CN105463306B - A kind of fluoride molten salt and/or molten chloride corrosion protection method - Google Patents
A kind of fluoride molten salt and/or molten chloride corrosion protection method Download PDFInfo
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- CN105463306B CN105463306B CN201510368867.7A CN201510368867A CN105463306B CN 105463306 B CN105463306 B CN 105463306B CN 201510368867 A CN201510368867 A CN 201510368867A CN 105463306 B CN105463306 B CN 105463306B
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Abstract
The invention discloses a kind of fluoride molten salt and/or molten chloride corrosion protection methods.It includes the following steps: the fluoride molten salt that stainless steel or corrosion resistant alloy are on active service and/or Chlorides molten salts and CrF2And/or CrCl2It is uniformly mixed；Cr2+Concentration be 100~5000ppm.Corrosion protection method simple possible of the invention, is easy to operate and control safety and environmental protection；The corrosion rate of stainless steel and corrosion resistant alloy in high-temperature fluorination object and molten chloride can be significantly reduced, intercrystalline corrosion problem is effectively inhibited and slow down, improves its service life in high-temperature fluorination object and molten chloride；The present invention can not only widen the selection range of fluoride and molten chloride medium alloy structure material, reduce device fabrication and processing cost, the unique advantage that fluoride and molten chloride can also be made full use of passes heat storage medium as new type high temperature and promotes and applies in high temperature energy field.
Description
Technical field
The present invention relates to protection of materials fields, and in particular to a kind of fluoride molten salt and/or molten chloride corrosion
Means of defence.
Background technique
Fluoride molten salt and molten chloride as a kind of new type high temperature pass heat storage medium high temperature for hydrogen production, nuclear reactor,
The energy fields such as solar energy thermal-power-generating, nuclear fuel post-processing, fuel cell have broad application prospects.However due to fluoride
Fused salt and molten chloride have corrosive nature to structural metallic materials, limit it in the extensive use in above-mentioned field.
Commercial stainless steel and corrosion resistant alloy are ASME standard engineering material, be widely used in nuclear energy, thermoelectricity, aviation,
The high-temperature fields such as space flight, especially stainless steel are even more to be widely applied because of its price advantage.These stainless steels and anti-corrosion conjunction
Gold has a preferable corrosion resistance in various aqueous solutions and high-temperature oxidation environment, surface will form chromium-rich passivating film or
Oxidation film, the skin covering of the surface have protective effect to alloy substrate, can inhibit further corroding for alloy, make it have good height
Warm nature energy and corrosion resistance.However stainless steel and corrosion resistant alloy can occur in fluoride molten salt and/or molten chloride it is bright
Aobvious corrosion, mainly due to improving its corrosion proof important alloying element chromium in stainless steel and corrosion resistant alloy in fluoride molten salt
It and/or is thermodynamic instability element in Chlorides molten salts, it may occur that selective dissolution not will form protectiveness surface
Film.
For this purpose, U.S.'s Oak Ridge National Laboratory (ORNL) specially has developed Ni-based Hastelloy N alloy.The alloy nickel
It is high with molybdenum element content, there is fabulous corrosion resistance in fluorination fused salt.However 700 DEG C or more its corrosion resisting properties and high temperature power
Reduced performance is learned, 700 DEG C of corrosion resisting properties below also have limitation.Meanwhile when containing H in fused salt2O, HF and metal oxidation
The impurity such as object, or when having the dissimilar materials such as graphite, pure nickel, Hastelloy N alloy can also occur obviously to corrode, and the alloy valence
Lattice are expensive, do not commercially produce both at home and abroad.To inhibit fused salt corrosion problem, U.S.'s Oak Ridge National Laboratory (ORNL) also benefit
With to LiF-BeF2(FLiBe) it is inserted into the corrosion that metallic beryllium stick inhibits 316 stainless steels in fused salt circuit, however contains beryllium in this method
Compound is severe poisonous chemicals, extremely harmful to experiment operator and environment.The pungent university of University of Wisconsin-Madison (UWM) utilizes addition
Metal zirconium inhibits 316L stainless steel to corrode in melting LiF-NaF-KF (FLiNaK) fused salt, however metal zirconium is not only in this method
Graphite can be seriously damaged, while zirconium deposits to alloy surface, the embrittlement of alloy can be caused.
