquid the ratio of zinc chloride and ammonium chloride and the relationship of wetability investigated.Tool
For body, using Wilhelmy method (flat band method), concentration is set as to 3mol/L is constant, acquires and changes zinc chloride and ammonium chloride
The minimal contact angle of the solder flux liquid of molar ratio.As a result, as shown in Figure 1, it is known that the zinc chloride of galvanizing by dipping solder flux and chlorination
The molar ratio (ratio recorded in Fig. 1) of ammonium is in zinc chloride: in the range of ammonium chloride=1:1~1:4, minimal contact angle is small, profit
It is moist excellent.For example, in Fig. 1, it is known that in the range that the ratio of zinc chloride and ammonium chloride is 1:1~1:4, minimal contact angle is special
It is small, about 55 ° or less (dotted portion), the particularly preferred range.Therefore, the zinc chloride of galvanizing by dipping solder flux and ammonium chloride
Molar ratio is preferably 1:1~1:4.
In addition, the concentration of solder flux liquid influences the adhesion amount of solder flux.In the present invention, the zinc chloride that preferably contains in solder flux liquid and
Total molar concentration of ammonium chloride is 3~10mol/L.As long as being 3mol/L, even if there is solder flux adhesion amount locally low part,
Also can not occur not carry out plating to plating.If the concentration of solder flux liquid is got higher, solder flux adhesion amount increases.On the other hand,
Even more than 10mol/L, adhesion amount is also saturated, and viscosity gets higher and is difficult to operate.Therefore, the concentration of solder flux liquid be preferably 3~
10mol/L.Since there are deviations, further preferably 5~10mol/L for the adhesion amount of solder flux.
From the viewpoint of wetability, the adhesion amount of solder flux the how the more preferred.Zinc chloride be in actual operation, mitigate because
The decomposition of ammonium chloride caused by heat disappears and extends the substance of the effective time of solder flux.But zinc chloride will not occur because of hot institute
The decomposition of cause, therefore the surface for eventually becoming zinc oxide and floating on fused zinc bath becomes top slag (top dross).The top slag is in steel
It is attached to steel surface when the fused zinc of material bathes dipping and when lifting, makes plating quality deterioration.In addition, the frequent removing of top slag
The main reason for as cost increase.Therefore, chlorination zinc concentration is preferably 600g/L or less.Further preferably 350g/L with
Under.
The solder flux that can be used in the present invention at least contains above-mentioned zinc chloride and ammonium chloride.In addition, instead of the chlorine of simple substance
The ammonium chloride for changing zinc and simple substance, can be used their double salt.In addition, zinc chloride and the total of ammonium chloride become principal component.
In turn, as long as not damaging effect of the invention, so that it may containing other chlorides, salt, water soluble compound and
The additives such as surfactant.Especially homogenize solder flux liquid to the adhesion amount of steel containing surfactant, therefore can the phase
The effect of solder flux to be saved, thus preferably.As the example of the surfactant in the present invention, anion surface active can be enumerated
Agent, cationic surfactant, amphoteric surfactant, nonionic surfactant etc..As the ingredient of solder flux, preferably make this
A little additives are 0 mass %, make above-mentioned zinc chloride, ammonium chloride and 100 matter of remainder as inevitable impurity
Measure %.
Solder flux adhesion amount in the present invention refers to the aggregate value of the zinc chloride and ammonium chloride that contain in solder flux, does not include other
Additive quality.
In the present invention, solder flux be sprayed with solution state, is coated with to the coating of steel surface, or is carried out in solder bath
In dipping after, spontaneously dry or force drying.In the present invention, the aqueous solution that above-mentioned solder flux can be dissolved in water is used as hot dipping
It is zinc-plated to use solder flux liquid.The usually water used in solder flux processing can be used in water as solvent.When carrying out dip coated, solder flux
It cannot get sufficient adhesion amount when the concentration of bath is too low, in addition, the viscosity of solder bath gets higher and occurs attached if excessive concentration
Bad, underdry.Therefore, the concentration of galvanizing by dipping solder bath of the invention can be suitable in the range for avoiding the above problem
Locality setting.
It is dried
In the present invention, when being dried after solder flux processing, following formula (1) is preferably satisfied.
FE=9.6 × exp (- 2500/T) × RH × t0.5≤0.85…(1)
In above-mentioned formula (1),
T: solder flux treated be plated steel from after flux bath comes out until entering drying oven between be detained
The environment temperature (K) of atmosphere
RH: solder flux treated be plated steel from after flux bath comes out until entering drying oven between be detained
The envionmental humidity (%) of atmosphere
T: solder flux treated be plated steel from flux bath come out after to enter drying oven until between residence time
(minute).
