CN110268079A - Austenitic heat-resistant alloy and its manufacturing method - Google Patents
Austenitic heat-resistant alloy and its manufacturing method Download PDFInfo
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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Abstract
A kind of Austenitic heat-resistant alloy, wherein, the chemical composition of alloy is calculated as C:0.02~0.12% with quality %, Si:2.0% or less, Mn:3.0% or less, P:0.030% or less, S:0.015% or less, Cr:20.0% is more than and less than 28.0%, Ni: greater than 35.0% and be 55.0% or less, Co:0~20.0%, W:4.0~10.0%, Ti:0.01~0.50%, Nb:0.01~1.0%, Mo: less than 0.50%, Cu: less than 0.50%, Al:0.30% or less, N: less than 0.10%, Mg:0~0.05%, Ca:0~0.05%, REM:0~0.50%, V:0~1.5% , B:0~0.01%, Zr:0~0.10%, Hf:0~1.0%, Ta:0~8.0%, Re:0~8.0%, surplus: Fe and impurity, in the section vertical with length direction of aforementioned alloy, the shortest distance from central part to outer surface portion is 40mm or more, outer surface portion autstenitic grain size number be -2.0~4.0, in the form of precipitate existing for Cr amount satisfaction [CrPB/CrPS≤ 10.0], [YS is met under room temperatureS/YSB≤ 1.5] and [TSS/TSB≤1.2]。
Description
Technical field
The present invention relates to Austenitic heat-resistant alloy and its manufacturing methods.
In the past, in the thermal power generation boiler used under high temperature environment and chemical industry equipment etc., using SUS304H,
The 18-8 series austenitic stainless steel such as SUS316H, SUS321H, SUS347H is as device material.
But in recent years, for high efficiency, the whole world is all in the ultra-supereritical pressure for improve vapor (steam) temperature and pressure
Boiler creates.The use condition of device is obviously extremely harsh under this hot environment, therewith to using material to be wanted
The performance asked also becomes stringent.Also, the 18-8 series austenitic stainless steel used in the past is in addition to corrosion resistance, high temperature is strong
Degree, particularly the obvious insufficient situation of creep rupture strength.
To solve the above-mentioned problems, various researchs have been carried out up to now.For example, disclosing one kind in Patent Documents 1 to 4
The good highly corrosion resistant austenitic steel of elevated temperature strength.In addition, disclosing a kind of elevated temperature strength in patent document 5 and corrosion resistance is excellent
Different austenite stainless steel.According to Patent Documents 1 to 5, by by Cr amount improve to 20% or more and make its contain W and/or
Mo realizes the raising of elevated temperature strength.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application 61-179833 bulletin
Patent document 2: Japanese Unexamined Patent Application 61-179834 bulletin
Patent document 3: Japanese Unexamined Patent Application 61-179835 bulletin
Patent document 4: Japanese Unexamined Patent Application 61-179836 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2004-3000 bulletin
Summary of the invention
Problems to be solved by the invention
But structural elements large-scale as the device material for thermal power generation boiler and chemical industry equipment etc.,
Since it does not implement to be cold worked after hot rolling or hot forging but implement final heat treatment and to be used, thus crystal particle diameter compares
Greatly.Therefore, 0.2% offset yield strength as material specification and under defined room temperature and tensile strength be typically, there are than cold
Implement problem low when final heat treatment after processing.
Moreover, in large-scale structural elements, cooling velocity when heat treatment can have relatively big difference according to position, because
This, the amount of the solid solution element for helping to strengthen when using under high temperature as precipitate can be different according to position.Due to this
Point, there is also lead to the problem of creep rupture strength unevenness.Accordingly, it is difficult to the steel recorded in Patent Documents 1 to 5 is applied to big
The structural elements of type.
It is an object of the present invention to solve the above problems, provides and show sufficient room temperature as large-scale structural elements
Under 0.2% offset yield strength and the creep rupture strength under tensile strength and high temperature Austenitic heat-resistant alloy and
Its manufacturing method.
The solution to the problem
The present invention is made to solve the above problem, is with following Austenitic heat-resistant alloys and its manufacturing method
Main idea.
(1) a kind of Austenitic heat-resistant alloy, wherein the chemical composition of alloy is calculated as with quality %
C:0.02~0.12%,
Si:2.0% or less,
Mn:3.0% or less,
P:0.030% or less,
S:0.015% or less,
Cr:20.0% more than and less than 28.0%,
Ni: greater than 35.0% and for 55.0% or less,
Co:0~20.0%,
W:4.0~10.0%,
Ti:0.01~0.50%,
Nb:0.01~1.0%,
Mo: less than 0.50%,
Cu: less than 0.50%,
Al:0.30% or less,
N: less than 0.10%,
Mg:0~0.05%,
Ca:0~0.05%,
REM:0~0.50%,
V:0~1.5%,
B:0~0.01%,
Zr:0~0.10%,
Hf:0~1.0%,
Ta:0~8.0%,
Re:0~8.0%,
Surplus: Fe and impurity,
In the section vertical with length direction of aforementioned alloy, the shortest distance from central part to outer surface portion is 40mm
More than,
The autstenitic grain size number in aforementioned external surfaces portion is -2.0~4.0,
Extract residue analysis obtain in the form of precipitate existing for Cr amount meet following (i) formula,
Mechanical property under the room temperature of the Austenitic heat-resistant alloy meets following (ii) formulas and (iii) formula.