Therefore, it develops a kind of simple possible, at low cost, safety and environmental protection, be easy to operate and control, effective high temperature fluorine
Compound fused salt and/or molten chloride corrosion protection method are a problem to be solved.
Summary of the invention
The present invention overcomes the chromiums in stainless steel and corrosion resistant alloy in the prior art in fluoride molten salt and/or chlorination
Selective dissolution occurs for thermodynamic instability in object molten salt system, can not form protectiveness skin covering of the surface, and occur obviously to corrode lacks
It falls into, provides a kind of fluoride molten salt and/or molten chloride corrosion protection method.Corrosion protection method of the invention simply may be used
Row safety and environmental protection, is easy to operate and control, significant effect；Can significantly reduce stainless steel and corrosion resistant alloy in high-temperature fluorination object and
Corrosion rate in molten chloride especially effectively can inhibit and slow down the intercrystalline corrosion problem of stainless steel, improve stainless
The service life of steel and corrosion resistant alloy in high-temperature fluorination object and molten chloride；In addition, the present invention can not only widen fluoride
With the molten chloride medium selection range of alloy structure material, device fabrication and processing cost are reduced, while can also be abundant
Using the unique advantage of fluoride and molten chloride, heat storage medium is passed as new type high temperature and is answered in the popularization of high temperature energy field
With；Even if the present invention also has protective action to alloy in the case where there is the carbon-based materials such as graphite to accelerate alloy corrosion.
The present inventor has found that corrosion product is flat in the corrosion rate and fused salt of material by lot of experiments
Weighing apparatus concentration has important relationship, i.e., when corrosion product concentration reaches balance in fused salt, material will not continue to corrode.Into one
The dissolution of Cr element mainly occurs in high-temperature fluorination object and/or molten chloride for step discovery, stainless steel and corrosion resistant alloy, therefore
Its corrosion rate is related with concentration of the Cr element in fluoride and/or molten chloride.Cr member is known as Cr (II) and Cr (III)
Two kinds of oxidation state, by comparative experiments, inventor's discovery, which is worked as in fused salt, is added CrF3Or CrCl3When, it cannot not only inhibit alloy rotten
Erosion, exacerbates the corrosion of alloy instead；But as addition CrF2Or CrCl2When, alloy corrosion can be significantly suppressed.Wherein,
Cr2+Concentration be affected to the corrosion protection of stainless steel in molten salt system or corrosion resistant alloy: work as Cr2+Concentration it is too low when, rise
Less than the effect of corrosion protection, as Cr in molten salt system2+Excessive concentration when, other problems may be brought, such as change fused salt
Physicochemical characteristics etc..
The present invention solves above-mentioned technical problem by the following technical programs.
The present invention provides a kind of fluoride molten salt and/or molten chloride corrosion protection methods comprising following steps:
The fluoride molten salt and/or Chlorides molten salts and CrF that stainless steel or corrosion resistant alloy are on active service2And/or CrCl2It is uniformly mixed,
?；Wherein, Cr2+Concentration be 100ppm~5000ppm.
In the present invention, when the system is fluoride molten salt, to keep the pure of fused salt, CrF is preferably added2Mixing
Uniformly.When the system is molten chloride, to keep the pure of fused salt, CrCl is preferably added2It is uniformly mixed.When described
When system is the fused salt mixt system of molten chloride and fluoride molten salt, CrF can be added2And/or CrCl2, it is only necessary to meet Cr2+
Concentration be that the effect of corrosion protection can be realized in 100ppm~5000ppm.
In the present invention, effect based on corrosion protection and from the point of view of reducing cost, the Cr2+Concentration preferably
For 1000ppm~1500ppm.
