CN109563594A - Corrosionproof steel against sulfuric acid at dew point - Google Patents
Corrosionproof steel against sulfuric acid at dew point Download PDFInfo
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- CN109563594A CN109563594A CN201780049872.9A CN201780049872A CN109563594A CN 109563594 A CN109563594 A CN 109563594A CN 201780049872 A CN201780049872 A CN 201780049872A CN 109563594 A CN109563594 A CN 109563594A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
Abstract
With defined at being grouped as, which meets the relationship of following (1) formulas, and the content of Cu, Ni, Sb and Co meet the relationship of following (2) formulas.Wherein, [%S], [%Cu], [%Ni], [%Sb], [%Co] and [%W] is respectively the content (quality %) at S, Cu, Ni, Sb, Co and W in being grouped as 0.50≤[%Cu]/(10 × [%S]+[%Sb]+[%W])≤5.00 ... (1) 0.50≤([%Ni]+5 × [%Co]) /≤2.50 ... (2) ([%Cu]+[%Sb]).
Description
Technical field
The present invention relates to as in the environment of with sulfuric acid contact or generate sulphuric acid dew point in the environment of heat exchanger,
The corrosionproof steel against sulfuric acid at dew point that the constituent material of tank, equipment etc. uses, more particularly in addition to excellent resistant to sulfuric acid dew point corrosion
Property other than also with excellent salt tolerant acidity and manufacturing and bendability and fatigue durability also excellent resistant to sulfuric acid dew point corrosion
Steel.
Background technique
In the heat exchanger or flue of the boiler or thermal power plant that make the fuel combustions such as the heavy oil containing sulphur or coal, give up
Oxysulfide contained in gas occurs moisture condensation and is accordingly changed into sulfuric acid as temperature reduces, and it is i.e. so-called that serious burn into occurs
" corrosion of sulfuric acid at dew point " becomes problem.
In addition, recently, in the equipment of near shore, garbage burning factory, due in air salinity, in combustion ash it is contained
Chlorine etc., hydrochloric acid is led to the problem of together with sulfuric acid to be become.Although sulfuric acid and hydrochloric acid generate identical acid environment, but the oxidation of sulfuric acid
Property it is stronger, for the steel under such sulphuric acid environment, formed in steel surface stable as caused by ferrous oxide
Rusty scale (corrosion products).But if adding hydrochloric acid wherein, chloride ion is easily destroyed above-mentioned rusty scale.Therefore, in this way
In the environment of, also require excellent acid resistance, particularly salt tolerant acid other than resistance to sulfuric acid dew point corrosion.
As the scheme to solve the above problems, propose by efficiently using the Sb and work that improve corrosion resistance against sulfuric acid
The Cu of element to improve acid resistance improves corrosion resistance against sulfuric acid and acid proof technology.
For example, Patent Document 1 discloses: a kind of " the low conjunction of hydrochloric acid corrosion resistant and excellent in resistance to corrosion by sulfuric acid
Jin Gang, which is characterized in that contain C:0.001~0.2%, Si:0.01~2.5%, Mn:0.1~2%, Cu in terms of quality %:
0.1~1%, Mo:0.001~1%, Sb:0.01~0.2%, P:0.05% or less, S:0.05% hereinafter, surplus by Fe and not
Evitable impurity is constituted, also, acid-resistant corrosion Index A I (AI/10000=0.0005+0.045 × Sb%-C% ×
It Mo%) is 0 or more.".
On the other hand, when adding the low Cu of fusing point ratio Fe, being easy to happen the Sb of segregation, add in casting, the such heat of rolling
Working hour generates crackle of steel billet, billet surface scar, needs the reparation for avoiding product quality from deteriorating, therefore, productivity reduction,
Cost, which increases, becomes problem.
As solve such problems scheme, in patent document 2, disclose pass through reduce S amount and add Mo with
And B come realize hot-workability improvement, " a kind of excellent acidproof dew point corrosion steel of hot-workability, which is characterized in that with weight
Measure % meter containing C:0.01~0.15%, Si:0.1~0.5%, Mn:0.1~0.5%, P:0.03% or less, S:0.005% with
Under, Cu:0.2~1.0%, Ni:0.5% or less, Cr:2.0% or less, Al:0.1% or less, V:0.2% or less, Nb:0.2%
Below, one or both of Ti:0.2% or less, Sn and Sb add up to 0.01~1.0% and B:0.001~0.01%
And one or more of Mo:0.01~0.5%, surplus are made of Fe and inevitable impurity.".
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2003-213367 bulletin
Patent document 2: Japanese Unexamined Patent Publication 10-110237 bulletin
Summary of the invention
Problem to be solved by the invention
The concentration of the sulfuric acid generated in sulphuric acid dew point environment also changes because of its temperature, for example, at 40 DEG C of low temperature
Lower sulfuric acid concentration is about 20 mass %, and sulfuric acid concentration is about 50 mass % at 70 DEG C of medium temperature, at 100 DEG C~140 DEG C of high temperature
Sulfuric acid concentration is 70~80 mass %.
Therefore, when corrosionproof steel against sulfuric acid at dew point being applied to actual equipment, it is desirable that in various corrosion of sulfuric acid at dew point environment
Under show the material of highly corrosion resistant.
But when the low-alloy steel of patent document 1 is applied to actual equipment, although about acid resistance, particularly resistance to
It is salt acidic to show more excellent corrosion resistance compared with previous corrosionproof steel against sulfuric acid at dew point, but there are the following problems:
The characteristic that satisfactory degree may not necessarily be accessed for resistance to sulfuric acid dew point corrosion, especially to highly concentrated under high temperature
The corrosion resistance (resistance to sulfuric acid dew point corrosion) of the sulfuric acid of degree is low.
