CN106086996A - A kind of reparation has been got rusty the composite surface treatment method of passivation for stainless steel state - Google Patents
A kind of reparation has been got rusty the composite surface treatment method of passivation for stainless steel state Download PDFInfo
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- CN106086996A CN106086996A CN201610712096.3A CN201610712096A CN106086996A CN 106086996 A CN106086996 A CN 106086996A CN 201610712096 A CN201610712096 A CN 201610712096A CN 106086996 A CN106086996 A CN 106086996A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention belongs to stainless steel surfaces process field; particularly relate to a kind of reparation got rusty the composite surface treatment method of passivation for stainless steel state; electrochemical passivation is used to add the compounding method of self assembly molecule membrane technology the stainless steel products that corrosion occurs; electrochemical passivation is carried out below protection potential; neither stimulate original spot corrosion to continue corrosion and can rebuild again the passivating film that the stainless steel surfaces that got rusty is completely fine and close; and with self-assembled monolayers, the passivating film after repairing is safeguarded, and it is allowed to keep stable.After electrochemical passivation adds self-assembled monolayers process, the corrosion resisting property of stainless steel products is significantly improved.The electrochemical passivation technical risk that the present invention uses is little, and safety is high, and good passivation effect is simple and easy to do, and engineer applied is strong, can become the important means that corrosion stainless steel products is repaired and safeguarded, have great Social benefit and economic benefit.
Description
Technical field
The invention belongs to stainless steel surfaces process field, particularly relate to a kind of reparation and got rusty the answering of passivation for stainless steel state
Close surface treatment method, the stainless steel products that corrosion occurs can be repaired and protected.
Background technology
Rustless steel has obtained applying widely because of its good corrosion resistance in practice.Its corrosion proof basis is that surface is blunt
Change mechanism, i.e. stainless steel surfaces and form the passivating film that can alleviate corrosion chance of occurrence.But, rustless steel is not necessarily referring in any situation
In all keep " stainless ".Therefore during actually used, if not noticing that stainless range and operation requirement are made
Becoming Damage of Passive Film, rustless steel still can corrode, especially local corrosion.The breaking-up of the stainless steel equipment thus caused and
Unexpected incidents, bring huge loss can to economy, environment, society.
Rustless steel has self-passivation function, can form natural passivation film with the oxygen in air, but natural passivation film resists
Corrosive effect is general.Utilizing this characteristic that rustless steel can be passivated, people's giving treatment in accordance with the tendency of pathological change has invented the method for artificial passivation,
To the artificial passivation film that more thicken finer and close than natural passivation film, so that rustless steel has more preferable anti-corrosion effect.At this
In a little methods, electrochemical passivation is considered as again a kind of more efficient method.
China Patent No. CN1030621 A, publication date on January 25th, 1989, invention entitled " stainless steel surfaces is corrosion-resistant
Property processing method ", this project discloses one and utilizes HNO3Solution, as electrolyte solution, utilizes constant potential technical controlling current potential
Value carries out the method for stainless steel electrochemical surface process.Finding out from patent, what it was stressed is before stainless steel products gets rusty, right
Rustless steel carries out surface modification, improves corrosion resisting property.But for getting rusty or even the stainless repair place of spot corrosion having occurred
Reason illustrates.
China Patent No. CN103074634 A, publication date on May 1st, 2013, invention entitled " a kind of stainless steel surfaces
Corrosion-resistant anti-oxidation treatment method ", this project discloses the double step current electrochemical treatments of a kind of employing, H2O2Chemical treatment with
And heat treatment phase combines, set up corrosion resistance and the method for oxidation resistant film layer at stainless steel surfaces.Find out from patent, its heat
Process part have employed muffle furnace, and requires that temperature reaches 100-500 DEG C, and these conditions and the equipment specific environment of needs can
Meet.The method carries out surface modification treatment for the rustless steel that corrosion does not occurs equally, and operation is more complicated.
The usual generation along with local corrosion of corrosion of stainless steel products, thus blunt to the surface of corrosion stainless steel products
Change the reparation of film, will consider to make original spot corrosion continued growth, realize the reconstruction of surface passivated membrane again.Additionally at certain
Under a little environment (environment as chloride), even if stainless steel products has been carried out electrochemical passivation repair process, when certain
Between, the passivating film being repaired is corroded again, and passivation effect is difficult to persistently.It addition, when stainless steel surfaces passive state obtains
After reparation, still suffering from again occurring the possibility of corrosion, therefore surface passivation state not only needs to repair but also needs to safeguard, ability
Reach the purpose of corrosion control.By literature search, in prior art, do not occur the stainless steel products of corrosion is carried out surface shape
State reparation and the technology safeguarded.