In the present invention, the CrF2To be in the art conventional, preferably purity is not less than 95% CrF2, it is more preferably hundred
The CrF that Ling Wei Science and Technology Ltd. purity is 95%2。
In the present invention, the CrCl2To be in the art conventional, preferably purity is the CrCl not less than 97%2, more preferably
Purity is the CrCl not less than 99.9%2, the CrCl for being most preferably 99.9% for Alpha's reagent Co., Ltd, U.S. purity2.It is pure
The CrCl that degree is 97%2Preferably it is purchased from U.S. Alpha reagent Co., Ltd.
In the present invention, the stainless steel is routine in the art, is preferably comprised austenitic stainless steel, ferrite stainless
One of steel, austenite-ferrite (two-phase) stainless steel, martensitic stain less steel and precipitation-hardening stainless steel are a variety of, more preferably
Ground is austenitic stainless steel.The austenitic stainless steel is routine in the art, and it is stainless to be preferably comprised 316 stainless steels, 316L
One of steel, 304 stainless steels and 304L stainless steel are a variety of.
In the present invention, the corrosion resistant alloy be it is in the art conventional, be preferably comprised iron abros and/or Ni-based
Corrosion resistant alloy more preferably includes Inconel 800, Inconel 600, Inconel 617,276 and of Hastelloy C
One of Hastelloy N or a variety of.
In the present invention, the fluoride is routine in the art, is preferably comprised LiF, NaF, KF, BeF2、MgF2、ZrF4
And NaBF4One of or it is a variety of.
In the present invention, the chloride is routine in the art, is preferably comprised NaCl, KCl, MgCl2And CaCl2In
It is one or more.
In the present invention, the mixed operation and assembling process are preferably carried out under inert atmosphere.The indifferent gas
Atmosphere is routine in the art, generally refers to the atmosphere that do not reacted with molten salt system of the invention, chloride or fluoride, compared with
It goodly is nitrogen and/or argon gas.
In the present invention, the system is preferably static state constant-temperature system or dynamic temperature difference system.
It preferably can also include carbon-based material, such as graphite in the system in the present invention.In general, if in system
Containing carbon-based materials such as graphite, carbon-based material can accelerate the corrosion of stainless steel or corrosion resistant alloy.However, corrosion protection of the invention
Even if method also has protective action to stainless steel or corrosion resistant alloy in the case where there is the carbon-based materials accelerated corrosion such as graphite.
In the present invention, CrF is added using into fluoride molten salt and/or Chlorides molten salts2And/or CrCl2To improve
Chromium ion concentration in fused salt, reduction are protected from the outside diffusion dissolution rate of chromium in rust steel or alloy, inhibit by protection gold
The corrosion of category.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
1, corrosion protection method simple possible of the invention, safety and environmental protection, be easy to operate and control, significant effect.Only need
By appropriate CrF2And/or CrCl2Be added in fluoride molten salt and/or molten chloride, be uniformly mixed, can reduce stainless steel and
The corrosion rate of corrosion resistant alloy.In high-temperature fluorination object fused salt and/or high-temperature chlorine compound fused salt, the present invention can be significantly reduced not
The corrosion rate of rust steel or corrosion resistant alloy especially effectively can inhibit and slow down the intercrystalline corrosion problem of stainless steel, improve not
Rust steel and corrosion resistant alloy service life have good promotional value.
2, the present invention can not only widen the selection range of fluoride and molten chloride medium alloy structure material, reduce
Device fabrication and processing cost, while the unique advantage of fluoride and molten chloride can also be made full use of, as new type high temperature
Heat storage medium is passed to promote and apply in high temperature energy field.
3, required CrF2And/or CrCl2Concentration is not high, to molten salt system and alloy Small side effects.In addition, the present invention is corroded
Even if the method for protection also has protective action to alloy in the case where there is graphite to accelerate alloy corrosion.
Detailed description of the invention
Fig. 1 is the SEM surface topography map of 316L stainless steel after comparative example 1 is handled.
Fig. 2 is the SEM Cross Section Morphology figure of 316L stainless steel after comparative example 1 is handled.
Fig. 3 is the SEM surface topography map of 316L stainless steel after embodiment 1 is handled.
