CN107587042A - Middle low chrome ferritic stainless steel cold-rolled steel sheet and its acid washing method - Google Patents
Middle low chrome ferritic stainless steel cold-rolled steel sheet and its acid washing method Download PDFInfo
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Abstract
The present invention provides a kind of acid washing method of middle low chrome ferritic stainless steel cold-rolled steel sheet, and it includes：Low chrome ferritic stainless steel cold-rolled steel sheet in annealing heat-treats, the cold-rolled steel sheet include：% by weight is counted, 0.01% or less carbon (C) (not including 0%), 0.45% to 0.90% silicon (Si), 0.20% to 0.40% manganese (Mn), 0.03% or less phosphorus (P), 0.005% or less sulphur (S), 11.0% to 14.3% chromium (Cr), 0.005% to 0.01% nitrogen (N), 0.15% to 0.25% titanium (Ti), 0.005% to 0.040% aluminium (Al) and 0.04% to 0.08% tin (Sn), wherein remaining ingredient is iron (Fe) and inevitable impurity, and meet relational expression (1)：28≤Si (%) × Sn (%) × 1000≤48；Carry out the cold-rolled steel sheet of neutral salt electrolysis pickling annealing heat-treats using the neutral salt electrolysis matter solution for containing sodium sulphate as electrolyte；And use and contain the cold-rolled steel sheet that sulfuric acid carrys out sulphuric acid electrolyte pickling neutral salt electrolysis pickling as the electrolyte sulfuric acid solution of electrolyte.
Description
The cross reference of related application
This application claims the Application No. 10-2016-0086580 submitted on July 8th, 2016 to Korean Intellectual Property Office
Korean patent application and Application No. 10-2016- from October 17th, 2016 to Korean Intellectual Property Office that submitted
The rights and interests of the priority of 0134535 korean patent application, the entire disclosure are incorporated herein by reference.
Technical field
This disclosure relates to a kind of content of chromium is acid of the 11 weight % to 14.3 weight % middle low chrome ferritic stainless steel
Washing method, in detail, it is related to a kind of using only neutral salt electrolysis acid cleaning process and sulphuric acid electrolyte acid cleaning process and without using mixing
The content of the chromium of sour acid cleaning process is acid washing methods of the 11 weight % to 14.3 weight % middle low chrome ferritic stainless steel.Enter one
Step ground, this disclosure relates to which the content of chromium is 11 weight % to 14.3 weight % and because its acid washing method has excellent acid
The middle low chrome ferritic stainless steel of pickling characteristic.
Background technology
Generally, one kind in the pickling in two ways of middle low chrome ferritic stainless steel is carried out.First method is it
In perform successively cold rolling, annealing heat-treats, fuse salt dipping and nitric acid electrolysis method.Second method is wherein to perform successively
Cold rolling, annealing heat-treats, neutral salt electrolysis pickling, sulphuric acid electrolyte pickling and mixed acid pickling are connected with using high speed pickling operation
The method of continuous facility.
On above-mentioned second method, KR2012-0075344 is shown in an illustrative manner.It is public in the patent document
Open and impregnated steel plate and the method for pickling in the mixed acid containing hydrofluoric acid.Due to using mixed acid, therefore exist by mixing
Risk caused by closing the hydrofluoric acid contained in acid.
Hydrofluoric acid is a kind of breakneck chemical substance.Hydrofluoric acid in tortoise tail National Industrial garden chemical plant leaks thing
Therefore in (on September 27th, 2012), due to the leakage of 8 to 10 tons of hydrofluoric acid, 5 people are dead, and 3000 people are injured, and plant is ruined, and
Underground water and drinking water source are contaminated.In addition, the hydrofluoric acid leakage accident (on January 27th, 2013) in chip factory of Samsung
In, two to three liters of a small amount of hydrofluoric acid leakage, a still people is dead and four people are injured.Therefore, in order to prevent similar accident
Occur, considering to be converted into the possibility of the alternate process technology without using hydrofluoric acid gravely.
In addition, when using mixed acid, the consumption of the hydrogen peroxide contained in mixed acid may be significantly high.Have determined
The use of a large amount of hydrogen peroxide is the reason for reducing the business efficiency of acid cleaning process.Therefore, in order to reduce the consumption of hydrogen peroxide,
It is proposed a kind of operating method of heat exchanger and cooler.Due to the operation of this optional equipment, running cost may increase.
On the other hand, when using fuse salt, it is convenient to omit mixed acid, but productivity ratio may be restricted.Additionally, it is possible to
Have the drawback that surface may be destroyed by the reaction between the fuse salt under high temperature and strip surface.