CrPB/CrPS≤10.0…(i)
YSS/YSB≤1.5…(ii)
TSS/TSB≤1.2…(iii)
Wherein, the meaning of each symbol in above-mentioned formula is as follows.
CrPB: at central part extract residue analysis obtain in the form of precipitate existing for Cr amount
CrPS: at outer surface portion extract residue analysis obtain in the form of precipitate existing for Cr amount
YSB: 0.2% offset yield strength of central part
YSS: 0.2% offset yield strength of outer surface portion
TSB: the tensile strength of central part
TSS: the tensile strength of outer surface portion
(2) Austenitic heat-resistant alloy according to above-mentioned (1), wherein afore mentioned chemical composition is contained in terms of quality %
It is selected from
Mg:0.0005~0.05%,
Ca:0.0005~0.05%,
REM:0.0005~0.50%,
V:0.02~1.5%,
B:0.0005~0.01%,
Zr:0.005~0.10%,
Hf:0.005~1.0%,
The and of Ta:0.01~8.0%
Re:0.01~8.0%
One or more of.
(3) Austenitic heat-resistant alloy according to above-mentioned (1) or (2), wherein aforesaid central portion is in mentioned length side
To 700 DEG C at 10,000 hours creep rupture strengths be 100MPa or more.
(4) a kind of manufacturing method of Austenitic heat-resistant alloy, has following process:
To steel ingot or the hot worked process of slab implementation with chemical composition described in above-mentioned (1) or (2)；And
Later, implement be heated to 1100~1250 DEG C range heat treatment temperature T (DEG C), keep 1000D/T~
The process that 1400D/T (minute) carries out the heat treatment of water cooling afterwards.
Wherein, D is in arbitrary point and outer rim in the section vertical with length direction of alloy in the outer rim in the section
Any other point between linear distance maximum value (mm).
(5) manufacturing method of the Austenitic heat-resistant alloy according to above-mentioned (4), wherein
In implementing aforementioned hot worked process, in direction implementation 1 time or more the processing substantially vertical with length direction.
The effect of invention
Unevenness in Austenitic heat-resistant alloy of the invention according to position engineering properties caused by different is few, in addition,
Creep rupture strength under high temperature is excellent.
Specific embodiment
Hereinafter, each feature of the invention is described in detail.
1. chemical composition
The restriction reason of each element is as follows.It should be noted that in the following description, " % " involved in content is indicated
" quality % ".
C:0.02~0.12%
C is for forming carbide and keeping disconnected as high temperature tensile strength, creep needed for Austenitic heat-resistant alloy
Necessary element for resistance to spalling.Therefore, C content needs to be set as 0.02% or more.But content is when being more than 0.12%, no
Non- solid solution carbides can be only generated, the carbide of Cr also will increase, and deteriorate the engineering properties such as ductility, toughness and weldability.Cause
This, C content is set as 0.02~0.12%.C content is preferably 0.05% or more, and preferably 0.10% or less.
Si:2.0% or less
Si is contained as deoxidant element.In addition, Si is for improving oxidative resistance, resistance to steam oxidation etc.
It is also effective element.In turn, or in casting material melt flows are made to become good element.But Si content is more than
When 2.0%, the generation of the equal intermetallic compound of σ can be promoted, therefore, the deterioration of structure stability under high temperature, cause toughness and
The reduction of ductility.In turn, weldability can also reduce.Therefore, Si content is set as 2.0% or less.In the feelings for paying attention to structure stability
Under condition, Si content is preferably set to 1.0% or less.It should be noted that having substantially ensured deoxidation by other elements
In the case of, it is set without the lower limit especially to Si content, still, is paying attention to deoxidation, oxidative resistance, the oxygen of resistance to vapor
In the case where property changed etc., Si content is preferably set to 0.05% or more, is more preferably set as 0.10% or more.
Mn:3.0% or less
Mn has deoxidation as Si, and has the S that will inevitably contain in alloy with the shape of sulfide
The fixed effect so as to improve the ductility under high temperature of formula.But Mn content can encourage σ equal intermetallic when being more than 3.0%
The precipitation of object, therefore the engineering properties such as structure stability and elevated temperature strength deteriorate.Therefore, Mn content is set as 3.0% or less.Mn contains
Amount preferably 2.0% or less, more preferably 1.5% or less.It should be noted that, although without being set to the lower limit of Mn content
It is fixed, but in the case where paying attention to the ductility improvement result under high temperature, Mn content is preferably set to 0.10% or more, is more preferably set as
0.20% or more.
P:0.030% or less
P is inevitably mixed into the alloy as impurity, significantly reduces the ductility under weldability and high temperature.Therefore, by P
Content is set as 0.030% or less.P content reduces as much as possible, is preferably set to 0.020% or less, is more preferably set as
0.015% or less.
S:0.015% or less
S is used as impurity to be inevitably mixed into the alloy as P, significantly reduces the ductility under weldability and high temperature.
Therefore, S content is set as 0.015% or less.In the case where paying attention to hot-workability, S content is preferably set to 0.010% or less,
It is more preferably set as 0.005% or less, is further preferably set as 0.003% or less.