Fig. 4 is the SEM Cross Section Morphology figure of 316L stainless steel after embodiment 1 is handled.
Fig. 5 is the SEM surface topography map of 316L stainless steel after embodiment 2 is handled.
Fig. 6 is the SEM Cross Section Morphology figure of 316L stainless steel after embodiment 2 is handled.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
In following embodiments, purity be 95% CrF2It is purchased from lark prestige Science and Technology Ltd., purity is 97%
CrCl2, purity 99.9% CrCl2It is purchased from Alpha's reagent Co., Ltd, the U.S..
Embodiment 1
The molten salt system of the present embodiment is static state constant-temperature system.
1, the pretreatment of 316L stainless steel
Using wire cutting method by 316L stainless steel cut at having a size of 10mm × 10mm × 2mm sample, and in sample
It is upper to make a call to the hole that a diameter is φ 2mm.All specimen surfaces are polishing to 2000 mesh with SiC sand paper step by step, then successively spend from
Sub- water and dehydrated alcohol ultrasonic cleaning, the drying of hair dryer cold wind.
2, corrosion protection method of the 316L stainless steel in 700 DEG C of FLiNaK fused salt
Pretreated 316L stainless steel sample is added in graphite crucible, 200g solid-state LiF-KF-NaF (46.5- is weighed
11.5-42mol%, FLiNaK) salt, the CrF of 500ppm is then added into FLiNaK salt2(purity 95%) is uniformly mixed.
Graphite crucible is added in mixed salt, graphite cover is covered, graphite crucible is put into 316 stainless steel crucible of outer layer, and will not
Become rusty steel crucible welded seal.To avoid the impurity such as oxygen and moisture in air from being mixed into fused salt, reaction kettle it is entire assembly and
Welding process carries out in the glove box of argon atmosphere protection.The autoclave body being sealed is put into Muffle furnace in 700 DEG C of constant temperature
Keep the temperature 200h.
Embodiment 2
The molten salt system of the present embodiment is static state constant-temperature system.
1, the pretreatment of 316L stainless steel
Using wire cutting method by 316L stainless steel cut at having a size of 10mm × 10mm × 2mm sample, and in sample
It is upper to make a call to the hole that a diameter is φ 2mm.All specimen surfaces are polishing to 2000 mesh with SiC sand paper step by step, then successively spend from
Sub- water and dehydrated alcohol ultrasonic cleaning, the drying of hair dryer cold wind.
2, corrosion protection method of the 316L stainless steel in 700 DEG C of FLiNaK fused salt
Pretreated 316L stainless steel sample is added in graphite crucible, 200g solid-state LiF-KF-NaF (46.5- is weighed
11.5-42mol%, FLiNaK) salt, the CrF of 2000ppm is then added into FLiNaK salt2(purity 95%), mixing are equal
It is even.Graphite crucible is added in mixed salt, graphite cover is covered, graphite crucible is put into 316 stainless steel crucible of outer layer, and will
Stainless steel crucible welded seal.To avoid the impurity such as oxygen and moisture in air from being mixed into fused salt, the entire assembly of reaction kettle
It is carried out in the glove box of argon atmosphere protection with welding process.The autoclave body being sealed is put into Muffle furnace in 700 DEG C of perseverances
Temperature heat preservation 200h.
Embodiment 3
The molten salt system of the present embodiment is static state constant-temperature system.
1, the pretreatment of 304 stainless steels
Using wire cutting method by 304 stainless steel cuts at having a size of 10mm × 10mm × 2mm sample, and on sample
Make a call to the hole that a diameter is φ 2mm.All specimen surfaces are polishing to 2000 mesh with SiC sand paper step by step, then successively use deionization
Water and dehydrated alcohol ultrasonic cleaning, the drying of hair dryer cold wind.