Solder flux is the substance for protecting steel surface not oxidized.However, since solder flux liquid contains ammonium chloride, liquid
Property display faintly acid, encourage the dissolution of steel, that is, iron point.Due to except the iron point dissolved out in deflux is also using solder flux, basis
From solder flux processing to the ambient condition of drying process, the deterioration of solder flux caused by the dissolution divided by iron is carried out.It is therefore preferable that welding
It is dry rapidly after agent processing.
FE value defined in above-mentioned formula (1) is to indicate the index of the deterioration condition of the solder flux, in the present invention, as long as FE value is
0.85 hereinafter, can be then bottom line by the degradation inhibiting of solder flux, and can obtain good plated steel material.
It should be noted that the drying in order to help solder flux liquid, carrying out heating to the solder flux liquid in flux bath is also effective side
Method.When heating solder flux liquid, from the viewpoint of the stability and heating cost that temperature is kept, the temperature of solder flux liquid is preferably 40 DEG C
~85 DEG C.
In addition, being dried is to evaporate the moisture in solder flux liquid after solder flux processing, it is formed uniformly surely in steel surface
The process of fixed solder flux envelope (flux layer).It is dry to be carried out for example in drying oven.If in not dry state
Lower long-time places steel, then steel surface dissolves out and deteriorates solder flux in solder flux liquid, solder flux can be hindered to act on.Also have dry
The example of burning waste gas, general atmosphere, the preferably dew point in control drying oven are imported in dry furnace and prevent from condensing.In addition, solder flux
When the temperature of liquid excessively rises or the residence time is too long, the dissolution of steel is carried out, if solder flux is opened when temperature is further got higher
Begin to decompose.Therefore, in the present invention, it is preferred to which atmosphere temperature is for 180 DEG C hereinafter, the dew point temperature of dry furnace atmosphere in drying oven
Degree is (into the steel surface temperature -10 of drying oven) DEG C hereinafter, the maximum temperature reached of steel surface when dry is 80 DEG C
The residence time is to be dried for 600 seconds or less in~140 DEG C and the drying oven of steel.
It is to inhibit the molten of solder flux that the temperature of the solder flux drying furnace atmosphere that treated is dried, which is 180 DEG C or less,
The dissolution of warm steel.In addition, the dew-point temperature of dry furnace atmosphere is set as (into the surface temperature-of the steel of drying oven
DEG C or less 10) it is the delay of the drying of solder flux in order to prevent, is efficiently dried.In addition, steel surface when dry is most
It is in order to sufficiently dry that it is that the residence time is 600 seconds or less in 80 DEG C~140 DEG C and the drying oven of steel that height, which reaches temperature,
While inhibit steel the amount of dissolution.When less than 80 DEG C, it is unable to fully drying, is easy to happen not plating.About the reason, although
It is still not clear, but is presumably due to remain the crystallization water in solder flux, and reduce and occur the moisture absorption of solder flux with temperature, it can not
It sufficiently keeps dry state, therefore steel surface dissolves, can not obtain solder flux therewith cleans effect.From the sight of heating cost
Point considers that the maximum temperature of steel when more preferably dry is 120 DEG C or less.
The manufacturing method of galvanizing by dipping steel more than utilization can obtain galvanizing by dipping steel of the invention.Obtained heat
The adhesion amount (coating weight) of the galvanizing by dipping of the steel surface of zinc immersion steel is preferably 300~700g/m2.Pass through
The adhesion amount of plating is set as 300g/m2More than, it can be ensured that sufficient corrosion resistance.On the other hand, more than 700g/m2Plating
The attachment covered becomes the main reason for cost increase, therefore is set as 700g/m2Below.In addition, from the viewpoint of environmental performance,
For each ingredient of the coating layer of steel surface, in terms of quality %, Zn and Fe's adds up to preferably each ingredient of dip galvanized
99.9% or more, Pb is 0.01% or less and Cd is 0.005% or less.
It should be noted that for steel (being plated steel) of the invention, as long as carry out to steel pipe, steel structure object etc. into
The steel of the galvanizing by dipping processing of capable so-called " batch hot-dip ", are just not particularly limited.But due to heat of the invention
Zinc immersion processing is different from the above-mentioned continous way galvanizing by dipping processing carried out to sheet metal (especially steel band), therefore sheet metal is not
As object.
Embodiment 1
Hereinafter, being illustrated based on the embodiment of steel pipe to galvanizing by dipping steel of the invention.It should be noted that the present invention is simultaneously
It is not limited to embodiment below.Below in an example, table 2-1 and table 2-2 are collectively referred to as table 2.