The content of the invention
The one side of the disclosure provides a kind of new acid washing method, when the content of manufacture chromium is 11 weight % to 14.3 weights
When measuring % middle low chrome ferritic stainless steel, it can be with high speed pickling steel, while omits and contain in the technique of pickling steel surface
There is the mixed acid acid cleaning process of hydrofluoric acid.
Further, the disclosure one side provide a kind of chromium suitable for above-mentioned acid washing method content be 11 weight % extremely
14.3 weight % middle low chrome ferritic stainless steel.
According to the one side of the disclosure, there is provided though it is a kind of can also ensure that when omitting mixed acid acid cleaning process it is excellent
The middle low chrome ferritic stainless steel plate of pickling characteristic, the steel plate include：% by weight is counted, and 0.01% or less carbon (C) is (no
Including 0%), 0.45% to 0.90% silicon (Si), 0.20% to 0.40% manganese (Mn), 0.03% or less phosphorus (P),
0.005% or less sulphur (S), 11.0% to 14.3% chromium (Cr), 0.005% to 0.01% nitrogen (N), 0.15% to
0.25% titanium (Ti), 0.005% to 0.040% aluminium (Al) and 0.04% to 0.08% tin (Sn), wherein remaining set
It is divided into iron (Fe) and inevitable impurity, and meets the relational expression of formula (1),
28≤Si (%) × Sn (%) × 1000≤48 (1).
Cold-rolled steel sheet may further include 0.3 weight % to 0.4 weight % niobium (Nb).
According to the one side of the disclosure, there is provided a kind of acid that can omit mixed acid acid cleaning process simultaneously with high speed pickling steel
Washing method, the acid washing method of middle low chrome ferritic stainless steel cold-rolled steel sheet include：Low chrome ferritic stainless steel in annealing heat-treats
Cold-rolled steel sheet, the steel plate include：% by weight is counted, 0.01% or less carbon (C) (not including 0%), 0.45% to 0.90%
Silicon (Si), 0.20% to 0.40% manganese (Mn), 0.03% or less phosphorus (P), 0.005% or less sulphur (S),
11.0% to 14.3% chromium (Cr), 0.005% to 0.01% nitrogen (N), 0.15% to 0.25% titanium (Ti), 0.005%
To 0.040% aluminium (Al) and 0.04% to 0.08% tin (Sn), wherein remaining ingredient is iron (Fe) and inevitable
Impurity, and meet the relational expression of formula (1), 28≤Si (%) × Sn (%) × 1000≤48 (1)；Using containing sulfuric acid
Sodium carrys out the heat treatment cold-rolled steel sheet of neutral salt electrolysis pickling annealing heat-treats as the neutral salt electrolysis matter solution of electrolyte；
And use and contain sulfuric acid and carry out sulphuric acid electrolyte pickling neutral salt electrolysis pickling as the electrolyte sulfuric acid solution of electrolyte
Cold-rolled steel sheet.
Cold-rolled steel sheet may further include 0.3 weight % to 0.4 weight % niobium (Nb).
Annealing heat-treats can perform 30 seconds to 2 minutes preferably in the range of 960 DEG C to 1040 DEG C.
There can be 0.12A/cm by applying2Or bigger and 0.25A/cm2Or the electric current of smaller current density 10 seconds is extremely
Perform each in neutral salt electrolysis pickling and sulphuric acid electrolyte pickling within 90 seconds.
It can be 70 DEG C to 85 DEG C to contain sodium sulphate as the temperature of the neutral salt electrolysis matter solution of electrolyte, and is contained
Sulfuric acid can be 40 DEG C to 55 DEG C as the temperature of the electrolyte sulfuric acid solution of electrolyte.
The concentration of the sodium sulphate contained in neutral salt electrolysis matter solution can be 180g/L to 250g/L, and sulphuric acid electrolyte
The concentration of the sulfuric acid contained in matter solution can be 60g/L to 100g/L.
Brief description of the drawings
From the detailed description below with reference to accompanying drawing, above and other aspect, feature and the advantage of the disclosure will more
Add and be more clearly understood from, wherein：
Fig. 1 be show after the cold rolling according to exemplary embodiment caused crackle and Si and Sn amount in surface product it
Between relation figure；And
Fig. 2 is the area for showing remaining oxide skin (scale) after pickling than the pass between the product of Si and Sn amount
The figure of system.
Embodiment
Hereinafter, embodiment of the disclosure will be described with reference to the accompanying drawings as follows.
However, the disclosure can illustrate in many different forms, and should not be construed as limited to set forth herein
Specific embodiment.Conversely, there is provided these embodiments so that the disclosure will be thorough and complete, and will be to art technology
Personnel fully pass on the scope of the present disclosure.