In addition, by reducing S, addition Mo, being remained on sometimes for the corrosionproof steel against sulfuric acid at dew point of patent document 2
It is unable to get desired resistance to sulfuric acid dew point corrosion.
The present invention is developed in view of above-mentioned status, rotten its purpose is to provide excellent resistance to sulphuric acid dew point is obtained simultaneously
Corrosion and excellent salt tolerant be acid and manufacturing and bendability and fatigue durability also excellent corrosionproof steel against sulfuric acid at dew point.
The method for solving problem
The present inventor to achieve the goals above, influence first to each addition element in corrosion of sulfuric acid at dew point environment into
It has gone tune Check, its effect has been studied in detail.
Specifically, in order to investigate each addition element for improving resistance to sulfuric acid dew point corrosion to salt tolerant acidity and manufacture
Property and bendability and fatigue durability bring influence and make salt tolerant acidity, manufacturing, bendability, fatigue durability raising it is each
Addition element gives resistance to sulfuric acid dew point corrosion bring to influence, and the steel of various composition composition has been manufactured, to making resistance to sulphuric acid dew point
Effective addition element in terms of excellent bendability and fatigue durability is obtained while corrosivity and salt tolerant are acid, manufacturing improves
Combination studied.
As a result, having obtained following opinion.
1) from the viewpoint of making resistance to sulfuric acid dew point corrosion simultaneously and salt tolerant is acid and manufacturing improves, in Cu, Sb
And compound addition Ni, Co and W are effective on the basis of S.
2) there are optimum ranges for the content of Cu, Sb, W and S, by that in the range, can ensure their controls
It is acid that excellent resistance to sulfuric acid dew point corrosion and salt tolerant are obtained while manufacturing and bendability and fatigue durability.
3) by containing suitable Ni and Co, Neng Gou relative to the Cu and Sb that improve resistance to sulfuric acid dew point corrosion
It maintains to greatly improve manufacturing, particularly hot-workability while resistance to sulfuric acid dew point corrosion and salt tolerant acidity.In addition, simultaneously
Also excellent bendability and fatigue durability can be obtained.
The present invention is further to be studied and completed repeatedly based on above-mentioned opinion.
That is, purport of the invention is constituted as described below.
1. a kind of corrosionproof steel against sulfuric acid at dew point, have in terms of quality % containing C:0.050~0.150%, Si:0.10~
0.80%, Mn:0.50~1.00%, P:0.050% or less, S:0.0020~0.0200%, Cu:0.20~0.50%, Ni:
0.10~0.80%, Cr:0.20~1.50%, Sb:0.050~0.300%, Co:0.002~0.020%, W:0.005~
0.200%, Ti:0.005~0.050%, Al:0.001~0.050% and N:0.0005~0.0050%, surplus by Fe and
Inevitable impurity constitute at being grouped as,
The content of S, Cu, Sb and W in mentioned component composition meet the relationship of following (1) formulas, Cu, Ni, Sb and Co
Content meet the relationships of following (2) formulas.
0.50≤[%Cu] /≤5.00 ... (1) (10 × [%S]+[%Sb]+[%W])
0.50≤([%Ni]+5 × [%Co]) /≤2.50 ... (2) ([%Cu]+[%Sb])
Wherein, [%S], [%Cu], [%Ni], [%Sb], [%Co] and [%W] be respectively in being grouped as S,
The content (quality %) of Cu, Ni, Sb, Co and W.
2. the corrosionproof steel against sulfuric acid at dew point as described in above-mentioned 1, wherein the content of C, Ti and N in mentioned component composition
Meet the relationship of following (3) formulas.
0.30≤[%Ti] /≤2.50 ... (3) (0.2 × [%C]+[%N])
Wherein, [%C], [%Ti] and [%N] is respectively the content (quality %) at C, Ti and N in being grouped as.
3. the corrosionproof steel against sulfuric acid at dew point as described in above-mentioned 1 or 2, wherein
It is the area ratio shared by 75% or more, pearlite phase with the area ratio shared by the ferritic phase in structure of steel entirety
Add up to shared structure of steel of the area ratio less than 5% less than the tissue other than 25%, above-mentioned ferritic phase and pearlite phase, and
And
Maximum Vickers hardness is 200 or less and average Vickers hardness is 80 or more.
4. the corrosionproof steel against sulfuric acid at dew point as described in above-mentioned any one of 1~3, wherein
Indicating electricity of the corrosionproof steel against sulfuric acid at dew point in the aqueous sulfuric acid that temperature is 70 DEG C, concentration is 50 mass %
It is 0.1A/cm by current density in the cathodic polarization curve of current density and the relationship of current potential2When current potential when being set as Va (V),
Cathodic polarization curve of the benchmark steel of above-mentioned Va and above-mentioned corrosionproof steel against sulfuric acid at dew point in above-mentioned aqueous sulfuric acid
In current density be 0.1A/cm2When the relationship of current potential Vg (V) meet following (4) formulas.
Vg-Va > 0.03 ... (4)
Invention effect
According to the present invention it is possible to obtain having excellent resistance to sulfuric acid dew point corrosion and salt tolerant acid and excellent manufacture
Property and bendability and fatigue durability also excellent corrosionproof steel against sulfuric acid at dew point.
Also, corrosionproof steel against sulfuric acid at dew point of the invention can be suitable as tank under various corrosion of sulfuric acid at dew point environment,
Therefore the constituent material of equipment etc. can be manufactured with low cost such tank, equipment etc. under high-quality and high production rate.
Detailed description of the invention
Fig. 1 is the corruption for showing the value and steel of [%Cu]/(10 × [%S]+[%Sb]+[%W]) in sulfuric acid immersion test
Lose the figure of the relationship of speed.