Cr:20.0% is more than and less than 28.0%
Cr is the excellent work that volatilizees in the improvement of the corrosion resistances such as oxidative resistance, resistance to steam oxidation, high temperature corrosion
Important element.But content less than 20.0% when can not obtain said effect.On the other hand, increase in Cr content, is special
It is not to lead to the destabilization of tissue due tos σ phase is precipitated etc. when reaching 28.0% or more, weldability can also deteriorate.Therefore, Cr contains
Amount is set as 20.0% more than and less than 28.0%.Cr content is preferably 21.0% or more, more preferably 22.0% or more.In addition,
Cr content is preferably 26.0% or less, more preferably 25.0% or less.
Ni: greater than 35.0% and be 55.0% or less
Ni is the element for keeping austenite structure stable, is also to ensure that the important element of corrosion resistance.From with above-mentioned Cr content
Balance from the point of view of, Ni is needed containing having more than 35.0%.On the other hand, it will lead to cost increase when Ni content is excessive, therefore be set as
55.0% or less.Ni content is preferably 40.0% or more, more preferably 42.0% or more.In addition, Ni content is preferably 50.0%
Below, it is more preferably 48.0% or less.
Co:0~20.0%
Co must not necessarily contain, but since it stablizes austenite structure as Ni, it is strong to additionally aid creep rupture
The raising of degree, therefore a part of Ni can be replaced containing it.But content, when being more than 20.0%, effect saturation is economical
Property can also reduce.Therefore, Co content is set as 0~20.0%.Co content is preferably 15.0% or less.It should be noted that uncommon
Hope that Co content is preferably set to 0.5% or more in the case where obtaining said effect.
W:4.0~10.0%
W is not only solid-solution in matrix and facilitates the raising or conduct of creep rupture strength as solution strengthening element
Fe2The Laves phase or Fe of W type7W6The μ phase of type is precipitated, greatly improves the important element of creep rupture strength.But W content is small
Foregoing advantages can not be obtained when 4.0%.On the other hand, even if the W containing the amount for having more than 10.0%, strength-enhancing effect are also
Saturation, and the ductility under structure stability, high temperature can also deteriorate.Therefore, W content is set as 4.0~10.0%.W content is excellent
It is selected as 5.0% or more, more preferably 5.5% or more.In addition, W content is preferably 9.0% or less, more preferably 8.5% or less.
Ti:0.01~0.50%
Ti is the element for having the effect of forming carbonitride, improving creep rupture strength.But Ti content is less than
Sufficient effect can not be obtained when 0.01%, on the other hand, ductility when more than 0.50% under high temperature reduces.Therefore, Ti content
It is set as 0.01~0.50%.Ti content is preferably set to 0.05 or more, is more preferably set as 0.10% or more.In addition, Ti content is preferred
It is set as 0.40% or less, is more preferably set as 0.35% or less.
Nb:0.01~1.0%
Nb has the function of forming carbonitride to improve creep rupture strength.But Nb content less than 0.01% when
Sufficient effect can not be obtained, on the other hand, ductility when more than 1.0% under high temperature reduces.Therefore, Nb content be set as 0.01~
1.0%.Nb content is preferably 0.10% or more.In addition, Nb content is preferably 0.90% or less, more preferably 0.70% or less.
Mo: less than 0.50%
In the past, Mo was as being solid-solution in matrix and helped to improve the member of creep rupture strength as solution strengthening element
Element, it is considered to be there is the element with W equivalent effect.But the inventors of the present invention distinguish through research, be W containing aforementioned quantities and
In the alloy of Cr it is compound include Mo in the case where, for a long time use when σ phase be precipitated sometimes, therefore, sometimes result in creep
The reduction of breaking strength, ductility and toughness.Therefore, it is desirable that reducing Mo content as much as possible, it is set as less than 0.50%.It needs
Illustrate, Mo content is preferably limited to less than 0.20%.
Cu: less than 0.50%
In the present invention, Cu can reduce fusing point, reduce hot-workability and weldability.Therefore, it is desirable that as much as possible
Low content of Cu is dropped, is set as less than 0.50%.It should be noted that it is preferred that Cu content is limited to less than 0.20%.
Al:0.30% or less
Al is the deoxidier as molten steel and the element contained.But ductility of Al content when being more than 0.30%, under high temperature
Deterioration.Therefore, Al content is set as 0.30% or less.Al content is preferably 0.25% or less, more preferably 0.20% or less.It needs
Illustrate, it is desirable that obtaining said effect, Al content is preferably set to 0.01% or more, is more preferably set as 0.02%
More than.
N: less than 0.10%
N is with making the element of the stabilized effect of austenite structure, is inevitable in the case where conventional fusion method
The element that ground contains.But must in the present invention containing Ti, in order to avoid being formed because of TiN caused by Ti consume, it is preferably most
Possibly reduce Ti.But, be difficult in the case where air melting reduces to heavens, and therefore, N content is set as being less than
0.10%.
In the chemical composition of Austenitic heat-resistant alloy of the invention, surplus is Fe and impurity.Fe preferably comprises 0.1~
40.0%.In addition, when " impurity " refers to industrial manufacture alloy herein due to the raw materials such as ore, waste material, manufacturing process it is various
Reason and mixed ingredient are permitted ingredients in the range of will not generate adverse effect to the present invention.