Throughout the specification, it will be appreciated that, when the element of such as layer, region or chip (substrate) is referred to as another
Element " on ", " being connected to " or during " being connected to " another element, its can directly another element " on ", " being connected to " or " connection
It is connected to " another element, or there may be intervenient other elements.On the contrary, when element is referred to as " directly in another element
On ", " being directly connected to " or during " being directly coupled to " another element, intervenient other elements or layer can be not present.Phase
Same reference represents identical element all the time.As used herein, term "and/or" is included listed by one or more correlations
Any and all combination of project.
It is evident that although term first, second, third, etc. can be used to describing herein various components,
Part, region, layer and/or part, but any this component, part, region, layer and/or part should not be limited by these terms.
These terms are only used for distinguishing a component, part, region, layer or part and another region, layer or part.Therefore, exist
In the case of the teaching for not departing from exemplary embodiment, first component discussed below, part, region, layer or part can be by
Referred to as second component, part, region, layer or part.
Can use herein the space relative terms of " top ", " top ", " lower section " and " bottom " etc. so as to
Relation in a description element as depicted relative to another element.It will be appreciated that in addition to the orientation described in figure,
Space relative terms be intended to including the use of or operation in device different azimuth.For example, if the device in figure is reversed,
Relative to other elements be described as " top " or " top " element will be oriented relative to other elements or feature " under
Side " or " bottom ".Therefore, term " top " can be included according to both the over-azimuth of the specific direction of figure and lower section orientation.
Device can otherwise be directed and (be rotated by 90 ° or at other orientation), and space used herein describes language relatively
It can be interpreted accordingly.
Terms used herein only describes specific embodiment, and disclosure not limited to this.As used herein, odd number shape
Formula " one ", "one" and "the" are also intended to including plural form, unless the context clearly indicates otherwise.It will be further understood that
It is, when in this manual in use, term " comprising " and/or " including " specify the feature, entirety, step, operation, structure
The presence of part, element and/or its group, but it is not excluded for one or more of the other feature, entirety, step, operation, component, element
And/or the presence or addition of its group.
Hereinafter, embodiment of the disclosure will be described with reference to showing the schematic diagram of embodiment of the disclosure.In accompanying drawing
In, for example, due to manufacturing technology and/or tolerance, the modification of shown shape can be estimated.Therefore, embodiment of the disclosure should not
It is construed as limited to the given shape of regions illustrated herein, it may for example comprise the change of shape result in manufacture.Following examples
Can also individually, combination or part form in combination.
Content of this disclosure described below can have various configurations, and only propose required configuration herein,
But not limited to this.
【The most preferred embodiment of invention】
The present inventor has furtherd investigate to come really while mixed acid acid cleaning process is omitted using only cathodic pickling technique
The method for the excellent surface quality protected after pickling, wherein using acid when central low chrome ferritic stainless steel cold-rolled steel sheet is acid washed.
As a result, confirming, the alloying element of middle low chrome ferritic stainless steel cold-rolled steel sheet can be with optimised, cold
The thickness of the oxide skin formed on the surface of rolled steel plate can be controlled, in the case where not performing mixed acid acid cleaning process, when
When the amount of silicon and tin is appropriately adjusted, pickling characteristic can be excellent, and may insure excellent surface matter after pickling
Amount, so as to complete the present invention.
Hereinafter, it will be described in detail the present invention.
Low chromium in preparing is included according to the acid washing method of the middle low chrome ferritic stainless steel cold-rolled steel sheet of exemplary embodiment
Ferritic stainless steel cold-rolled steel sheet, and the cold-rolled steel of neutral salt electrolysis pickling and sulphuric acid electrolyte pickling annealing heat-treats
Plate.
In this case, middle low chrome ferritic stainless steel cold-rolled steel sheet is preferably cold-rolled steel sheet, and it includes：% by weight
Meter, 0.01% or less C (not including 0%), 0.45% to 0.90% Si, 0.20% to 0.40% Mn, 0.03% or
Less P, 0.005% or less S, 11.0% to 14.3% Cr, 0.005% to 0.01% N, 0.15% to 0.25%
Ti, 0.005% to 0.040% Al, 0.04% to 0.08% Sn, wherein remaining ingredient be Fe and inevitably it is miscellaneous
Matter.In addition, cold-rolled steel sheet can be further containing 0.3% to 0.4% Nb.
Hereinafter, will be described in limitation the present invention middle low chrome ferritic stainless steel cold-rolled steel sheet alloying element and
The reason for element relation.Herein, unless otherwise stated, the content of each element refers to weight %.
C (carbon)：Not 0.01% or less (not including 0%)
C is advantageous for improving the element of the intensity of steel.However, when C is excessively added, it may occur however that toughness, corrosion resistant
The problem of corrosion etc. reduces.In consideration of it, in the exemplary embodiment, C (does not include preferably with 0.01% or less
0%) amount is added.