The manufacture of hot-dip galvanized steel pipe is carried out by process below.Steel pipe (125A, 5.5m long are plated to after degreasing
Degree, each 11 of every 1 condition) pickling is carried out, remove the casting skin (oxide film thereon of the steel tube surface formed when hot rolling on surface
(oxide layer)).Pickling solution is the 12 mass % aqueous hydrochloric acid solutions containing inhibitor, and liquid temperature is 30 DEG C, dip time 60
Minute.It after pickling, is washed, solder flux is handled, be dried and galvanizing by dipping bath impregnates.
Solder flux liquid is the aqueous solution of the mixture of zinc chloride and ammonium chloride, and the molar ratio of zinc chloride and ammonium chloride mainly uses
1:1.Total molar concentration of zinc chloride and ammonium chloride for containing in by change solder flux liquid shown in table 2, zinc oxide concentration, with
And lift after being impregnated steel pipe 30 seconds in the solder flux liquid of solder flux liquid temperature.
In addition, measurement steel pipe from flux bath come out after to enter drying oven time, the temperature of comprehensive drying furnace nearby and
The measurement result of relative humidity, formula (1) according to the present invention calculate FE value.
For being dried, the atmosphere temperature in drying oven, the dew point in drying oven, steel tube surface maximum temperature reached
It is as shown in table 2 with maximum surface temperature, in addition, into the steel tube surface temperature in drying oven be 35 DEG C.
Impregnation is bathed for galvanizing by dipping, plating bath, which is used, contains microelement in the electrolytic zinc without containing Pb and Cd
8 kinds of A~H and as conventional example distilled zinc.Chemical composition is shown in table 1.Plating bath temperature and dip time are 450
DEG C, 90 seconds or 470 DEG C, 150 seconds.It is bathed from galvanizing by dipping after lifting, extra fused zinc is removed by wiping, passes through water cooling
It is cooled down.
To the hot-dip galvanized steel pipe manufactured by above-mentioned condition, plating layer surface is observed in detail, to not the presence or absence of plating, is not plated
The average generation number covered, attachment based on top slag the surface texture of coating layer evaluated.Specifically, to above-mentioned item is pressed
It is bad to will confirm that the hot-dip galvanized steel pipe of 1 or more not plating is calculated as bad by hot-dip galvanized steel pipe 10 of part manufacture
Rate, fraction defective be more than 10% be denoted as it is unqualified.For each average generation number of not plating, 0 is denoted as-, 1~2
A to be denoted as △, 3~5 are denoted as, 6 or more be denoted as ×, × be unqualified.In addition, to the surface texture of coating layer, it is good to remember
Zero is denoted as ◎, slight coarse (roughness) being less than at φ 10mm and only 1 that adhere to for pushing up slag, it is seen that the φ more than at 1
The attachment of the top slag of 10mm or more sees that the coarse of moderate of the attachment of the top slag of φ more than at 2 less than 10mm is denoted as
△, push up slag attachment be φ 10mm or more just look at severe to more than at 10 it is coarse be denoted as ×.◎, zero, △ are denoted as qualification.It answers
Explanation is given, is tested when above-mentioned fraction defective is more than 10% (unqualified) without the surface texture of coating layer.
In addition, adhesion amount and dip galvanized to the galvanizing by dipping of the steel surface of obtained hot-dip galvanized steel pipe is each
Ingredient is measured.For the adhesion amount of galvanizing by dipping, the coating layer of the steel pipe cut out is dissolved and is removed, according to its area and again
Amount, which subtracts, to be calculated.Each ingredient of dip galvanized uses ICP emission spectrographic analysis by equally dissolution coating layer
(inductively-coupled plasma emission spectrometry) method acquires.
[table 1]
[table 2-1]
[table 2-2]
The not plating of the hot-dip galvanized steel pipe sample (No.3~8,10~30) of example occurs as 10% hereinafter, with making
It is qualification with the same comprehensive judgement of the conventional example (No.9) of distilled zinc.This means that by containing in plating bath of the invention
Mg, even if not plating does not occur yet for Mg, Pb concentration is extremely low, the condition of not plating occurs in plating bath in comparative example,
Can in the same manner as the conventional example containing Pb plating.On the other hand, the hot-dip galvanized steel pipe sample (No.1,2) of comparative example is not
It is qualified.
Not plating, all qualifications do not occur or seldom occur for example of the present invention.On the other hand, it is known that comparative example is unqualified,
And related not plating is poor.
Industrial availability
As described above, according to the present invention, even if the situation that the Pb concentration contained in galvanizing by dipping bath is extremely low, can also use
The sufficiently excellent manufacturing method of wetability to fused zinc manufactures galvanizing by dipping steel.