Austenitic heat-resistant alloy of the invention can also contain 1 in Mg, Ca, REM, V, B, Zr, Hf, Ta and Re
Kind or more.
Mg, Ca and REM all have the effect fixed S in the form of sulfide so as to improve high temperature ductility.Therefore, uncommon
It hopes in the case where obtaining more good high temperature ductility, it can be in following range energetically containing one or more of these elements.
Mg:0.05% or less
Mg has the function of hindering the S of ductility under high temperature to fix in the form of sulfide so as to improve high temperature ductility, because
This, can contain Mg to obtain the effect.But Mg content when being more than 0.05% cleannes reduce, damage high temperature instead and prolong
Property.Therefore, 0.05% or less is set as containing Mg amount sometimes.Mg content is more preferably set as 0.02% or less, is further preferably set as
0.01% or less.On the other hand, in order to effectively obtain said effect, Mg content is preferably set to 0.0005% or more, more preferably
It is set as 0.001% or more.
Ca:0.05% or less
Ca has the function of hindering the S of ductility under high temperature to fix in the form of sulfide so as to improve high temperature ductility, because
This, can contain Ca to obtain the effect.But Ca content when being more than 0.05% cleannes reduce, damage high temperature instead and prolong
Property.Therefore, 0.05% or less is set as containing Ca amount sometimes.Ca content is more preferably set as 0.02% or less, is further preferably set as
0.01% or less.On the other hand, in order to effectively obtain said effect, Ca content is preferably set to 0.0005% or more, more preferably
It is set as 0.001% or more.
REM:0.50% or less
REM has the function of in the form of sulfide fixing S so as to improve high temperature ductility.In addition, REM, which has, improves steel
The Cr on surface2O3It protects the adaptation of overlay film, particularly improves the effect of oxidative resistance when aoxidizing repeatedly, and then also have
The effect for helping intercrystalline strengthening, improving creep rupture strength and creep rupture ductility.But REM content is when being more than 0.50%, oxygen
The field trashes such as compound become more, and processability and weldability are impaired.REM amount when therefore, containing REM is set as 0.50% or less.REM contains
Amount is more preferably set as 0.30% or less, is further preferably set as 0.15% or less.On the other hand, in order to effectively obtain above-mentioned effect
Fruit, REM content is preferably set to 0.0005% or more, is more preferably set as 0.001% or more, be further preferably set as 0.002% with
On.
It should be noted that REM refers to that Sc, Y and lanthanide series amount to 17 kinds of elements, the content of aforementioned REM indicates these
The total content of element.
The total content of above-mentioned Mg, Ca and REM can be 0.6% hereinafter, but more preferably 0.4% or less, further preferably
It is 0.2% or less.
V, B, Zr and Hf all have the effect for improving elevated temperature strength and creep rupture strength.Therefore, it is desirable that obtaining bigger
Elevated temperature strength and creep rupture strength in the case where, can in following range energetically containing a kind in these elements with
On.
V:1.5% or less
V has the function of forming carbonitride to improve elevated temperature strength and creep rupture strength.Therefore, in order to obtain this
A little effects can contain V.But V content, when being more than 1.5%, high temperature corrosion reduces, and then will lead to the analysis because of brittle phase
The deterioration of ductility and toughness caused by out.Therefore, 1.5% or less is set as containing V amount sometimes.V content is more preferably set as 1.0%
Below.On the other hand, in order to effectively obtain said effect, V content is preferably set to 0.02% or more, is more preferably set as 0.04%
More than.
B:0.01% or less
B is present in carbide or matrix, can not only promote be precipitated carbide miniaturization, also have strengthen crystal boundary from
And improve the effect of creep rupture strength.But B content, when being more than 0.01%, the ductility under high temperature reduces, and fusing point can also drop
It is low.B amount when therefore, containing B is set as 0.01% or less.B content is more preferably 0.008% or less, is more preferably
0.006% or less.On the other hand, in order to effectively obtain said effect, B content is preferably set to 0.0005% or more, more preferably
It is set as 0.001% or more, is further preferably set as 0.0015% or more.
Zr:0.10% or less
Zr is the miniaturization for promoting carbonitride and the member that creep rupture strength is improved as boundary-strengthening element
Element.But Zr content, when being more than 0.10%, the ductility under high temperature reduces.Therefore, 0.10% or less is set as containing Zr amount sometimes.
Zr content is more preferably 0.06% or less, is even more preferably 0.05% or less.On the other hand, above-mentioned in order to effectively obtain
Effect, Zr content are preferably set to 0.005% or more, are more preferably set as 0.01% or more.
Hf:1.0% or less
Hf has the function of helping precipitation strength as carbonitride, improves creep rupture strength, therefore, in order to obtain this
A little effects can contain Hf.But Hf content, when being more than 1.0%, processability and weldability are impaired.Therefore, containing Hf amount sometimes
It is set as 1.0% or less.Hf content is more preferably set as 0.8% or less, is further preferably set as 0.5% or less.On the other hand, in order to
Conscientiously said effect is obtained, Hf content is preferably set to 0.005% or more, is more preferably set as 0.01% or more, further preferably sets
It is 0.02% or more.
The total content of above-mentioned V, B, Zr and Hf are preferably 2.6% or less, more preferably 1.8% or less.