Si (silicon)：0.45% to 0.9%
Si be during steel-making allow deoxidation of molten steel, have high-temperature oxidation resistance and due to the interaction with Sn without
The element of hydrofluoric acid pickling occurs.If Si exists with the amount less than 0.45%, pickling characteristic may reduce.If Si's
Content is more than 0.9%, then formability significantly reduces.Therefore, as described above, Si is preferably added with 0.45% to 0.9% amount
Add.
Mn (manganese)：0.2% to 0.4%
Mn is the element for effectively improving corrosion resistance.In the exemplary embodiment, preferably comprising 0.2% or more amount
Mn.However, when Mn content is more than 0.40%, the generation of the smog containing Mn increases sharply during welding, therefore weldability can
It can reduce.In addition, MnS precipitation may be excessive, it is thus possible to the problem of ductility and corrosion resistance reduction occurs.Therefore, Mn
Amount be preferably no more than 0.40%.
P (phosphorus)：0.03% or less
P is the impurity being inevitably included in steel, and is as causing intercrystalline corrosion or suppression during pickling
The element of the main reason for hot-workability.Therefore, it is desirable to it is as low as possible by P content control.In the exemplary embodiment, it is excellent
Choosing is to control P content for 0.03% or less.
S (sulphur)：0.005% or less
S is the impurity being inevitably included in steel, and is to suppress hot-working as due to being segregated in crystal boundary
The element of the main reason for property.It is preferred, therefore, to it is as low as possible by S content control.In the exemplary embodiment, preferably
Be by the control of S content be 0.005% or less.
Cr (chromium)：11.0% to 14.3%
Cr is the element for the corrosion resistance for effectively improving steel.The stainless steel being classified as such means what is wherein contained
Cr content is 11% or more.However, if Cr content is excessive and more than 14.3%, do not sent out in cathodic pickling technique
The dissolving of raw base material, therefore Cr- depleted layers are there may be after cathodic pickling.If there is Cr- depleted layers, then corrosion resistance can
It can reduce, this is undesirable.
N (nitrogen)：0.005% to 0.01%
N is to promote the element of recrystallization by separating out austenite in ferritic phase during hot rolling.Therefore, N is preferred
Added with 0.005% or more amount on ground.However, if N content is excessive and more than 0.01%, prolonging for steel may occur
The problem of malleability reduces, this is undesirable.
Ti (titanium)：0.15% to 0.25%
Ti is effectively to reduce the amount of the nitrogen of the carbon being dissolved in steel and solid solution by fixed carbon and nitrogen and effectively improve steel
Corrosion resistance element.In the exemplary embodiment, Ti is preferably added with 0.15% or more amount.If however,
Ti content is excessive and more than 0.25%, then not only manufacturing cost may increase, but also may be due to forming Ti base field trashes
And causing surface defect, this is undesirable.
Al (aluminium)：0.005% to 0.040%
Al is a kind of strong deoxidier, and for reducing the oxygen content in molten steel.Therefore, Al preferably with 0.005% or
It is more to measure to add.However, if Al content is excessive and more than 0.040%, due to the increase of non-metallic inclusion, hair
The sleeve defect (sleeve defect) of raw and cold strip, while the problem of weldability deteriorates may occur, this is undesirable
's.
Sn (tin)：0.04% to 0.08%
In the exemplary embodiment, Sn is the essential elements for the thickness for controlling oxide skin and oxide.In detail, Sn be
Suppress effective member that the diffusion into the surface of oxidizing elemental (such as Si, Cr etc.) in steel is not concentrated on the surface simultaneously during high annealing
Element.In order to fully obtain the effect above, Sn is preferably added with 0.04% or more amount.However, if Sn content surpasses
0.08% is crossed, then may be occurred as caused by Sn phenomena such as such as face checking, this is undesirable.
Nb (niobium)：0.3% to 0.4%
Nb is effectively to reduce the amount of the nitrogen of the carbon being dissolved in steel and solid solution by fixed carbon and nitrogen and effectively improve steel
Corrosion resistance element.In the exemplary embodiment, Nb is preferably added with 0.3% or more amount.If however, Nb
Content it is excessive and more than 0.4%, then not only manufacturing cost increase, but also table may be caused due to forming Nb bases field trash
Planar defect, this is undesirable.
The remaining ingredient of exemplary embodiment is iron (Fe).However, in the steel making technique according to correlation technique, may
Unintentionally impurity is inevitably introduced from raw material or surrounding environment so that these impurity can not be excluded.Such impurity exists
Do not referred to specifically in this specification, because they are known for the technical staff of field of steel-making.
On the other hand, the middle low chrome ferritic stainless steel cold rolling according to exemplary embodiment of above-mentioned alloying element is being met
In steel plate, the content that the Si and Sn of the formation of oxide skin are influenceed in element preferably meets the element relation represented by formula (1).