2, KCl-MgCl of 304 stainless steels at 750 DEG C2Corrosion protection method in fused salt
Pretreated 304 stainless steel sample is added in graphite crucible, 200g solid-state KCl-MgCl is weighed2(68-
32mol%) salt, then to KCl-MgCl2The CrCl of 1000ppm is added in salt2(purity 99.9%) is uniformly mixed.It will mixing
Graphite crucible is added in rear salt, covers graphite cover, graphite crucible is put into 316 stainless steel crucible of outer layer, and by stainless steel earthenware
Crucible welded seal.To avoid the impurity such as oxygen and moisture in air from being mixed into fused salt, reaction kettle is entirely assembled and was welded
Cheng Jun is carried out in the glove box that argon atmosphere is protected.The autoclave body being sealed is put into Muffle furnace and is kept the temperature in 750 DEG C of constant temperature
500h。
Embodiment 4
The molten salt system of the present embodiment is static state constant-temperature system.
1, the pretreatment of Inconel 800
Inconel 800 is cut into having a size of 10mm × 10mm × 2mm sample using wire cutting method, is beaten on sample
The hole that one diameter is φ 2mm.All specimen surfaces are polishing to 2000 mesh with SiC sand paper step by step, then successively use deionized water
It is cleaned by ultrasonic with dehydrated alcohol, the drying of hair dryer cold wind.
2, KF-ZrF of the Inconel 800 at 800 DEG C4Corrosion protection method in fused salt
Pretreated 800 sample of Inconel is added in graphite crucible, 300g solid-state KF-ZrF is weighed4(58-
42mol%) salt, then to KF-ZrF4The CrF of 5000ppm is added in salt2(purity 95%) is uniformly mixed.It will be mixed
Graphite crucible is added in salt, covers graphite cover, graphite crucible is put into 316 stainless steel crucible of outer layer, and stainless steel crucible is welded
Connect sealing.To avoid the impurity such as oxygen and moisture in air from being mixed into fused salt, the entire assembly of reaction kettle and welding process are equal
It is carried out in the glove box of argon atmosphere protection.The autoclave body being sealed is put into Muffle furnace and keeps the temperature 300h in 800 DEG C of constant temperature.
Embodiment 5
The fused salt of the present embodiment is static state constant-temperature system
1, the pretreatment of Inconel 600
Inconel 600 is cut into having a size of 5mm × 10mm × 2mm sample by wire cutting method, makes a call to one on each sample
A diameter is the hole of φ 1.5mm.All specimen surfaces are polishing to 2000 mesh with SiC sand paper step by step, then successively use deionized water
It is cleaned by ultrasonic with dehydrated alcohol, the drying of hair dryer cold wind.
2, NaF-CaCl of the Inconel 600 at 750 DEG C2Corrosion protection method in fused salt
Pretreated 600 sample of Inconel is added in graphite crucible, 300g solid state N aF-CaCl is weighed2(40-
60mol%) salt, then to NaF-CaCl2The CrCl of 100ppm is added in salt2(purity 97%) is uniformly mixed.After mixing
Salt graphite crucible is added, cover graphite cover, graphite crucible be put into 316 stainless steel crucible of outer layer, and by stainless steel crucible
Welded seal.To avoid the impurity such as oxygen and moisture in air from being mixed into fused salt, the entire assembly of reaction kettle and welding process
Carried out in the glove box of nitrogen atmosphere protection.The autoclave body being sealed is put into Muffle furnace and keeps the temperature 500h in 750 DEG C of constant temperature.
Embodiment 6
The fused salt of the present embodiment is static state constant-temperature system
1, the pretreatment of Hastelloy N alloy
Hastelloy N alloy is cut into having a size of 5mm × 10mm × 2mm sample by wire cutting method, on each sample
Make a call to the hole that a diameter is φ 1.5mm.All specimen surfaces are polishing to 2000 mesh with SiC sand paper step by step, then successively spend from
Sub- water and dehydrated alcohol ultrasonic cleaning, the drying of hair dryer cold wind.