Ta and Re is solid-solution in the austenite as matrix, has solution strengthening effect.Therefore, iting is desirable to pass through solid solution
In the case that invigoration effect obtains higher elevated temperature strength and creep rupture strength, it can energetically contain this in following range
One of a little elements or both.
Ta:8.0% or less
Ta has the work for forming carbonitride and improving elevated temperature strength and creep rupture strength as solution strengthening element
With.Therefore, Ta can be contained in order to obtain these effects.But Ta content is when being more than 8.0%, processability and engineering properties by
Damage.Therefore, 8.0% or less is set as containing Ta amount sometimes.Ta content is more preferably set as 7.0% or less, is further preferably set as
6.0% or less.On the other hand, in order to effectively obtain said effect, Ta content is preferably set to 0.01% or more, is more preferably set as
0.1% or more, further preferably it is set as 0.5% or more.
Re:8.0% or less
Re mainly has the function of improving elevated temperature strength and creep rupture strength as solution strengthening element, therefore, is
Re can be contained by obtaining these effects.But Re content, when being more than 8.0%, processability and engineering properties are impaired.Therefore, contain
Sometimes Re amount is set as 8.0% or less.Re content is more preferably set as 7.0% or less, is further preferably set as 6.0%.Another party
Face, in order to effectively obtain said effect, Re content is preferably set to 0.01% or more, is more preferably set as 0.1% or more, is further
It is preferably set to 0.5% or more.
The total content of above-mentioned Ta and Re is preferably 14.0% or less, more preferably 12.0% or less.
2. grain size
The autstenitic grain size of outer surface portion is numbered: -2.0~4.0
When the austenite grain of outer surface portion spends thick, 0.2% offset yield strength and tensile strength under room temperature are lower,
And when meticulous, it cannot keep the high creep rupture strength under high temperature.Therefore, outer surface portion autstenitic grain size number be set as-
2.0~4.0.It should be noted that passing through the heat treatment temperature after appropriate adjustment hot-working in the manufacturing process of Ni based alloy
With retention time and cooling means, the grain size number of the outer surface portion after can making final heat treatment is above range.
3. size
The shortest distance from central part to outer surface portion: 40mm or more
As described above, in large-scale structural elements, in addition under room temperature 0.2% offset yield strength and tensile strength be lower
In addition, creep rupture strength unevenness is led to the problem of there is also the difference according to position.But austenite of the invention is resistance to
Thermalloy as large-scale structural elements show 0.2% offset yield strength under sufficient room temperature and tensile strength and
Creep rupture strength under high temperature.That is, effect of the invention is able to play for the component of heavy wall significantly.
It therefore,, will be from central part in the section vertical with length direction for Austenitic heat-resistant alloy of the invention
The shortest distance to outer surface portion is set as 40mm or more.In order to obtain effect brought by the present invention more significantly, from central part
The shortest distance to outer surface portion is preferably 80mm or more, more preferably 100mm or more.Here, for from central part to appearance
The shortest distance of face is the radius (mm) in section when such as alloy is cylindric, is the short of section when for quadrangular shape
The half (mm) of edge lengths.
It should be noted that as described later, heat-resisting alloy of the invention is for example, by casting to steel ingot or using continuous
It the obtained slab such as makes to implement obtained from the hot-working such as hot forging or hot rolling.Also, for the length direction of heat-resisting alloy, lead to
Often, it is the direction of the top and bottom of connection steel ingot using steel ingot, is length side using slab
To.
4. extract residue analysis obtain in the form of precipitate existing for Cr amount
CrPB/CrPS≤10.0…(i)
Wherein, (i) meaning of each symbol in formula is as follows.
CrPB: at central part extract residue analysis obtain in the form of precipitate existing for Cr amount
CrPS: at outer surface portion extract residue analysis obtain in the form of precipitate existing for Cr amount
In the manufacturing process of alloy, after the heat treatment after implementing hot-working, it can be generated not in crystal grain boundary or crystal grain
The precipitate (predominantly carbide) of the Cr of solid solution.Especially in the central part of alloy, due to speed cooling compared with outer surface portion
Spend slack-off, thus there are the increased tendencies of the amount of the precipitate of Cr.Therefore, CrPB/CrPSValue when being more than 10.0, cannot keep
High creep rupture strength under high temperature.On the other hand, although without setting CrPB/CrPSLower limit value, but from there are central parts
From the point of view of tendency of the amount of precipitate more than outer surface portion, it is preferably set to 1.0 or more.
It is carried out it should be noted that extracting residue analysis according to sequence below.Firstly, from alloy sample and length side
The test film for measuring Cr precipitate is acquired to the central part and outer surface portion in vertical section.Find out the table of above-mentioned test film
Area, then respectively in 10% -1% tetramethyl ammonium chloride of acetylacetone,2,4-pentanedione-methanol solution with 20mA/cm2Electrolytic condition only
It is electrolysed the base material of alloy sample completely.Then, 0.2 μm of filter of the solution after electrolysis is filtered, is mentioned in the form of residue
Take out precipitate.Then, after to the sour decomposition of residue progress is extracted, inductance coupling plasma emissioning spectral analysis device is used
(ICP-AES) it is analyzed, to determine the content (quality %) for the Cr for including in the form of the Cr precipitate not being dissolved, base
Cr is found out in its measured valuePB/CrPSValue.