28≤Si (%) × Sn (%) × 1000≤48 (1)
When formula (1) is satisfied, in the case where not including mixed acid acid cleaning process, merely with cathodic pickling technique,
Pickling is performed in the case of can not ftractureing on a surface of a steel sheet after pickling.If according to the Si and Sn of formula (1)
Between relation be less than 28, then the Sn's of barrier element for being used as preventing during oxidizing process aoxidizing as caused by Si movement
Content may deficiency.If according to the relation between the Si and Sn of formula (1) more than 48, intensity increase, therefore in rolling work
Face checking may be caused during skill.
As described above, when the alloying element in central low chrome ferritic stainless steel cold-rolled steel sheet is controlled, only by using
Neutral salt electrolysis pickling and sulphuric acid electrolyte pickling are easy with scale removal.Even if when omission mixed acid acid cleaning process
When, the residual oxidization skin after pickling can also be zeroed, therefore the excellent surface on steel plate is may insure after pickling
Quality.
It is as described above, cold in the optimised middle low chrome ferritic stainless steel according to exemplary embodiment of wherein alloying element
In rolled steel plate, after performing annealing heat-treats in the range of constant temperature, cathodic pickling processing is preferably carried out.
Annealing heat-treats preferably perform within the temperature range of 960 DEG C to 1040 DEG C.When annealing heat-treats are less than 960
When being carried out at a temperature of DEG C, recrystallization is suppressed or ferrite exists actually in the form of being extruded in the rolling direction, because
The characteristic of this ductility etc. may reduce.Therefore, annealing heat-treats preferably perform at a temperature of higher than 960 DEG C.Hold
The upper limit of the temperature of row annealing heat-treats is not particularly limited, it is contemplated that energy efficiency, manufacturing cost etc., do not surpass preferably
Cross 1040 DEG C.
In this case, annealing heat-treats are preferably performed in 2 minutes in the range of said temperature, preferably 30 seconds to 2
Minute.Target operation speed, linear velocity (m/min) are 125/ thickness (mm), its thickness according to material and change.For example, work as
When thickness is that 1.25mm material is heat-treated, heat treatment is performed due to 125/1.25, therefore with 100mpm speed.Therefore,
When the length of heat-treatment furnace is 100m, confirmation is to be heat-treated the required time as 1 minute.In addition, when the thickness of material increases
Add, during for example, 2.5mm, heat treatment is performed due to 125/2.5, therefore with 50mpm speed, so the time needed for heat treatment
For 2 minutes.According to this relation, heat treatment time can increase to most 2 minutes.
After annealing heat-treats are completed as previously described, cathodic pickling is performed to perform pickling.In this case, electrolysis acid
Wash bags include wherein permission neutral salt electrolysis pickling of the steel plate by neutral salt electrolysis pond, and wherein allow steel plate to pass through sulfuric acid electricity
Xie Chi sulphuric acid electrolyte pickling.Cathodic pickling is for present on the surface of low chrome ferritic stainless steel cold-rolled steel sheet in removal
The acid cleaning process of oxide skin.
Preferably, neutral salt electrolysis pickling is performed using the neutral salt electrolyte for containing sodium sulphate as electrolyte.Upper
State in the neutral salt electrolysis pond containing neutral salt electrolysis matter solution, its temperature preferably in the range of 70 DEG C to 85 DEG C, and its
In the concentration of sodium sulphate that contains preferably in the range of 180g/L to 250g/L.If at a temperature below 70 DEG C, react
Speed is slow, it is thus possible to is difficult to perform pickling at a high speed.If its temperature is higher than 85 DEG C, the stability of reactor may drop
It is low.If the concentration of neutral salt is less than 180g/L, electric conductivity is low, therefore pickling efficiency may reduce.If neutral salt is dense
Degree then obtains identical efficiency, therefore the concentration of neutral salt is restricted to above range according to economy more than 250g/L.
In the neutral salt electrolysis pond controlled as described above, in the middle low chrome ferritic stainless steel according to exemplary embodiment
Cold-rolled steel sheet it is impregnated wherein after, there is 0.12A/cm2Or the electric current of bigger current density is applied in perform neutral salt
Cathodic pickling.Preferably, the current density of electric current is 0.12A/cm2It is or bigger.
If the magnitude of current that electrolytic cell is applied to during neutral salt electrolysis pickling is less than 0.12A/cm2, then energy is not formed
The surface potential for the oxide skin that enough dissolvings are formed on the superficial layer of cold-rolled steel sheet, it can occur in which that neutral salt electrolysis pickling is imitated
The problem of fruit is insufficient.The upper limit of the magnitude of current is not particularly limited.However, because the base material below oxide skin is likely to be broken,
Therefore the magnitude of current is preferably 0.25A/cm2It is or smaller.