To corroding the ignorance that stainless steel products is repaired, the concept being firstly because rustless steel " stainless " usually makes people produce
Misread, and ignore its use condition and preventive means during rustless steel uses.Secondly stainless corrosion belongs to local
Corrosion, is different from homogeneous corrosion, has disguise and corrosion effects once occurs, the most remediable.Existing to not
The technology of rust steel surface electrochemistry passivation, general idea is all to improve stainless by strengthening passivating film before corrosion occurs
Decay resistance, and the premise that a lot of technological means realizes is all laboratory operation；But stainless steel products process under arms
Middle corrode on the premise of, carry out the most at the scene safely and effectively and the Corrosion Repair and the control method that are easily achieved are little
It is considered.
China Patent No. CN1401824 A, publication date on March 12nd, 2003, invention entitled " one can passive metal material
The electrochemical repair method of material local corrosion ", this disclosure of the invention is a kind of applies alternating electric field rotten to local in repairing medium
The method that the metal material of erosion carries out repairing.Find out from patent, which employs alternating electric field reparation and add the mode of post processing, this side
Although method is the repair process to metallic material local corrosion, but for execute-in-place, alternating electric field is used to add work
Journey difficulty, reduces the probability of large-scale application.Local corrosion especially be should give simultaneously attention protection potential Ep this
Characteristic, illustrates, if passivation potential E is more than protection potential Ep, situation about may cause is other rustless steels outside spot corrosion
Surface is passivated, and spot corrosion position is stimulated growth, and speed is exceedingly fast；If passivation potential is the least, may cause stainless
The sufficiently complete densification of passivating film on steel surface.
Summary of the invention
The purpose of the present invention is i.e. the shortcoming overcoming prior art, it is provided that one repairs passivation for stainless steel state of having got rusty
Composite surface treatment method, the stainless steel products got rusty is carried out field repair, rebuilds its surface passivation film system,
And carry out stablizing and safeguarding at passivating film surface applying self assembly molecule membrane technology.
The present invention adopts the following technical scheme that:
Pending rustless steel protection potential Ep in passivating solution medium and the blunt electricity of cause of having got rusty is measured by anode polarization
The value of position Epp, to determine the reparation parameter of electrochemistry；
To getting rusty, rustless steel carries out processing of rust removing；
The rustless steel that gets rusty is passivated front surface process；
The rustless steel that gets rusty carrying out electrochemistry and forces Passivation Treatment, passivation potential E meets: (Ep+Epp)/2 ＜ E ＜ Ep；
Carry out self-assembled monolayers technical finesse, suitable self assembly molecule film system is coated on the stainless steel watch that gets rusty
Face.
Wherein, the electrochemical passivation liquid group that described electrochemistry forces Passivation Treatment to use consists of: HNO3Volume fraction
10%-35%, Na2MoO20.01M-0.1M, H3PO4 0.05M-1M。
Further, described processing of rust removing uses pickling paste to process, and carries out wiping, then rinse with clear water straight after pickling
To getting rusty, stainless steel surfaces pH detects in neutrality, finally uses deionized water wiping.
Further, described passivation front surface processes and uses the method that the rustless steel that gets rusty carries out mechanical grinding polishing to go
Except the uneven place of the stainless steel surfaces that gets rusty, after alkali liquor oil removing, use clear water to rinse some times, then wipe with deionized water
Wipe.
Wherein, described electrochemistry forces Passivation Treatment to use three-electrode system using the pending rustless steel that got rusty as anode
Carry out constant potential passivation, determine that the pending rustless steel that got rusty corrodes electricity in passivating solution medium certainly by anodic polarization behavior
Position Ecorr, cause the value of blunt current potential Epp and protection potential Ep to determine scope (Ep+Epp)/2～the Ep of passivation potential E.
Further, in the scope (Ep+Epp)/2～Ep of fixed passivation potential E, a potential value is selected, in correspondence
Passivating solution medium in carry out constant potential Passivation Treatment；After electrochemical passivation, with clear water rinse got rusty rustless steel some all over after
Use deionized water wiping and be dried.
Preferably, described electrochemistry forces the passivation time of Passivation Treatment to be 15 minutes-90 minutes.
Preferably, described self assembly molecule film system includes silanes, alkyl sulfide alcohols, imidazolines and Schiff bases.