5. engineering properties
YSS/YSB≤1.5…(ii)
TSS/TSB≤1.2…(iii)
Wherein, the meaning of each symbol in above-mentioned formula is as follows.
YSB: 0.2% offset yield strength of central part
YSS: 0.2% offset yield strength of outer surface portion
TSB: the tensile strength of central part
TSS: the tensile strength of outer surface portion
In large-scale structural elements, cooling velocity when due to heat treatment can be different according to position, thus exist each
The engineering properties at position generates the tendency of relatively large deviation.In large scale structure component, if 0.2% offset yield under room temperature is strong
Degree and tensile strength have larger difference with outer surface portion in center portion, then the difference according to position can occur and be unsatisfactory for specification
The problem of.
Therefore, the mechanical property under Austenitic heat-resistant alloy setting room temperature of the invention meet above-mentioned (ii) formula and
(iii) alloy of formula.It should be noted that, although without being set respectively to lower limit value, but from there are the machinery of central part
Characteristic is inferior to from the point of view of the tendency of the mechanical property of outer surface portion, and (ii) formula and (iii) formula are preferably set as 1.0 or more.
0.2% offset yield strength and tensile strength are found out in the following way: by machining, from the center of alloy
Portion and outer surface portion cut out parallel portion length for the pole tension test sheet of 40mm, in room temperature in a manner of being parallel to length direction
Lower implementation tension test, so as to find out.In addition, tension test is carried out according to JIS Z 2241 (2011).
6. creep rupture strength
Austenitic heat-resistant alloy of the invention due to using under high temperature environment, thus demanding elevated temperature strength, spy
It is not high creep rupture strength.Therefore, for heat-resisting alloy of the invention, the center portion thereof 10 at 700 DEG C of length direction,
Creep rupture strength is preferably 100MPa or more within 000 hour.
Creep rupture strength is found out by the following method.Firstly, by machining, from the central part of alloy to be parallel to
The mode of length direction cuts out the pole creep rupture of the diameter 6mm, gauge length 30mm that record in JIS Z 2241 (2011)
Test film.Then, implement creep rupture test in 700 DEG C, 750 DEG C, 800 DEG C of atmosphere, use Larson-Miller parameter
Method finds out the creep rupture strength of 700 DEG C, 10,000 hours.In addition, creep rupture test according to JIS Z 2271 (2010) into
Row.
7. manufacturing method
Austenitic heat-resistant alloy of the invention can be by steel ingot or slab implementation heat with above-mentioned chemical composition
Processing is to manufacture.It should be noted that in above-mentioned hot procedure, using the length direction of the final shape of alloy with as base
The steel ingot of material or the consistent mode of the length direction of slab are handled.Hot-working can be carried out only in length direction, but in order to
Higher working modulus, obtained tissue more evenly are assigned, can also be implemented 1 time to the substantially vertical direction of above-mentioned length direction
The above hot-working.In addition, the heat that also can according to need the further distinct methods such as implementation hot extrusion adds after the hot-working
Work.
When manufacturing Austenitic heat-resistant alloy of the invention, after above-mentioned operation, in order to inhibit the metal at each position
The unevenness of tissue and engineering properties keeps high creep rupture strength, implements final heat treatment described below.
Firstly, the alloy after hot-working to be heated to the heat treatment temperature T (DEG C) of 1100~1250 DEG C of range, at this
1000D/T~1400D/T (minute) is kept in range.Here, D is the diameter (mm) of alloy when such as alloy is cylindric,
It is diagonal distance (mm) when for quadrangular shape.That is, D is the outer rim in the section in the section vertical with length direction of alloy
On arbitrary point and the outer rim on any other point between linear distance maximum value (mm).
When above-mentioned heat treatment temperature is lower than 1100 DEG C, chromium carbide not being dissolved etc. increases, and creep rupture strength reduces.Separately
When on the one hand, more than 1250 DEG C, thus Grain Boundary Melting Down or the obvious coarsening of crystal grain cause ductility to reduce.It more preferably will be hot
Treatment temperature is set as 1150 DEG C or more, is more preferably set to 1230 DEG C or less.In addition, the above-mentioned retention time is less than 1000D/T
When (minute), central part is not dissolved chromium carbide increase, CrPB/CrPSBecome outside the framework of the present definition.On the other hand,
When more than 1400D/T (minute), the coarse grains of outer surface portion, autstenitic grain size number becomes the framework of the present definition
Outside.
After heating is kept, at once by alloy water cooling.This is because when cooling velocity is slack-off, especially in alloy
It can largely be generated in center portion, crystal grain boundary or crystal grain and not be dissolved Cr precipitate, may cause and be unable to satisfy above-mentioned (i) formula.
Hereinafter, carrying out more specific description to the present invention by embodiment, but the present invention is not limited to these embodiments.
Embodiment
Melting is carried out to the alloy with chemical composition shown in table 1 with high-frequency vacuum melting furnace, be made outer diameter 550mm,
The steel ingot of weight 3t.
[table 1]
Obtained steel ingot is processed into the cylindric of 120~480mm of outer diameter by being hot-forged, with the implementation of condition shown in table 2
Final heat treatment obtains alloy components sample.It should be noted that for alloy 1,2 and 4, after the hot forging of length direction and
Before final heat treatment, forged in the direction substantially vertical with length direction, it is then final in length direction further progress
Hot forging.