Fig. 2 is the relationship for showing the evaluation of value and manufacturing of ([%Ni]+5 × [%Co])/([%Cu]+[%Sb])
Figure.
Fig. 3 be by the evaluation result of resistance to sulfuric acid dew point corrosion and manufacturing to [%Cu]/(10 × [%S]+[%Sb]+
[%W]) and ([%Ni]+5 × [%Co])/([%Cu]+[%Sb]) value mapped obtained from figure.
Fig. 4 is show cathodic polarization curve in the aqueous sulfuric acid that temperature is 70 DEG C, concentration is 50 mass % one
The figure of example.
Specific embodiment
Hereinafter, the present invention is concretely demonstrated.Firstly, to by steel at being grouped as the reasons why being limited to above range
It is illustrated.It should be noted that the unit of the content at the element in being grouped as of steel is " quality % ", as long as hereinafter,
There is no special declaration, is abbreviated as " % ".
C:0.050~0.150%
C is the element for improving the intensity of steel.Desired intensity in order to obtain, C amount are set as 0.050% or more.Another party
Face deteriorates resistance to sulfuric acid dew point corrosion when C amount is more than 0.150%, and makes the toughness of weldability and welding heat affected zone
Deterioration.Therefore, C amount is set as 0.050~0.150% range.Preferably 0.060~0.100% range.
Si:0.10~0.80%
Si is the ingredient as deoxidier addition, and has the effect of improving the intensity of steel.Therefore, Si amount is set as
0.10% or more.But Si amount is when being more than 0.80%, the toughness deterioration of steel.Therefore, Si amount is set as 0.10~0.80% model
It encloses.It should be noted that Si forms anticorrosion overlay film under aqueous sulfuric acid environment and helps to improve resistant to sulfuric acid dew point corrosion
Property.Si amount is preferably set as 0.25% or more by the improvement effect of such resistance to sulfuric acid dew point corrosion in order to obtain.
Mn:0.50~1.00%
Mn is the element for improving the intensity of steel.Mn amount is set as 0.50% or more by desired intensity in order to obtain.It is another
Aspect when Mn amount is more than 1.00%, reduces the toughness of steel and weldability.Therefore, Mn amount is set as 0.50~1.00%
Range.It should be noted that from maintaining intensity and inhibiting the sight for making the formation of the field trash of resistance to sulfuric acid dew point corrosion deterioration
Point sets out, and Mn amount is preferably set as to 0.50~0.70% range.
P:0.050% or less
P is in the harmful element that segregation occurs for crystal boundary and reduces the toughness of steel.It is tough when especially P amount is more than 0.050%
Property significantly reduce.Therefore, P amount is set as 0.050% or less.
It should be noted that it is preferred that be reduced as far as P, but will lead to manufacturing cost to the reduction less than 0.005%
It increases.Therefore, the lower limit of P amount is preferably set to 0.005%.
S:0.0020~0.0200%
S is to contribute to form Cu2S overlay film in the presence of Cu, inhibit the corrosion reaction of steel surface and make resistance to sulphuric acid dew point
The element that corrosivity improves.On the other hand, S is also to form the MnS as non-metallic inclusion, the MnS as local corrosion
Starting point and the harmful element for reducing resistance to local corrosion.Therefore, from the viewpoint of ensuring resistance to sulfuric acid dew point corrosion, S amount
It is set as 0.0020% or more.On the other hand, from the viewpoint of the reduction for avoiding resistance to local corrosion, S amount is set as
0.0200% or less.It should be noted that S amount is preferably set from the viewpoint of further increasing resistance to sulfuric acid dew point corrosion
It is 0.0050% or more.
Cu:0.20~0.50%
Cu is the essential elements for improving acid resistance in the corrosive environment as caused by acid.Here, Cu amount is less than 0.20%
When, effect is small.On the other hand, when Cu amount is more than 0.50%, acid resistance improvement effect saturation, and cause manufacturing, especially
It is the deterioration of hot-workability.Therefore, Cu amount is set as 0.20~0.50% range.
Ni:0.10~0.80%
Ni is the element that hot-workability caused by inhibiting because of addition Cu, Sb deteriorates.But Ni amount less than 0.10% when,
Effect is small.On the other hand, when Ni amount is more than 0.80%, inhibit the effect saturation of hot-workability deterioration, and lead to the liter of cost
It is high.Therefore, Ni amount is set as 0.10~0.80% range.
Cr:0.20~1.50%
Although Cr does not greatly facilitate the improvement effect of the resistance to sulfuric acid dew point corrosion in normal temperature environment, be
The element for improving resistance to sulfuric acid dew point corrosion when 120 DEG C of use environment or more of high temperature.When Cr amount is less than 0.20%, this
A little effects are small.On the other hand, when Cr amount is more than 1.50%, these effects saturation, and lead to the raising of cost.Therefore, Cr amount
It is set as 0.20~1.50% range.Preferably 0.40~1.50% range.
Sb:0.050~0.300%
Sb is to pass through the compound addition with Cu and be enriched in steel surface in the form of Cu compound to make acid resistance improve
Element.But Sb amount less than 0.050% when, effect is small.On the other hand, when Sb amount is more than 0.300%, effect saturation,
And deteriorate manufacturing, particularly hot-workability.Therefore, Sb amount is set as 0.050~0.300% range.In addition, from simultaneous
From the perspective of caring for resistance to sulfuric acid dew point corrosion and manufacturing, Sb amount is preferably set to 0.100~0.200% range.