In this case, the electric current with current density can be applied in tens seconds, preferably 10 seconds to 90 seconds.Consider
To its centerline velocities TV, (thickness) × (rotating speed (velocity)) be usually 100 or bigger high speed electrolytic acid cleaning process in can
The pickling time of permission, it is preferably carried out electric current and applies 10 seconds to 90 seconds.
After the completion of neutral salt electrolysis pickling, sulphuric acid electrolyte pickling is performed.Using containing sulfuric acid of the sulfuric acid as electrolyte
Electrolyte performs sulphuric acid electrolyte pickling.In the above-mentioned sulphuric acid electrolyte pond containing electrolyte sulfuric acid solution, its temperature is preferably 40
DEG C in the range of 55 DEG C, and the concentration of the sulfuric acid wherein contained is preferably in the range of 60g/L to 100g/L.If its
Temperature is less than 40 DEG C, then reaction speed is slow.If its temperature is higher than 55 DEG C, the temperature of reactor due to reaction heat and drastically on
Rise, it is thus possible to perform uneven pickling operation.Meanwhile if the concentration of the sulfuric acid contained in electrolyte sulfuric acid solution is low,
It is, for example, less than 60g/L, then electric conductivity may reduce, therefore pickling efficiency may reduce.If its concentration, can more than 100g/L
Uneven pickling can occur.
In the sulphuric acid electrolyte pond controlled as described above, according to exemplary embodiment by neutral salt electrolysis pickling
After the middle low chrome ferritic stainless steel cold-rolled steel sheet of processing is dipped into wherein, there is 0.12A/cm2Or bigger current density
Electric current be applied in perform sulphuric acid electrolyte pickling.
If the magnitude of current that electrolytic cell is applied to during sulphuric acid electrolyte pickling is less than 0.12A/cm2, then cathodic pickling phase
Between surface potential be formed it is low, it is thus possible to occur surface quality decline the problem of.Meanwhile the upper limit of the magnitude of current is without spy
Do not limit.However, the base material below oxide skin is likely to be broken, therefore the magnitude of current to be applied is preferably 0.25A/cm2Or
It is smaller.
In this case, the electric current with current density can be applied in tens seconds, preferably 10 seconds to 90 seconds.Consider
To its centerline velocities TV, (thickness) × (rotating speed) be usually 100 or bigger high speed electrolytic acid cleaning process in admissible pickling
Time, it is preferably carried out electric current and applies 10 seconds to 90 seconds.
In detail, if the current density of the electric current applied during neutral salt electrolysis acid cleaning process is unsatisfactory for according to example
The scope of property embodiment, then regardless of the current density of the electric current applied during subsequent sulphuric acid electrolyte acid cleaning process, all
The not pickling or damage to base material may be caused.The current density of the electric current applied during neutral salt electrolysis acid cleaning process
In appropriate scope, but when the current density of the electric current applied during sulphuric acid electrolyte pickling also meets according to exemplary implementation
During the scope of example, it is only possible to that the damage to base material will not be caused.In the exemplary embodiment, applied during neutral salt electrolysis pickling
The current density of the electric current added and the current density of the electric current applied during sulphuric acid electrolyte pickling preferably meet according to example
The scope of property embodiment.
Not only it can perform continuously but also intermittently neutral salt electrolysis acid cleaning process and sulphuric acid electrolyte acid cleaning process.
However, these techniques are not particularly limited, and preferably continuously perform.
Meanwhile according to correlation technique, after above-mentioned neutral salt electrolysis pickling and sulphuric acid electrolyte pickling is performed, perform steel
Plate is immersed in the mixed acid acid cleaning process to pass through from it in the mixing acid tank containing hydrofluoric acid, all outside base material to remove
Oxide.However, above-mentioned mixed acid acid cleaning process is omitted in the exemplary embodiment.In other words, according to exemplary embodiment
Middle low chrome ferritic stainless steel cold-rolled steel sheet in, even if when omitting mixed acid acid cleaning process, can also be in neutral salt electrolysis
Excellent surface quality is obtained after pickling and sulphuric acid electrolyte pickling.
【The embodiment of invention】
Hereinafter, the present invention will be more fully described with reference to exemplary embodiment.Following exemplary embodiment be intended into
The one step explanation present invention, it is no intended to the limitation present invention.
Exist in each middle low chrome ferritic stainless steel cold-rolled steel sheet for being cold-rolled to the 1.2mm element with table 1
Annealing heat-treats are after 60 seconds at 1000 DEG C, and the concentration of the sodium sulphate contained wherein is 230g/L and its temperature is 80 DEG C
In neutral salt electrolysis pond containing neutral salt electrolysis matter solution, it is applied with 0.17A/cm2Current density electric current with
Perform cathodic pickling.