[table 2]
Table 2
* is indicated except the condition for the manufacturing method that the present invention limits.
For each sample, from the test film of outer surface portion acquisition structure observation, with sand paper and abrasive wheel to length direction
Section ground after, corroded with nitration mixture and carry out optical microscopy observation.The grain size number of viewing surface is according to JIS G
What is limited in 0551 (2013) is found out using the determination method for intersecting line segment (partial size).
Then, it acquires from the central part and outer surface portion in the section vertical with length direction of each sample for measuring Cr analysis
The test film of object out.The surface area of above-mentioned test film is found out, then respectively in 10% -1% tetramethyl ammonium chloride of acetylacetone,2,4-pentanedione-first
With 20mA/cm in alcoholic solution2Electrolytic condition be electrolysed the base material of alloy sample completely.Then, the solution after electrolysis is with 0.2
The filtering of μm filter, extracts precipitate in the form of residue.Then, after to the sour decomposition of residue progress is extracted, ICP-AES is carried out
Measurement to determine the content (quality %) for the Cr for including in the form of the Cr precipitate not being dissolved, and is based on this measurement
Value finds out CrPB/CrPSValue.
In addition, being cut in a manner of being parallel to length direction by machining from the central part and outer surface portion of each sample
Parallel portion length is the tension test sheet of 40mm out, implements tension test, at room temperature so as to find out 0.2% offset yield strength
And tensile strength.In turn, by machining, parallel portion is cut out in a manner of being parallel to length direction from the central part of each sample
Length is the creep rupture test piece of 30mm.Then, implement creep rupture test in 700 DEG C, 750 DEG C, 800 DEG C of atmosphere,
The creep rupture strength of 700 DEG C, 10,000 hours is found out using Larson-Miller parametric method.
Their result is shown in table 3 together.
[table 3]
Table 3
* it indicates except the framework of the present definition.
# is 700 DEG C, 10,000 small creep rupture strengths at present.
Alloy A and B are almost the same with the chemical composition of alloy 1 and the conjunction of identical final shape are made up of hot forging
Gold.However, retention time when heat treatment is except the range for the manufacturing condition that the present invention limits.Due to this point, for closing
Golden A, the grain size for causing outer surface portion are numbered except restriction range of the invention, YSS/YSBAnd TSS/TSBValue this
The result to become larger except the restriction range of invention, according to the deviation of the different mechanical properties at position.In addition, being caused for alloy B
Creep rupture strength except the restriction range of the invention, compared with alloy 1 obvious low result.
Alloy C, D and E are almost the same with the chemical composition of alloy 2, and identical final shape is made by hot forging
Alloy.Alloy C due to heat treatment temperature be lower than restriction range of the invention, cause outer surface portion grain size number
And CrPB/CrPSValue except restriction range of the invention, creep rupture strength obvious low result compared with alloy 2.
Alloy D due to heat treatment temperature be higher than restriction range of the invention, cause outer surface portion grain size compile
Number and YSS/YSBAnd TSS/TSBValue except restriction range of the invention, creep rupture strength it is obvious low compared with alloy 2
Result.
In addition, cooling means of the alloy E in final heat treatment is air-cooled rather than water cooling, cooling velocity is obviously slow, due to
This point, CrPB/CrPSValue except restriction range of the invention, as a result, creep rupture strength is obvious compared with alloy 2
It is low.On the other hand, the deviation for all meeting the mechanical property in the alloy 1~9 of restriction of the invention is small, creep rupture strength
Well.
Industrial availability
Austenitic heat-resistant alloy of the invention is few according to the deviation of position engineering properties caused by different, and under high temperature
Creep rupture strength it is excellent.Therefore, Austenitic heat-resistant alloy of the invention can suitably serve as and make under high temperature environment
The large scale structures component such as thermal power generation boiler and chemical industry equipment.
Claims (5)
1. a kind of Austenitic heat-resistant alloy, wherein the chemical composition of alloy is calculated as with quality %
C:0.02~0.12%,
Si:2.0% or less,
Mn:3.0% or less,
P:0.030% or less,
S:0.015% or less,
Cr:20.0% more than and less than 28.0%,
Ni: greater than 35.0% and for 55.0% or less,
Co:0~20.0%,
W:4.0~10.0%,
Ti:0.01~0.50%,
Nb:0.01~1.0%,
Mo: less than 0.50%,
Cu: less than 0.50%,
Al:0.30% or less,
N: less than 0.10%,
Mg:0~0.05%,
Ca:0~0.05%,
REM:0~0.50%,
V:0~1.5%,
B:0~0.01%,
Zr:0~0.10%,
Hf:0~1.0%,
Ta:0~8.0%,
Re:0~8.0%,
Surplus: Fe and impurity,
In the section vertical with length direction of the alloy, the shortest distance from central part to outer surface portion be 40mm with
On,
The autstenitic grain size number of the outer surface portion is -2.0~4.0,
The Cr amount existing for extract obtained from residue analysis in the form of precipitate meets following (i) formula,
Mechanical property under the room temperature of the Austenitic heat-resistant alloy meets following (ii) formulas and (iii) formula,
CrPB/CrPS≤10.0…(i)
YSS/YSB≤1.5…(ii)
TSS/TSB≤1.2…(iii)
Wherein, the meaning of each symbol in above-mentioned formula is as follows:
CrPB: at central part extract residue analysis obtain in the form of precipitate existing for Cr amount,
CrPS: at outer surface portion extract residue analysis obtain in the form of precipitate existing for Cr amount,
YSB: 0.2% offset yield strength of central part,
YSS: 0.2% offset yield strength of outer surface portion,
TSB: the tensile strength of central part,
TSS: the tensile strength of outer surface portion.