Electrochemical passivation in the present invention uses three-electrode system, and as anode, the pending rustless steel that got rusty is carried out perseverance
Current potential is passivated；Owing to the pressure of extra electric field is passivated, the passivating film that the stainless steel surfaces that got rusty obtains is more compact and complete, performance
The most excellent.
It is very big to there is the probability of spot corrosion in the surface of stainless steel product corroded, if E > Ep, outside spot corrosion other not
Although rust steel surface can be passivated, but spot corrosion position will be stimulated growth, and speed is exceedingly fast, and causes spot corrosion position
Corrosion continues to deepen；And if passivation potential E is the least, the energy needed for passivation is not enough, will cause the passivating film of stainless steel surfaces not
Enough complete fine and close.Application claims must provide enough fine and close passivation while will not continue to growth ensureing original spot corrosion
Film.Therefore, the present invention claim passivation potential must meet: the concrete numerical value of (Ep+Epp)/2 ＜ E ＜ Ep, Ep and Epp needs root
According to stainless concrete material in the passivating solution that the present invention selectes, it is measured by anode polarization.
Self assembly molecule film system is coated on the rustless steel of electrochemical passivation, and the tight molecular film of formation neither changes
Stainless outward appearance, plays again the effect of protection to rustless steel.
A kind of reparation that the present invention provides has been got rusty the composite surface treatment method of passivation for stainless steel state, Applied Electrochemistry
Force passivation that the rustless steel that gets rusty carries out onsite surface reparation, and apply self assembly molecule membrane technology that passivating film is maintained
And protection, the pending rustless steel that got rusty is carried out below protection potential electrochemical rehabilitation and adds the compound place of self-assembled monolayers
Reason.The stainless steel products corrosion potential after repairing in 3.5%NaCl solution that got rusty is more than 150mV (vs Ag/
AgCl), pitting potential is more than 1V (vs Ag/AgCl).It is coated with one layer of self-assembled monolayers after electrochemical passivation, has got rusty not
The outward appearance of rust steel does not the most change, and makes the duration in the atmospheric environment of strand of the passivating film after reparation improve 5
More than Bei.This high for stainless composite surface treatment method safety of getting rusty, application property is strong, and risk is little, processes effect
Rate is high, is used for repairing the stainless surface passivated membrane that the most gets rusty, and promotes its corrosion resisting property to sensitive environment (such as chloride ion),
Effect is obvious, simple and easy to do, and the reparation for stainless steel products is significant with maintenance.
Detailed description of the invention
The embodiment of the present invention provides the composite surface treatment method that passivation for stainless steel state has been got rusty in a kind of reparation, specifically grasps
Include as step:
(1) electrochemical parameter of the pending stainless steel products that got rusty is determined: determined pending by anodic polarization behavior
Got rusty stainless steel material natural corrosion potential in passivating solution medium, cause blunt current potential Epp and the value of protection potential Ep,
Thereby determine that scope (Ep+Epp)/2～the Ep of passivation potential E.
(2) acid pickling and rust removing: by pickling paste uniform application in the surface of stainless steel product of corrosion, the time that processes is according to actual feelings
Depending on condition；After process, use cotton or the like wiping, then rinse with clear water until stainless steel surfaces pH detects in neutrality,
Finally use deionized water wiping, prevent halide ion from remaining.
(3) passivation pre-treatment: after acid pickling and rust removing, the pending stainless steel products that got rusty is carried out mechanical grinding polishing, to the greatest extent
The uneven of stainless steel surfaces may be removed, improve surface smoothness；After alkali liquor oil removing, clear water is used to rinse some times,
Use deionized water wiping again.
(4) electrochemistry forces Passivation Treatment: according to the difformity of stainless steel products, can use electrolysis bath, voluble wrapping
Or the passivation mode such as brush realizes electrochemical passivation three-electrode system, three-electrode system is accessed electrochemical workstation, is having determined that
The scope (Ep+Epp)/2 of passivation potential E～Ep in select a current potential to carry out constant potential passivation in corresponding passivating solution medium
Process；After electrochemical passivation, rinse some times rear use deionized water wipings of rustless steel with clear water and be dried.
(5) it is not limited to use the mode brushed, spray, suitable self assembly molecule film system is coated on stainless steel watch
Face, self assembly molecule film system includes and is not limited to silanes, alkyl sulfide alcohols, imidazolines and Schiff bases.