Claims (10)
1. a kind of manufacturing method of galvanizing by dipping steel will after being plated steel surface progress solder flux processing and being dried
It is plated steel and is impregnated in plating bath and carry out galvanizing by dipping bath impregnation, the plating bath is used as at being grouped as containing Zn:
97.5 mass % or more, Fe:1.5 mass % or less, Pb:0.10 mass % or less, Cd:0.01 mass % or less, Mg:0.001
The mass of quality %~0.05 %, wherein
When being dried after solder flux processing, meet following formula (1),
FE=9.6 × exp (- 2500/T) × RH × t0.5≤0.85…(1)
In the formula (1),
T: treated is plated the environment of atmosphere that steel are detained until entering drying oven after flux bath comes out for solder flux
Temperature, unit K
RH: treated is plated steel in the ring of atmosphere being detained until entering drying oven after flux bath comes out for solder flux
Border relative humidity, unit %
T: residence time of solder flux treated the steel after flux bath comes out until entering drying oven, unit is minute.
2. the manufacturing method of galvanizing by dipping steel according to claim 1, wherein in the plating bath at being grouped as
In, further containing a kind in Ti:0.001 mass mass %, the V:0.001 mass mass of %~0.05 of %~0.05 %
Or 2 kinds.
3. the manufacturing method of galvanizing by dipping steel according to claim 1 or 2, wherein in the plating bath at grouping
Cheng Zhong, further contain Al:0.001 mass %~0.02 mass %, further satisfaction ([Mg]+[Ti]+[V])/2 >=[Al],
Wherein, [Mg], [Ti], [V], the content that [Al] is each element.
4. the manufacturing method of galvanizing by dipping steel according to claim 1 or 2, wherein in solder flux processing, solder flux
The molar ratio of the zinc chloride and ammonium chloride that contain in liquid is 1:1~1:4, the zinc chloride contained in solder flux liquid and the chlorination
Total molar concentration of ammonium is 3~10mol/L, and the chlorination zinc concentration is 600g/L hereinafter, and the solder flux liquid
Temperature is 40 DEG C~85 DEG C.
5. the manufacturing method of galvanizing by dipping steel according to claim 3, wherein in solder flux processing, solder flux liquid
In the molar ratio of zinc chloride and ammonium chloride that contains be 1:1~1:4, the zinc chloride and the ammonium chloride contained in solder flux liquid
Total molar concentration be 3~10mol/L, the chlorination zinc concentration be 600g/L hereinafter, and the solder flux liquid temperature
Degree is 40 DEG C~85 DEG C.
6. the manufacturing method of galvanizing by dipping steel according to claim 1 or 2, wherein dry in the drying process
The temperature of furnace atmosphere is 180 DEG C hereinafter, the dew-point temperature of dry furnace atmosphere is the steel surface temperature than entering drying oven
Low 10 DEG C of temperature is hereinafter, the maximum temperature reached of steel surface when dry is the drying oven of 80 DEG C~140 DEG C and steel
The interior residence time is 600 seconds or less.
7. the manufacturing method of galvanizing by dipping steel according to claim 3, wherein in the drying process, drying oven
The temperature of interior atmosphere is 180 DEG C hereinafter, the dew-point temperature of dry furnace atmosphere is lower than entering the steel surface temperature of drying oven
10 DEG C of temperature is hereinafter, the maximum temperature reached of steel surface when dry is in 80 DEG C~140 DEG C and the drying oven of steel
Residence time is 600 seconds or less.
8. the manufacturing method of galvanizing by dipping steel according to claim 4, wherein in the drying process, drying oven
The temperature of interior atmosphere is 180 DEG C hereinafter, the dew-point temperature of dry furnace atmosphere is lower than entering the steel surface temperature of drying oven
10 DEG C of temperature is hereinafter, the maximum temperature reached of steel surface when dry is in 80 DEG C~140 DEG C and the drying oven of steel
Residence time is 600 seconds or less.
9. the manufacturing method of galvanizing by dipping steel according to claim 5, wherein in the drying process, drying oven
The temperature of interior atmosphere is 180 DEG C hereinafter, the dew-point temperature of dry furnace atmosphere is lower than entering the steel surface temperature of drying oven
10 DEG C of temperature is hereinafter, the maximum temperature reached of steel surface when dry is in 80 DEG C~140 DEG C and the drying oven of steel
Residence time is 600 seconds or less.
10. a kind of galvanizing by dipping steel are by the manufacturing method of galvanizing by dipping steel according to any one of claims 1 to 9
It is fabricated.