Next, the concentration of the sulfuric acid contained wherein is 80g/L and its temperature is 50 DEG C and contains electrolyte sulfuric acid
In the sulphuric acid electrolyte pond of solution, it is applied with 0.17A/cm2Current density electric current to perform cathodic pickling.
In the cold-rolled steel sheet obtained by neutral salt electrolysis pickling and sulphuric acid electrolyte pickling, face crack after pickling
Length and the amount of residual oxidization skin are measured, and its result is shown in table 1.
In addition, the length of face crack and result of each in the amount of residual oxidization skin with formula (1) after pickling
Between relation show in fig. 1 and 2 respectively.Fig. 1 is the length for the face crack for showing the result according to formula (1)
Figure, Fig. 2 is the figure of the amount for the residual oxidization skin for showing the result according to formula (1).
As shown in table 1 and Fig. 1, wherein according to the Si and Sn of formula (1) product be 48 or smaller (comparative example 1 to
14 and invention example 1 to 6) in the case of, confirmation is that face checking does not occur during rolling mill practice.However, Si wherein
With Sn product more than 48 (comparative example 15 to 22) in the case of, confirmation is that face checking occurs during rolling mill practice.
Meanwhile as shown in table 1 and Fig. 2, wherein according to the Si and Sn of formula (1) product be less than 28 (comparative example 1 to
14) in the case of, confirmation is the non-acid wash for occurring on surface to exist after wherein pickling residual oxidization skin.However, wherein
In the case that Si and Sn product is more than 28 (invention example 1 to 6 and comparative example 15 to 22), the surface after being pickling of confirmation
On not residual oxidization skin.
In detail, as shown in table 1, in the case of comparative example 11, according to formula (1), Si and Sn product are 16.Though
Face checking does not so occur after cold rolling, annealing heat-treats and cathodic pickling, it has been observed that residual caused by non-acid wash
It is 4% to stay oxide skin.On the other hand, in the case of invention example 3, Si and Sn product are 36.Although in cold rolling, annealing heat
Face checking does not occur after processing and cathodic pickling, but does not observe the residual oxidization skin caused by non-acid wash.
As described above, according to exemplary embodiment, the mixed acid acid cleaning process using hydrofluoric acid is omitted, therefore by hydrofluoric acid
Caused risk can be lowered, while cost can be lowered.
In addition, even if omitting mixed acid acid cleaning process, but can be provided with excellent pickling characteristic after pickling
And the middle low chrome ferritic stainless steel cold-rolled steel sheet with excellent surface quality.
Although being shown and described herein exemplary embodiment above, will be apparent to those skilled in the art
It is that, in the case where not departing from the scope of the present invention being defined by the following claims, modifications and variations can be carried out.
Claims (8)
1. a kind of middle low chrome ferritic stainless steel cold-rolled steel sheet, it includes：
0.01 weight % or less carbon be C (not including 0 weight %), 0.45 weight % to 0.90 weight % silicon i.e. Si,
0.20 weight % to 0.40 weight % manganese are Mn, 0.03 weight % or less phosphorus i.e. P, 0.005 weight % or less sulphur
That is S, 11.0 weight % to 14.3 weight % chromium are Cr, 0.005 weight % to 0.01 weight % nitrogen i.e. N, 0.15 weight %
Titanium to 0.25 weight % is Ti, 0.005 weight % to 0.040 weight % aluminium i.e. Al and 0.04 weight % to 0.08 weight
The tin for measuring % is Sn, and wherein remaining ingredient is that iron is Fe and inevitable impurity, and
Meet relational expression (1)
28≤Si (weight %) × Sn (weight %) × 1000≤48 (1).
2. middle low chrome ferritic stainless steel cold-rolled steel sheet according to claim 1, the cold-rolled steel sheet further comprise：
0.3 weight % to 0.4 weight % niobium be Nb.
3. a kind of acid washing method of middle low chrome ferritic stainless steel cold-rolled steel sheet, it includes：
Low chrome ferritic stainless steel cold-rolled steel sheet in annealing heat-treats, the cold-rolled steel sheet include 0.01 weight % or less carbon
That is C (not including 0 weight %), 0.45 weight % to 0.90 weight % silicon are Si, 0.20 weight % to 0.40 weight % manganese
That is Mn, 0.03 weight % or less phosphorus are P, 0.005 weight % or less sulphur i.e. S, 11.0 weight % to 14.3 weight %
Chromium be Cr, 0.005 weight % to 0.01 weight % nitrogen i.e. N, 0.15 weight % to 0.25 weight % titanium i.e. Ti, 0.005
Weight % to 0.040 weight % aluminium are Al and 0.04 weight % to 0.08 weight % tin i.e. Sn, and wherein remaining ingredient is
Iron is Fe and inevitable impurity, and meets relational expression (1)
28≤Si (weight %) × Sn (weight %) × 1000≤48 (1)；
Carry out neutral salt electrolysis pickling annealing heat-treats using the neutral salt electrolysis matter solution for containing sodium sulphate as electrolyte
The cold-rolled steel sheet；And
Carry out sulphuric acid electrolyte pickling neutral salt electrolysis pickling using the electrolyte sulfuric acid solution for containing sulfuric acid as electrolyte
The cold-rolled steel sheet.