The current potential related in the embodiment of the present invention refers both to relative to Ag/AgC l reference electrode, the most non-deoxygenation of solution, temperature
For room temperature condition, pending object is the 304 rustless steel pipelines (φ 20) of corrosion, uses the mode of voluble wrapping to realize three electrodes
System, specific embodiment is shown in Table 1.
Table 1 embodiment
Passivation potential E in the most each embodiment, is at passivating solution Anodic corresponding to each embodiment by 304 rustless steels
Cause blunt current potential Epp that polarization curve obtains and protection potential Ep, and then after determining passivation scope, the value determined.Implement
Within passivation potential E in example fully falls in corresponding passivation potential scope (Ep+Epp)/2～Ep.
Each embodiment in 3.5%NaCl solution to natural corrosion potential, polarization resistance Rp and the pitting potential Eb property done
Can test.Wherein, natural corrosion potential characterizes metal stable status in media as well, and its value is the highest to be typically more not susceptible to
Reaction；Polarization resistance Rp value characterizes the blocking capability of passivating film opposing corrosive medium, its value the highest opposing corrosive medium
Blocking capability is the strongest；Pitting potential Eb value represents the critical potential of metal generation spot corrosion, and its value the highest expression pitting corrosion resistant performance is more
By force.
Make a service test and obtain following laboratory data, be shown in Table 2-4.
The performance data of table 2 embodiment 1
| Pipeline 1 | Ecorr/V | Rp/Ω·cm<sup>2</sup> | Eb/V |
| Initial condition | -0.105 | 1.23E5 | 0.28 |
| After electrochemical passivation processes | 0.288 | 4.51E5 | 1.02 |
| After electrochemical passivation+coating self-assembled monolayers | 0.291 | 1.04E6 | 1.11 |
The performance data of table 3 embodiment 2
| Pipeline 2 | Ecorr/V | Rp/Ω·cm<sup>2</sup> | Eb/V |
| Initial condition | -0.098 | 1.57E5 | 0.32 |
| After electrochemical passivation processes | 0.416 | 8.01E5 | 1.13 |
| After electrochemical passivation+coating self-assembled monolayers | 0.424 | 2.88E6 | 1.20 |
The performance data of table 4 embodiment 3
| Pipeline 3 | Ecorr/V | Rp/Ω·cm<sup>2</sup> | Eb/V |
| Initial condition | -0.12 | 1.56E5 | 0.35 |
| After electrochemical passivation processes | 0.343 | 5.82E5 | 1.10 |
| After electrochemical passivation+coating self-assembled film processes | 0.363 | 1.71E6 | 1.21 |
During by table 2-4 it can be seen that the passivation potential using the present invention to propose meets (Ep+Epp)/2 ＜ E ＜ Ep, electricity
After chemical passivation processes, 304 stainless Ecorr value Rp values and Eb value are the most substantially increased, and show its stability, opposing
The blocking capability of corrosive medium is all significantly strengthened with pitting corrosion resistant performance；Through electrochemical passivation+coating self assembly molecule
After film processes, after electrochemical passivation processes on the basis of existing performance, polarization resistance Rp of 304 stainless steel pipes obtains into one
Step improves, and shows that the blocking capability of its opposing corrosive medium is significantly strengthened.
Above are only the detailed description of the invention of the present invention, but the design concept of the present invention is not limited thereto, all utilize this
Design carries out the change of unsubstantiality to the present invention, all should belong to the behavior invading scope.
Claims (8)
1. the composite surface treatment method repairing passivation for stainless steel state of having got rusty, it is characterised in that:
The pending rustless steel protection potential Ep in passivating solution medium and the blunt current potential Epp of cause that got rusty is measured by anode polarization
Value, with determine electrochemistry force passivation reparation parameter；
To getting rusty, rustless steel carries out processing of rust removing；
The rustless steel that gets rusty is passivated front surface process；
The rustless steel that gets rusty carrying out electrochemistry and forces Passivation Treatment, passivation potential E meets: (Ep+Epp)/2 ＜ E ＜ Ep；
Carry out self-assembled monolayers technical finesse, suitable self assembly molecule film system is coated on the stainless steel surfaces that gets rusty.
A kind of reparation the most as claimed in claim 1 has been got rusty the composite surface treatment method of passivation for stainless steel state, its feature
Being, the electrochemical passivation liquid that described electrochemistry forces Passivation Treatment to use consists of: HNO3Volume fraction 10%-35%,
Na2MoO20.01M-0.1M, H3PO4 0.05M-1M。
A kind of reparation the most as claimed in claim 1 has been got rusty the composite surface treatment method of passivation for stainless steel state, its feature
Being, described processing of rust removing uses pickling paste to process, and carries out wiping, then rinse until having got rusty stainless with clear water after pickling
Steel surface p H detects in neutrality, finally uses deionized water wiping.