2, corrosion protection method of the Hastelloy N alloy in 850 DEG C of LiF-KF-NaF fused salt
Pretreated Hastelloy N alloy sample is added in graphite crucible, 300g solid-state LiF-KF-NaF is weighed
Then the CrF of 5000ppm is added in (46.5-11.5-42mol%, FLiNaK) salt into LiF-KF-NaF salt2(purity is
95%) it, is uniformly mixed.Graphite crucible is added in mixed salt, covers graphite cover, it is stainless that graphite crucible is put into outer layer 316
In steel crucible, and by stainless steel crucible welded seal.To avoid the impurity such as oxygen and moisture in air from being mixed into fused salt, react
The entire assembly of kettle and welding process carry out in the glove box of nitrogen atmosphere protection.The autoclave body being sealed is put into Muffle furnace
In in 850 DEG C of constant temperature keep the temperature 800h.
Embodiment 7
The fused salt of the present embodiment is static state constant-temperature system
1, the pretreatment of Hastelloy C276 alloy
Hastelloy C276 alloy is cut into having a size of 5mm × 10mm × 2mm sample, each sample by wire cutting method
It is upper to make a call to the hole that a diameter is φ 1.5mm.All specimen surfaces are polishing to 2000 mesh with SiC sand paper step by step, then successively spend
Ionized water and dehydrated alcohol ultrasonic cleaning, the drying of hair dryer cold wind.
2, NaF-NaBF of the Hastelloy C276 alloy at 800 DEG C4Corrosion protection method in fused salt
Pretreated Hastelloy C276 alloy sample is added in graphite crucible, 300g solid state N aF- is weighed
NaBF4(8-92mol%) salt, then to NaF-NaBF4The CrF of 1000ppm is added in salt2(purity 95%) is uniformly mixed.
Graphite crucible is added in mixed salt, graphite cover is covered, graphite crucible is put into 316 stainless steel crucible of outer layer, and will not
Become rusty steel crucible welded seal.To avoid the impurity such as oxygen and moisture in air from being mixed into fused salt, reaction kettle it is entire assembly and
Welding process carries out in the glove box of nitrogen atmosphere protection.The autoclave body being sealed is put into Muffle furnace in 800 DEG C of constant temperature
Keep the temperature 500h.
Embodiment 8
The fused salt of the present embodiment is dynamic temperature difference system.
1, the pretreatment of 316 stainless steels
316 stainless steel cuts at having a size of 5mm × 10mm × 2mm sample, are made a call to one on each sample by wire cutting method
Diameter is the hole of φ 1.5mm.All specimen surfaces are polishing to 2000 mesh with SiC sand paper step by step, then successively with deionized water and
Dehydrated alcohol ultrasonic cleaning, the drying of hair dryer cold wind.
2,316 stainless steels in FLiNaK temperature difference circuit (750 DEG C of high temperature, 650 DEG C of low temperature) corrosion protection method
316 stainless steel samples are fixed on inside and fill solid-state LiF-KF-NaF (46.5-11.5-42mol%, FLiNaK)
316 stainless steel U-tube one end of salt.Contain 1500ppm CrF in the FLiNaK salt2(purity 95%).U-tube both ends are used
Flange seal, flange are equipped with water-cooled jacket.It is protected with argon gas inside.U-tube there is into sample heating one end to 750 DEG C, the other end
It is heated to 650 DEG C.When temperature reaches set temperature, 316 stainless steel samples are inserted into FLiNaK fused salt, are kept the temperature in 750 DEG C
1000h。
Comparative example 1
CrF is not added in this comparative example2, other control conditions are same as Example 1.
Effect example 1
Examples 1 to 7 and comparative example 1 after the test, take out autoclave body, and cooled to room temperature cuts crucible, take out examination
Sample.After embodiment 8 tests the test period, sample is promoted, is allowed to separate with fused salt.Cooled to room temperature opens flange,
Take out sample.
Using precision be the electronic balance weighing Examples 1 to 2 of 0.01mg, 316L stainless steel sample is corroded in comparative example 1
Front and back weight change.The results are shown in Table 1.