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| JP2014156389 | 2014-07-31 | ||
| PCT/JP2015/003869 WO2016017186A1 (en) | 2014-07-31 | 2015-07-31 | Method for producing hot-dip galvanized steel material, and hot-dip galvanized steel material |
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| JP6769276B2 (en) * | 2016-12-08 | 2020-10-14 | 日本製鉄株式会社 | Manufacturing method of hot-dip galvanized steel pipe and hot-dip galvanized steel pipe |
| CN111094828B (en) * | 2017-09-26 | 2022-02-08 | 日立金属株式会社 | Method for producing black-cored malleable cast iron member formed by plating, and black-cored malleable cast iron member and pipe joint formed by plating |
| WO2019131562A1 (en) * | 2017-12-25 | 2019-07-04 | 日本製鉄株式会社 | Hot-dip galvanizing method, method of producing alloyed hot-dip galvanized steel sheet using hot-dip galvanizing method, and method of producing hot-dip galvanized steel sheet using hot-dip galvanizing method |
| JP7375809B2 (en) * | 2019-03-20 | 2023-11-08 | 株式会社プロテリアル | Method for manufacturing plated black core malleable cast iron member and plated black core malleable cast iron member |
| JP7252922B2 (en) * | 2019-08-19 | 2023-04-05 | Ｊｆｅスチール株式会社 | Flux solution for hot-dip galvanizing and method for manufacturing hot-dip galvanized steel pipe |
| JP7311767B2 (en) * | 2019-08-30 | 2023-07-20 | 日本製鉄株式会社 | FLUX AND METHOD FOR MANUFACTURING Zn-Al-Mg-BASED PLATED STEEL PRODUCT USING THE SAME |
| KR20240086470A (en) | 2022-12-09 | 2024-06-18 | 한국생산기술연구원 | Manufacturing method of zn-al-mg hot-dip galvanized steel and zn-al-mg hot-dip galvanized steel by the method |
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| JP4331915B2 (en) * | 2001-07-12 | 2009-09-16 | 新日本製鐵株式会社 | High strength and high ductility hot dip galvanized steel sheet excellent in fatigue durability and corrosion resistance and method for producing the same |
| JP3631710B2 (en) * | 2001-10-01 | 2005-03-23 | 新日本製鐵株式会社 | Si-containing high-strength hot-dip galvanized steel sheet with excellent corrosion resistance and ductility and method for producing the same |
| JP3781055B1 (en) | 2005-03-31 | 2006-05-31 | 田中亜鉛鍍金株式会社 | Hot dip galvanizing method |
| JP5559479B2 (en) | 2008-01-22 | 2014-07-23 | Ｊｆｅスチール株式会社 | Hot-dip galvanized steel pipe and method for producing hot-dip galvanized steel pipe |
| JP5663840B2 (en) | 2008-02-19 | 2015-02-04 | Ｊｆｅスチール株式会社 | Hot-dip galvanized steel pipe and method for producing hot-dip galvanized steel pipe |
| JP2009221604A (en) | 2008-02-19 | 2009-10-01 | Jfe Steel Corp | Hot dip galvanized steel tube and manufacturing method of hot dip galvanized material |
| JP5617170B2 (en) | 2008-02-19 | 2014-11-05 | Ｊｆｅスチール株式会社 | Hot-dip galvanized steel pipe and method for producing hot-dip galvanized steel pipe |
| EP2213758A1 (en) * | 2009-01-16 | 2010-08-04 | Galva Power Group N.V. | Flux and fluxing bath for hot dip galvanization, process for the hot dip galvanization of an iron or steel article |
| JP5476651B2 (en) | 2009-07-21 | 2014-04-23 | Ｊｆｅスチール株式会社 | Hot-dip galvanized steel pipe and method for producing hot-dip galvanized material |
| JP5672727B2 (en) * | 2010-03-12 | 2015-02-18 | 田中亜鉛鍍金株式会社 | Hot-dip galvanizing method with less environmental impact and hot-dip galvanized steel using the same |
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2015
- 2015-07-31 CN CN201580041381.0A patent/CN106661708B/en active Active
- 2015-07-31 JP JP2015555314A patent/JP6137339B2/en active Active
- 2015-07-31 WO PCT/JP2015/003869 patent/WO2016017186A1/en active Application Filing
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| JPWO2016017186A1 (en) | 2017-04-27 |
| JP6137339B2 (en) | 2017-05-31 |
| CN106661708A (en) | 2017-05-10 |
| WO2016017186A1 (en) | 2016-02-04 |
| KR20170024023A (en) | 2017-03-06 |
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