A kind of reparation the most as claimed in claim 1 has been got rusty the composite surface treatment method of passivation for stainless steel state, its feature
Being, described passivation front surface processes and uses the method removal that the rustless steel that gets rusty carries out mechanical grinding polishing to get rusty stainless
The uneven place on steel surface, after alkali liquor oil removing, uses clear water to rinse some times, then uses deionized water wiping.
A kind of reparation the most as claimed in claim 1 has been got rusty the composite surface treatment method of passivation for stainless steel state, its feature
Being, described electrochemistry forces Passivation Treatment to use three-electrode system that as anode, the pending rustless steel that got rusty is carried out permanent electricity
Position passivation, by anodic polarization behavior determine the pending rustless steel natural corrosion potential in passivating solution medium that got rusty,
Cause blunt current potential Epp and the value of protection potential Ep, to determine that passivation potential E is in the range of (Ep+Epp)/2～Ep.
A kind of reparation the most as claimed in claim 5 has been got rusty the composite surface treatment method of passivation for stainless steel state, its feature
It is, in the scope (Ep+Epp)/2～Ep of fixed passivation potential E, selects a potential value, at corresponding passivating solution medium
In carry out constant potential Passivation Treatment；After electrochemical passivation, rinse, with clear water, the rustless steel that got rusty some all over rear use deionized water
Wiping is also dried.
A kind of reparation the most as claimed in claim 1 has been got rusty the composite surface treatment method of passivation for stainless steel state, its feature
Being, described electrochemistry forces the passivation time of Passivation Treatment to be 15 minutes-90 minutes.
A kind of reparation the most as claimed in claim 1 has been got rusty the composite surface treatment method of passivation for stainless steel state, its feature
Being, described self assembly molecule film system includes silanes, alkyl sulfide alcohols, imidazolines and Schiff bases.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107366010A (en) * | 2017-08-21 | 2017-11-21 | 厦门昕钢防腐工程科技有限公司 | A kind of stainless steel pipes and device context highly corrosion resistant processing method |
| CN107419276A (en) * | 2017-05-09 | 2017-12-01 | 上海建冶科技工程股份有限公司 | A kind of anti-corrosion handling process of austenitic stainless steel |
| CN109022899A (en) * | 2018-09-13 | 2018-12-18 | 慈溪市万金电子元件有限公司 | The preparation method of resistance to plug copper alloy plate against corrosion |
| CN111850534A (en) * | 2020-06-16 | 2020-10-30 | 中国石油天然气集团有限公司 | Martensite stainless steel oil pipe low-stress pre-passivation film and preparation method thereof |
| CN115161630A (en) * | 2022-07-25 | 2022-10-11 | 华迪钢业集团有限公司 | Pickling and passivating treatment process for seamless stainless steel pipe |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107419276A (en) * | 2017-05-09 | 2017-12-01 | 上海建冶科技工程股份有限公司 | A kind of anti-corrosion handling process of austenitic stainless steel |
| CN107419276B (en) * | 2017-05-09 | 2019-01-18 | 上海建冶科技工程股份有限公司 | A kind of anti-corrosion treatment process of austenitic stainless steel |
| CN107366010A (en) * | 2017-08-21 | 2017-11-21 | 厦门昕钢防腐工程科技有限公司 | A kind of stainless steel pipes and device context highly corrosion resistant processing method |
| CN109022899A (en) * | 2018-09-13 | 2018-12-18 | 慈溪市万金电子元件有限公司 | The preparation method of resistance to plug copper alloy plate against corrosion |
| CN111850534A (en) * | 2020-06-16 | 2020-10-30 | 中国石油天然气集团有限公司 | Martensite stainless steel oil pipe low-stress pre-passivation film and preparation method thereof |
| CN111850534B (en) * | 2020-06-16 | 2022-03-01 | 中国石油天然气集团有限公司 | Martensite stainless steel oil pipe low-stress pre-passivation film and preparation method thereof |
| CN115161630A (en) * | 2022-07-25 | 2022-10-11 | 华迪钢业集团有限公司 | Pickling and passivating treatment process for seamless stainless steel pipe |
| CN115161630B (en) * | 2022-07-25 | 2023-07-21 | 华迪钢业集团有限公司 | Pickling passivation treatment process of seamless stainless steel tube |
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