Co:0.002~0.020%
Co is the element that hot-workability caused by inhibiting together with Ni because of addition Cu, Sb deteriorates.In addition, Co is even if micro
Also contribute to the element of resistance to sulfuric acid dew point corrosion raising.But Co amount less than 0.002% when, effect is small.On the other hand,
When Co amount is more than 0.020%, lead to the raising of cost.Therefore, Co amount is set as 0.002~0.020% range.Preferably
0.002~0.010% range.
W:0.005~0.200%
W is the element for improving acid resistance, particularly salt tolerant acidity.That is, the WO formed in a corrosive environment4 2-Ion hair
The barriering effect to anion such as chloride ions is waved, and forms insoluble FeWO4And inhibit the progress of corrosion.In addition, in sulphur
It is densified due to there are W under acid environment in the rusty scale (corrosion product) that surface of steel plate is formed.In addition, W, which has, inhibits chloride ion resistance
Hinder the stabilisation of such rusty scale and repairs the effect of such rusty scale.In this way, W passes through chemical action and physical action
And inhibit corrosion in the environment of being added with hydrochloric acid in acid environment, particularly sulfuric acid, so that salt tolerant acidity be made to greatly improve.?
This, when W amount is less than 0.005%, cannot fully obtain said effect.On the other hand, when W amount is more than 0.200%, said effect
Saturation, and lead to the raising of cost.Therefore, W amount is set as 0.005~0.200% range.Preferably 0.020~
0.100% range.
It should be noted that about salt tolerant acidity, it is same as resistance to sulfuric acid dew point corrosion, it can be obtained by adding Cu, Sb
Its improvement.But corrosion product can exist more stablely in sulphuric acid environment, in contrast, add in sulfuric acid
In the environment of having hydrochloric acid, the influence of chloride ion is big, and such chloride ion makes that the corrosion product corroded is inhibited to become unstable.About
This point, W have the function of keeping above-mentioned corrosion product stable, in order to improve it is such in sulfuric acid added with hydrochloric acid in the environment of
Salt tolerant is acid, and it is extremely effective that corrosion resistance as W and Cu, Sb, which is improved compound addition together with element,.
Ti:0.005~0.050%
Ti is the purpose for the intensity and toughness that improve steel and the element that adds.But Ti amount is less than 0.005%
When, it is unable to get desired effect.On the other hand, when Ti amount is more than 0.050%, the effect of the intensity and toughness that improve steel is full
With.Therefore, Ti amount is set as 0.005~0.050% range.
Al:0.001~0.050%
Al is the element added as deoxidier.From the viewpoint of obtaining such effect, Al amount needs are set as
0.001% or more.On the other hand, when Al amount is more than 0.050%, the toughness of steel is reduced.Therefore, Al amount be set as 0.001~
0.050% range.Preferably 0.010~0.050% range.
N:0.0005~0.0050%
N is the element for deteriorating the toughness of steel with solid solution condition, is preferably reduced as far as, and N amount is 0.0050% or less
When can permit.On the other hand, it is technically difficult to completely remove N, in addition, reduction more than necessity will lead to the liter of manufacturing cost
It is high.Therefore, the lower limit set of N amount is 0.0005%.
In addition, each ingredient only meet above-mentioned range be it is insufficient, the content of S, Cu, Sb and W meet following (1) formulas
Relationship and the content of Cu, Ni, Sb and Co meet the relationships of following (2) formulas and be important.
0.50≤[%Cu] /≤5.00 ... (1) (10 × [%S]+[%Sb]+[%W])
0.50≤([%Ni]+5 × [%Co]) /≤2.50 ... (2) ([%Cu]+[%Sb])
Wherein, [%S], [%Cu], [%Ni], [%Sb], [%Co] and [%W] be respectively in being grouped as S,
The content (quality %) of Cu, Ni, Sb, Co and W.
[experiment]
Will containing C:0.050~0.150%, Si:0.10~0.80%, Mn:0.50~1.00%, P:0.050% or less,
Cr:0.20~1.50%, Ti:0.005~0.050%, Al:0.001~0.050% and N:0.0005~0.0050% and
The steel (surplus Fe and inevitable impurity) for making the content of S, Cu, Ni, Sb, Co and W that various change occur utilizes converter
Melting is carried out, the steel billet with a thickness of 200mm is made by continuous metal cast process.After steel billet cooling, it is again heated to 1200 DEG C of implementations heat
It rolls, the hot rolled steel plate that plate thickness is 4.5mm is made.
It should be noted that being set as following condition: in hot rolling, it is 850 that reduction ratio 97.75%, finish rolling, which terminate temperature,
DEG C, coiling temperature be 560 DEG C, in the range of the average cooling rate from 800 DEG C to 650 DEG C is 3.0~8.0 DEG C/sec.
In order to which the influence to each addition element in corrosion of sulfuric acid at dew point environment carries out tune Check, from the hot-rolled steel as above obtained
Width 20mm × length 30mm × thickness 3mm corrosion test piece is cut on plate, by the corrosion test piece being cut into for
6 hours sulfuric acid immersion corrosion experiments of dipping in aqueous sulfuric acid (temperature is 70 DEG C, concentration is 50 mass %), measurement corrosion subtract
Amount, the corrosion rate of each test film is calculated by corrosion weight loss.
Also, according to benchmark below, resistance to sulfuric acid dew point corrosion is evaluated.
Qualified (zero): 280g/ (m2Hour) below
Unqualified (×): corrosion rate is greater than 280g/ (m2Hour)
In addition, injurious surface mark depth when casting for steel billet, scar is confirmed by being coloured to surface, and carry out
It visually observes and is observed by being cut into section, manufacturing (hot-workability) is carried out according to benchmark below as a result,
Evaluation.