4. the acid washing method of middle low chrome ferritic stainless steel cold-rolled steel sheet according to claim 3, wherein the cold-rolled steel
Plate further comprises 0.3 weight % to 0.4 weight % niobium, i.e. Nb.
5. the acid washing method of middle low chrome ferritic stainless steel cold-rolled steel sheet according to claim 3, wherein the annealing heat
Processing performs 30 seconds to 2 minutes in the range of 960 DEG C to 1040 DEG C.
6. the acid washing method of middle low chrome ferritic stainless steel cold-rolled steel sheet according to claim 3, wherein having by applying
There is 0.12A/cm2Or bigger and 0.25A/cm2Or the electric current of smaller current density 10 seconds performed the neutral salt electricity to 90 seconds
Solve each in pickling and the sulphuric acid electrolyte pickling.
7. the acid washing method of middle low chrome ferritic stainless steel cold-rolled steel sheet according to claim 3, wherein containing sodium sulphate
Temperature as the neutral salt electrolysis matter solution of electrolyte is 70 DEG C to 85 DEG C, and
It is 40 DEG C to 55 DEG C to contain sulfuric acid as the temperature of the electrolyte sulfuric acid solution of electrolyte.
8. the acid washing method of middle low chrome ferritic stainless steel cold-rolled steel sheet according to claim 3, wherein the neutral salt
The concentration of the sodium sulphate contained in electrolyte solution be 180g/L to 250g/L, and
The concentration of the sulfuric acid contained in the electrolyte sulfuric acid solution is 60g/L to 100g/L.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2016-0086580 | 2016-07-08 | ||
| KR1020160086580A KR101795948B1 (en) | 2016-07-08 | 2016-07-08 | Electrolytic pickling method for ferrite-base heat treated cold-rolled stainless steel sheet |
| KR10-2016-0134535 | 2016-10-17 | ||
| KR1020160134535A KR101819376B1 (en) | 2016-10-17 | 2016-10-17 | Ferritic stainless cold-rolled steel sheet having excellent acid eletrolytic cleaning |
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| CN107587042B CN107587042B (en) | 2020-05-19 |
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| JPH1192872A (en) * | 1997-09-12 | 1999-04-06 | Nippon Steel Corp | Ferritic stainless steel excellent in surface characteristic, and its production |
| JP2013147705A (en) * | 2012-01-19 | 2013-08-01 | Nippon Steel & Sumikin Stainless Steel Corp | Ferritic stainless steel wire rod and steel wire, and method for producing them |
| CN103403230A (en) * | 2010-12-28 | 2013-11-20 | Posco公司 | Eco-friendly high-speed pickling process for producing a low-chrome ferrite-based cold-rolled stainless steel sheet having superior surface quality |
| CN104870674A (en) * | 2012-12-24 | 2015-08-26 | Posco公司 | Ferritic stainless steel for automotive exhaust system, which have excellent corrosion resistance against condensate, moldability, and high-temperature oxidation resistance, and method for manufacturing same |
| CN104968823A (en) * | 2013-02-04 | 2015-10-07 | 新日铁住金不锈钢株式会社 | Ferritic stainless steel sheet with excellent workability and process for producing same |
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| JPH1192872A (en) * | 1997-09-12 | 1999-04-06 | Nippon Steel Corp | Ferritic stainless steel excellent in surface characteristic, and its production |
| CN103403230A (en) * | 2010-12-28 | 2013-11-20 | Posco公司 | Eco-friendly high-speed pickling process for producing a low-chrome ferrite-based cold-rolled stainless steel sheet having superior surface quality |
| JP2013147705A (en) * | 2012-01-19 | 2013-08-01 | Nippon Steel & Sumikin Stainless Steel Corp | Ferritic stainless steel wire rod and steel wire, and method for producing them |
| CN104870674A (en) * | 2012-12-24 | 2015-08-26 | Posco公司 | Ferritic stainless steel for automotive exhaust system, which have excellent corrosion resistance against condensate, moldability, and high-temperature oxidation resistance, and method for manufacturing same |
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