2. Austenitic heat-resistant alloy according to claim 1, wherein the chemical composition is contained in terms of quality % to be selected from
Mg:0.0005~0.05%,
Ca:0.0005~0.05%,
REM:0.0005~0.50%,
V:0.02~1.5%,
B:0.0005~0.01%,
Zr:0.005~0.10%,
Hf:0.005~1.0%,
The and of Ta:0.01~8.0%
Re:0.01~8.0%
One or more of.
3. according to claim 1 or Austenitic heat-resistant alloy as claimed in claim 2, wherein the central part is in the length
Spending 10,000 hours creep rupture strengths at 700 DEG C of direction is 100MPa or more.
4. a kind of manufacturing method of Austenitic heat-resistant alloy, has following process:
Steel ingot or the hot worked process of slab implementation with chemical composition described in claim 1 or claim 2；With
And
Later, implement to be heated to the heat treatment temperature T (DEG C) of 1100~1250 DEG C of range, keep 1000D/T~1400D/T
The process that (minute) carries out the heat treatment of water cooling afterwards,
Wherein, D be alloy the section vertical with length direction in the section outer rim on arbitrary point and the outer rim on its
The maximum value (mm) of linear distance between his arbitrary point.
5. the manufacturing method of Austenitic heat-resistant alloy according to claim 4, wherein
In implementing the hot worked process, in direction implementation 1 time or more the processing substantially vertical with length direction.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2017/004824 WO2018146783A1 (en) | 2017-02-09 | 2017-02-09 | Austenitic heat-resistant alloy and method for producing same |
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| Country | Link |
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| US (1) | US20200232081A1 (en) |
| EP (1) | EP3581669A4 (en) |
| JP (1) | JP6816779B2 (en) |
| KR (1) | KR20190117598A (en) |
| CN (1) | CN110268079A (en) |
| CA (1) | CA3052547C (en) |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109735757A (en) * | 2019-01-18 | 2019-05-10 | 株洲金佰利硬质合金有限公司 | A kind of sintered hard alloy boat contact material |
| CN112593120A (en) * | 2020-12-09 | 2021-04-02 | 上海蓝铸特种合金材料有限公司 | Nickel-based multi-element alloy, pipe made of nickel-based multi-element alloy and preparation method of pipe |
| CN113584350A (en) * | 2021-07-30 | 2021-11-02 | 湖北精利机电科技有限公司 | High-temperature oxidation resistant cast high-tungsten-nickel-based alloy and preparation method thereof |
| CN115461477A (en) * | 2020-04-30 | 2022-12-09 | 日本制铁株式会社 | Method for producing austenitic heat-resistant steel |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102471375B1 (en) | 2018-01-10 | 2022-11-28 | 닛폰세이테츠 가부시키가이샤 | Austenitic heat-resistant alloy, manufacturing method thereof, and austenitic heat-resistant alloy material |
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| CN102066594A (en) * | 2008-06-16 | 2011-05-18 | 住友金属工业株式会社 | Heat-resistant austenitic alloy, heat-resistant pressure-resistant member comprising the alloy, and process for producing the same |
| JP2014141713A (en) * | 2013-01-24 | 2014-08-07 | Nippon Steel & Sumitomo Metal | Austenitic heat-resistant alloy member |
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| KR100532877B1 (en) * | 2002-04-17 | 2005-12-01 | 스미토모 긴조쿠 고교 가부시키가이샤 | Austenitic stainless steel excellent in high temperature strength and corrosion resistance, heat resistant pressurized parts, and the manufacturing method thereof |
| JP4631986B1 (en) * | 2009-09-16 | 2011-02-23 | 住友金属工業株式会社 | Ni-based alloy product and manufacturing method thereof |
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- 2017-02-09 US US16/483,049 patent/US20200232081A1/en not_active Abandoned
- 2017-02-09 KR KR1020197026299A patent/KR20190117598A/en not_active Application Discontinuation
- 2017-02-09 JP JP2018566714A patent/JP6816779B2/en active Active
- 2017-02-09 CN CN201780086046.1A patent/CN110268079A/en not_active Withdrawn
- 2017-02-09 CA CA3052547A patent/CA3052547C/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2018146783A1 (en) | 2018-08-16 |
| JPWO2018146783A1 (en) | 2019-11-07 |
| JP6816779B2 (en) | 2021-01-20 |
| CA3052547A1 (en) | 2018-08-16 |
| CA3052547C (en) | 2020-06-02 |
| EP3581669A1 (en) | 2019-12-18 |
| EP3581669A4 (en) | 2020-08-19 |
| US20200232081A1 (en) | 2020-07-23 |
| KR20190117598A (en) | 2019-10-16 |
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Application publication date: 20190920 |