Qualified (zero): injurious surface mark depth is less than 0.2mm
Unqualified (×): injurious surface mark depth is 0.2mm or more
By the evaluation result of these resistance to sulfuric acid dew point corrosion and manufacturing with [%Cu]/(10 × [%S]+[%
Sb]+[%W]) and/or the form of relationship of ([%Ni]+5 × [%Co])/([%Cu]+[%Sb]) be shown in Fig. 1~3.
Known to: as shown in Figure 1, by controlling [%Cu]/(10 × [%S]+[%Sb]+[%W]) 0.50~5.00
Range, the improvement effect of excellent resistance to sulfuric acid dew point corrosion can be obtained.In addition we know: as shown in Fig. 2, passing through ([%
Ni]+5 × [%Co])/([%Cu]+[%Sb]) control 0.50~2.50 range, excellent manufacturing can be obtained.
And know: as shown in figure 3, by [%Cu]/(10 × [%S]+[%Sb]+[%W]) is set as 0.50~
5.00 range and by ([%Ni]+5 × [%Co])/([%Cu]+[%Sb]) control 0.50~2.50 range, energy
Enough take into account excellent resistance to sulfuric acid dew point corrosion and manufacturing.
The present inventor has found according to above-mentioned experimental result: by meeting above-mentioned (1) formula and (2) formula, available energy simultaneously
It enough takes into account excellent resistance to sulfuric acid dew point corrosion and manufacturing and salt tolerant acidity, bendability and fatigue durability is also sufficient
Steel, to develop the present invention.
0.50≤[%Cu]/(10 × [%S]+[%Sb]+[%W])≤5.00
As described above, by adding appropriate S, Sb and W according to Cu amount, specifically, passing through [%Cu]/(10 × [%
S]+[%Sb]+[%W]) be adjusted to 0.50~5.00 range, can ensure acid manufacturing and salt tolerant, bendability and
Resistance to sulfuric acid dew point corrosion is obtained while fatigue durability greatly improves effect.
Therefore, for the content of S, Cu, Sb and W, need to meet 0.50≤[%Cu]/(10 × [%S]+[%Sb]+
[%W])≤5.00 relationship.
In addition, the value of [%Cu]/(10 × [%S]+[%Sb]+[%W]) be preferably 3.50 hereinafter, more preferably 3.00 with
Under, further preferably 2.50 or less.
0.50≤([%Ni]+5 × [%Co])/([%Cu]+[%Sb])≤2.50
In addition, as described above, by adding appropriate Ni and Co according to Cu amount and Sb amount, specifically, pass through by
([%Ni]+5 × [%Co])/([%Cu]+[%Sb]) is adjusted to 0.50~2.50 range, can maintain resistance to sulphuric acid dew point
Manufacturing, particularly hot-workability are obtained while corrosivity and salt tolerant acidity greatly improves effect.
Therefore, for the content of Cu, Ni, Sb and Co, need to meet 0.50≤([%Ni]+5 × [%Co])/([%
Cu]+[%Sb])≤2.50 relationship.
In addition, the value of ([%Ni]+5 × [%Co])/([%Cu]+[%Sb]) is preferably 0.55 or more, more preferably
0.60 or more.
It should be noted that if only from the viewpoint of improving manufacturing, only provide ([%Ni]+5 × [%Co])/
The lower limit of ([%Cu]+[%Sb]), but when Ni amount increases, it is possible to adverse effect is brought to resistance to sulfuric acid dew point corrosion,
Therefore, it for the upper limit of ([%Ni]+5 × [%Co])/([%Cu]+[%Sb]), is also provided herein.
Furthermore it is preferred that the content of C, Ti and N meet the relationship of following (3) formulas.
0.30≤[%Ti] /≤2.50 ... (3) (0.2 × [%C]+[%N])
Wherein, [%C], [%Ti] and [%N] is respectively the content (quality %) at C, Ti and N in being grouped as.
0.30≤[%Ti]/(0.2 × [%C]+[%N])≤2.50
The inventors discovered that by the relationship for suitably controlling Ti, C and N amount in mentioned component composition, specifically,
By the way that [%Ti]/(0.2 × [%C]+[%N]) control in 0.30~2.50 range, can be greatly improved fatigue durability.
Therefore, for the content of Ti, C and N in mentioned component composition, preferably further meet the relationship of above-mentioned (3) formula.
In addition, the value of [%Ti]/(0.2 × [%C]+[%N]) is more preferably 0.40 or more and 2.00 hereinafter, more preferably
0.50 or more and 1.50 hereinafter, further preferably 0.50 or more and 1.10 or less.
Ingredient other than the above is Fe and inevitable impurity.
It should be noted that inevitable impurity described herein is because iron and steel raw material ore and waste material etc. can not
Avoid mixed element, refer to inadvertently addition and it is miscellaneous in the range of not affected to effect of the invention
Matter ingredient.As such inevitable impurity, such as O (oxygen) can be enumerated, be limited to about 0.0050% thereon.
Then, the preferred structure of steel of corrosionproof steel against sulfuric acid at dew point of the invention is illustrated.
As the preferred structure of steel of corrosionproof steel against sulfuric acid at dew point of the invention, the iron element in structure of steel entirety can be enumerated
The area ratio shared by body phase is the area ratio shared by 75% or more, pearlite phase less than 25%, above-mentioned ferritic phase and pearlite
Remaining tissue other than phase adds up to shared structure of steel of the area ratio less than 5%.
It should be noted that such tissue in order to obtain, aftermentioned hot-rolled condition is suitably controlled, particularly by 800
DEG C~650 DEG C within the temperature range of average cooling rate be set as 1.0 DEG C/sec or more and 20.0 DEG C/sec or less it is critically important.
The area ratio of ferritic phase: 75% or more
Corrosionproof steel against sulfuric acid at dew point uses after implementing bending machining because of shape of final products etc. sometimes.Here, iron is plain
When the area ratio of body phase is less than 75%, it is possible to be cracked in bending machining.Therefore, ferritic phase is in structure of steel entirety
Shared the area ratio is preferably set to 75% or more.More preferably 80% or more.It should be noted that the area ratio of ferritic phase
It can be 100%.
The area ratio: less than 25% of pearlite phase
Corrosionproof steel against sulfuric acid at dew point uses after implementing bending machining because of shape of final products etc. sometimes.Here, pearly-lustre
When the area ratio of body phase is 25% or more, it is possible to be cracked in bending machining.Therefore, pearlite is mutually in structure of steel entirety
In shared the area ratio be preferably set to less than 25%.More preferably 20% or less.It should be noted that the area of pearlite phase
Rate can be 0%.
As the residue tissue other than above-mentioned ferritic phase and pearlite phase, it is equal to enumerate bainite, is being mixed into
Bainite phase, martensite can worry the crackle when bending machining when equal.Therefore, the residue other than ferritic phase and pearlite phase
The total the area ratio of tissue is preferably set to less than 5%.
In addition, when maximum Vickers hardness is more than 200, when bending machining, is easy to produce crackle, and fatigue durability is also easy
Deterioration.When average Vickers hardness is less than 80, it is difficult to ensure defined intensity.
It is therefore preferable that being set as that maximum Vickers hardness is 200 or less and the Vickers hardness that is averaged is 80 or more.
In addition, for corrosionproof steel against sulfuric acid at dew point of the invention, indicating temperature is 70 DEG C, concentration is 50 matter
It is 0.1A/cm by current density in the cathodic polarization curve for measuring the relationship of the current density and current potential in the aqueous sulfuric acid of %2
When current potential when being set as Va (V), cathode of the benchmark steel of the Va and the corrosionproof steel against sulfuric acid at dew point in above-mentioned aqueous sulfuric acid
Current density in polarization curve is 0.1A/cm2When the relationship of current potential Vg (V) to meet following (4) formulas be preferred.
Vg-Va > 0.03 ... (4)
That is, dissolution of the corrosion of the steel in aqueous sulfuric acid by hydrionic reduction reaction and iron in aqueous sulfuric acid
It reacts and carries out.In Fig. 4, illustrate that hydrionic in the aqueous sulfuric acid that temperature is 70 DEG C, concentration is 50 mass %
It the cathodic polarization curve of the relationship of the current density and current potential of reduction reaction and indicates temperature is 70 DEG C, concentration is 50 mass %
Aqueous sulfuric acid in iron dissolution reaction current density and current potential relationship anodic polarization curves an example.In Fig. 4,
The point that cathodic polarization curve intersects with anodic polarization curves is the point for actually corroding progress.
Here, the present inventor finds out the cathodic polarization curve of various steel under various conditions, for cathodic polarization curve with
Research has further been repeated in the relationship of resistance to sulfuric acid dew point corrosion.
Itself as a result, it has been found that, for improving resistance to sulfuric acid dew point corrosion, inhibiting cathode reaction is effective, and resistant to sulfur
Acid dew piont corrosion and the electric current in the cathodic polarization curve in the aqueous sulfuric acid that temperature is 70 DEG C, concentration is 50 mass %
Density is 0.1A/cm2When current potential it is closely related.
Also, current density is by further progress the study found that in the cathodic polarization curve as the steel of object
0.1A/cm2When current potential when being set as Va (V), Va and the benchmark steel as so-called ordinary steel temperature be 70 DEG C, concentration 50
The current density of cathodic polarization curve in the aqueous sulfuric acid of quality % is 0.1A/cm2When current potential, that is, Vg (V) relationship it is full
Above-mentioned (4) formula of foot is that preferably, by meeting such relationship, resistance to sulfuric acid dew point corrosion is further increased.
It is therefore preferable that meeting the relationship of Vg-Va > 0.03.More preferably Vg-Va > 0.05.In addition, about the upper of Vg-Va
Limit is not particularly limited, and typically about 0.15.
It should be noted that using Hg/Hg (SO4) reference electrode carry out potential measurement when, Va and Vg are illustrated as bearing
Value still even in this case, keep Va relatively small also critically important compared with Vg.
In addition, selecting the current density in cathodic polarization curve for 0.1A/cm2Current potential be because are as follows: current density is less than
When above-mentioned value, noise etc. is generated because of determination condition sometimes, on the other hand, when current density is greater than above-mentioned value, cathode sometimes
It reacts meeting speed limit itself and is difficult to accurately measure current potential.
In addition, benchmark steel described herein refer to have in terms of quality % containing C:0.050~0.150%, Si:0.10~
0.80%, Mn:0.50~1.00%, P:0.050% or less, S:0.0020~0.0200%, Al:0.001~0.050% and
N:0.0005~0.0050%, surplus be made of Fe and inevitable impurity at be grouped as steel (especially Cu: less than
0.02%, Ni: less than 0.02%, Cr: less than 0.02%, Sb: less than 0.010%, Co: less than 0.002%, W: less than
0.005% and Ti: less than 0.005%).It should be noted that being 70 in temperature when for as at the steel being grouped as
DEG C, concentration be 50 mass % aqueous sulfuric acid in cathodic polarization curve it is roughly the same.
Then, the preferred manufacturing method of corrosionproof steel against sulfuric acid at dew point of the invention is illustrated.
Corrosionproof steel against sulfuric acid at dew point of the invention be will be adjusted to mentioned component composition steel former material be finish-machined to sheet metal,
Steel after the various shapes such as thick steel plate and fashioned iron as its manufacturing method, such as can be listed below method: turn utilizing
After the generally well-known method of furnace, electric furnace, vacuum degasser etc. carries out melting, steel billet is made using continuous metal cast process etc., later will
The steel billet is reheated immediately or after cooling and carries out hot rolling.In addition, in the case where cold-rolled steel sheet is made, further progress
Pickling and cold rolling and annealing, are made product.
It should be noted that as hot-rolled condition, from ensure required mechanical property, i.e. intensity (hardness), bendability,
From the perspective of fatigue durability, reduction ratio is preferably set as 50~99%, finish rolling is terminated to temperature is set as 650~950 DEG C,
Coiling temperature is set as 400~650 DEG C, the average cooling rate from 800 DEG C to 650 DEG C is set as 1.0~20.0 DEG C/sec.
In addition, from the viewpoint of meeting above-mentioned (4) formula, preferably the average cooling rate from 800 DEG C to 650 DEG C is set
It is 1.0~10.0 DEG C/sec.
Embodiment
It will be melted at the steel (surplus is Fe and inevitable impurity) being grouped as using converter shown in formation table 1
Refining, is made the steel billet with a thickness of 200mm by continuous metal cast process.After steel billet cooling, 1200 DEG C of implementation hot rollings are again heated to, are made
Plate thickness is the hot rolled steel plate of 4.5mm.
It should be noted that reduction ratio is set as 97.75% in hot rolling, finish rolling is terminated to temperature is set as 850 DEG C,
Coiling temperature is set as 560 DEG C, sets the average cooling rate from 800 DEG C to 650 DEG C as shown in table 2.
For the hot rolled steel plate obtained in this way, the area ratio and dimension of each phase in structure of steel are carried out by method as shown below
The measurement of family name's hardness and the evaluation of resistance to sulfuric acid dew point corrosion, salt tolerant acidity, manufacturing, bendability and fatigue durability.By this
A little results are shown in Table 2.
The measurement of the area ratio of each phase in structure of steel
Using 3% nital reagent (3% nitric acid+ethyl alcohol), hang down to the parallel with rolling direction of hot rolled steel plate
Straightforward face (depth location of plate thickness 1/4) is corroded, and is seen using the optical microscopy that multiplying power is 100 times to the part
It examines, shoot, the area ratio of ferrite and pearlite is found out using the macrograph of shooting.Here, about ferrite and pearl
The area ratio of body of light, carries out the observation in 5 visuals field respectively, and point of use counting method (according to ASTM E562-83 (1988)) is surveyed
It is fixed.In addition, the area ratio of the remaining tissue other than above-mentioned ferrite and pearlite can be by subtracting ferrite from 100%
And the total the area ratio of pearlite and find out.
The measurement of Vickers hardness
About Vickers hardness, according to JIS Z 2244 to the hot rolled steel plate as above obtained under conditions of load is 9.8N
Any 20 points of surface layer (position away from surface 0.5mm) are measured, and find out their average value and maximum value.
Resistance to sulfuric acid dew point corrosion
Width 20mm × length 30mm × thickness 3mm corrosion test piece is cut into from the hot rolled steel plate as above obtained,
By the corrosion test piece being cut into for the 6 hours sulphur of dipping in aqueous sulfuric acid (temperature: 70 DEG C, concentration: 50 mass %)
Acid dip corrosion test measures corrosion weight loss, the corrosion rate of each test film is calculated by corrosion weight loss.
Also, according to benchmark below, the resistance to sulfuric acid dew point corrosion under medium temperature is evaluated.
Qualified, particularly excellent (◎): corrosion rate is less than 250g/ (m2Hour)
Qualified (zero): corrosion rate is 250g/ (m2Hour) more than and 280g/ (m2Hour) below
Unqualified (×): corrosion rate is greater than 280g/ (m2Hour)
In addition, being in addition cut into width 20mm × length 30mm × thickness 3mm corruption from the hot rolled steel plate as above obtained
Corrosion test piece, by the corrosion test piece being cut into for the dipping in aqueous sulfuric acid (temperature: 140 DEG C, concentration: 80 mass %)
3 hours sulfuric acid immersion corrosion experiments measure corrosion weight loss, the corrosion rate of each test film are calculated by corrosion weight loss.
Also, according to benchmark below, resistance to sulfuric acid dew point corrosion at high temperature is evaluated.
Qualified, particularly excellent (◎): corrosion rate is less than 92g/ (m2Hour)
Qualified (zero): corrosion rate is 92g/ (m2Hour) more than and 97g/ (m2Hour) below unqualified (×): it is rotten
It loses speed and is greater than 97g/ (m2Hour)
Salt tolerant is acid
Width 20mm × length 30mm × thickness 3mm corrosion test piece is cut into from the hot rolled steel plate as above obtained,
Dipping 6 hours, measurement corrosion in aqueous hydrochloric acid solution (temperature: 80 DEG C, concentration: 5 mass %) by the corrosion test piece being cut into
Decrement, the corrosion rate of each test film is calculated by corrosion weight loss.
Also, according to benchmark below, salt tolerant acidity is evaluated.
Qualified (zero): corrosion rate is 50g/ (m2Hour) below
Unqualified (×): corrosion rate is greater than 50g/ (m2Hour)
Manufacturing
About manufacturing, injurious surface mark depth when casting for steel billet confirms scar by being coloured to surface,
And visually observed and observed by being cut into section, it is evaluated as a result, according to benchmark below.
Qualified, particularly excellent (◎): injurious surface mark is not observed
Qualified (zero): injurious surface mark depth is less than 0.2mm
Unqualified (×): injurious surface mark depth is 0.2mm or more
Bendability
Width 50mm × length 100mm × thickness 3.2mm test film is cut into from the hot rolled steel plate as above obtained, it is right
In the test film being cut into, implement 180 ° of curved processing (3T bending) in the case where inside clips the plate of 3 identical plate thickness,
The situation for observing bending section by visual observation, according to benchmark evaluation bendability below.
Qualified (zero): flawless
Unqualified (×): there is crackle
Fatigue durability
About fatigue durability, sample is cut in the length direction mode vertical with the rolling direction of steel plate, according to JIS Z
2275 (1978) carry out plain bending fatigue test under conditions of alternation (stress ratio: -1), frequency are 10Hz.
In alternation plain bending fatigue test, measurement recycles the stress for also not confirming fracture up to 1,000,000 times, will
The stress is as fatigue strength, according to benchmark evaluation fatigue durability below.
Qualified, particularly excellent (◎): fatigue strength is 200MPa or more
Qualified (zero): fatigue strength is 150MPa more than and less than 200MPa
Unqualified (×): fatigue strength is less than 150MPa
In addition, being cut into the test material having a size of 10mm × 10mm from the hot rolled steel plate as above obtained, protection is utilized
Coating covers end face and the back side for the test film being cut into be protected.By the test material aqueous sulfuric acid (temperature:
70 DEG C, concentration: 50 mass %) middle dipping 10 minutes, then, with 1mV/ seconds speed to cathode side scanning current potential until about
0.4V acquires cathodic polarization curve.Using obtained cathodic polarization curve, finding out current density by mapping is 0.1A/cm2
When current potential Va (V), find out with as the current density in the cathodic polarization curve of the No.18 of benchmark steel be 0.1A/cm2When
The potential difference of current potential Vg (V).It should be noted that using Hg/Hg (SO when carrying out potential measurement4) reference electrode.By result one
And remember in table 2.
According to table 2, example is in terms of resistance to sulfuric acid dew point corrosion, manufacturing, bendability and fatigue durability
It is excellent.
On the other hand, comparative example in resistance to sulfuric acid dew point corrosion, manufacturing, bendability and fatigue durability at least
Desired characteristic is not able to satisfy in one.
Claims (4)
1. a kind of corrosionproof steel against sulfuric acid at dew point, have in terms of quality % containing C:0.050~0.150%, Si:0.10~
0.80%, Mn:0.50~1.00%, P:0.050% or less, S:0.0020~0.0200%, Cu:0.20~0.50%, Ni:
0.10~0.80%, Cr:0.20~1.50%, Sb:0.050~0.300%, Co:0.002~0.020%, W:0.005~
0.200%, Ti:0.005~0.050%, Al:0.001~0.050% and N:0.0005~0.0050%, surplus by Fe and
Inevitable impurity constitute at being grouped as,
The content at S, Cu, Sb and W in being grouped as meets the relationship of following (1) formulas, and Cu, Ni, Sb and Co's contains
Amount meets the relationship of following (2) formulas,
0.50≤[%Cu] /≤5.00 ... (1) (10 × [%S]+[%Sb]+[%W])
0.50≤([%Ni]+5 × [%Co]) /≤2.50 ... (2) ([%Cu]+[%Sb])
Wherein, [%S], [%Cu], [%Ni], [%Sb], [%Co] and [%W] be respectively in being grouped as S, Cu, Ni,
The content (quality %) of Sb, Co and W.
2. corrosionproof steel against sulfuric acid at dew point as described in claim 1, wherein the content at C, Ti and N in being grouped as
Meet the relationship of following (3) formulas,
0.30≤[%Ti] /≤2.50 ... (3) (0.2 × [%C]+[%N])
Wherein, [%C], [%Ti] and [%N] is respectively the content (quality %) at C, Ti and N in being grouped as.
3. corrosionproof steel against sulfuric acid at dew point as claimed in claim 1 or 2, wherein
It is that the area ratio shared by 75% or more, pearlite phase is less than with the area ratio shared by the ferritic phase in structure of steel entirety
25%, the tissue other than the ferritic phase and pearlite phase adds up to shared structure of steel of the area ratio less than 5%, also,
Maximum Vickers hardness is 200 or less and average Vickers hardness is 80 or more.
4. corrosionproof steel against sulfuric acid at dew point according to any one of claims 1 to 3, wherein
Indicating that electric current of the corrosionproof steel against sulfuric acid at dew point in the aqueous sulfuric acid that temperature is 70 DEG C, concentration is 50 mass % is close
It is 0.1A/cm by current density in the cathodic polarization curve of the relationship of degree and current potential2When current potential when being set as Va (V),
The benchmark steel of the Va and the corrosionproof steel against sulfuric acid at dew point is in the cathodic polarization curve in the aqueous sulfuric acid
Current density is 0.1A/cm2When the relationship of current potential Vg (V) meet following (4) formulas,
Vg-Va > 0.03 ... (4).
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KR20200065990A (en) * | 2018-11-30 | 2020-06-09 | 주식회사 포스코 | Corrosion resistant steel having high resistance to corrosion at sulfuric and sulfuric/hydrochloric acid condensing environment and manufacturing method the same |
JP7348463B2 (en) * | 2019-01-11 | 2023-09-21 | 日本製鉄株式会社 | steel material |
JP7269467B2 (en) * | 2019-01-11 | 2023-05-09 | 日本製鉄株式会社 | steel |
CN114080465B (en) | 2019-07-09 | 2022-11-22 | 杰富意钢铁株式会社 | Seamless steel pipe having excellent sulfuric acid dew point corrosion resistance and method for producing same |
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CN115747637B (en) * | 2022-10-18 | 2024-02-13 | 武汉钢铁有限公司 | Economical ocean atmospheric corrosion resistant steel and production method thereof |
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