It can be obtained by table 1, obvious corrosion weight loss occurs for 316L stainless steel in comparative example 1, and this is mainly due to Cr in stainless steel
Caused by the selective dissolution of element, illustrate that 316L stainless steel occurs obviously to corrode in FLiNaK fused salt.In embodiment 1,2
316L stainless steel is in addition CrF2FLiNaK fused salt in surrosion occurs, this is mainly due to added CrF2Inhibit 316L
The dissolution of Cr element in stainless steel, while metal cations Fe in fused salt and Ni etc. deposit to 316L stainless steel surface, cause to increase
Weight.Thus illustrate, CrF is added in embodiment 1,22It can inhibit corrosion of the 316L stainless steel in FLiNaK fused salt.
Corrosion weight loss of the table 1316L stainless steel in 700 DEG C of FLiNaK
Utilize sample corrosion front and back weight change in the electronic balance weighing embodiment 3~8 that precision is 0.01mg.Sample exists
Surrosion occurs in fused salt, shows that sample does not corrode.Thus illustrate, to fluoride molten salt and/or molten chloride
Appropriate CrF is added in system2And/or CrCl2It can inhibit the corrosion of stainless steel and corrosion resistant alloy.
Effect example 2
Fig. 1 is scanning electron microscope (SEM) surface topography map of 316L stainless steel after comparative example 1 is handled.Fig. 2 is comparison
Scanning electron microscope (SEM) Cross Section Morphology figure of 316L stainless steel after the processing of example 1.By Fig. 1 and Fig. 2 it is found that in comparative example 1,
316L stainless steel is being not added with CrF2FLiNaK fused salt in obvious intercrystalline corrosion occurs.
Fig. 3 is scanning electron microscope (SEM) surface topography map of 316L stainless steel after embodiment 1 is handled.Fig. 4 is to implement
Scanning electron microscope (SEM) Cross Section Morphology figure of 316L stainless steel after the processing of example 1.By Fig. 3,4 it is found that in addition CrF2It is (dense
In FLiNaK fused salt of the degree for 500ppm), since the impurity in fused salt deposits to material surface, 316L stainless steel surface occurs
The deposit of rich Fe and Ni illustrates that 316L stainless steel does not have by its Cross Section Morphology it is found that specimen surface and matrix do not have significant difference
Have and corrodes.Therefore compared with Fig. 1, Fig. 2, the 316L stainless steel intercrystalline corrosion of embodiment 1 is inhibited, and is almost stale-proof
Erosion.
Fig. 5 is scanning electron microscope (SEM) surface topography map of 316L stainless steel after embodiment 2 is handled.Fig. 6 is to implement
Scanning electron microscope (SEM) Cross Section Morphology figure of 316L stainless steel after the processing of example 2.By Fig. 5,6 it is found that in addition CrF2It is (dense
In FLiNaK fused salt of the degree for 2000ppm), since the impurity in fused salt deposits to material surface, 316L stainless steel surface occurs
The deposit of rich Fe and Ni by its Cross Section Morphology it is found that specimen surface and matrix do not have significant difference illustrates 316L stainless steel
There is no corrosion.Therefore compared with Fig. 1, Fig. 2, the 316L stainless steel intercrystalline corrosion of embodiment 2 is inhibited, and is almost stale-proof
Erosion.
Claims (10)
1. a kind of fluoride molten salt and/or molten chloride corrosion protection method, which is characterized in that its include the following steps: by
The fluoride molten salt and/or Chlorides molten salts and CrF that stainless steel or corrosion resistant alloy are on active service2And/or CrCl2It is uniformly mixed, i.e.,
It can；Wherein, Cr2+Concentration be 100ppm~5000ppm.
2. the method as described in claim 1, which is characterized in that the Cr2+Concentration be 1000ppm~1500ppm.
3. the method as described in claim 1, which is characterized in that the CrF2It is not less than 95% CrF for purity2；
And/or the CrCl2It is not less than 97% CrCl for purity2。
4. method as claimed in claim 3, which is characterized in that the CrCl2It is not less than 99.9% CrCl for purity2。
5. the method as described in claim 1, which is characterized in that the stainless steel includes austenitic stainless steel, ferrite stainless
One of steel, austenite-ferrite two phase stainless steel, martensitic stain less steel and precipitation-hardening stainless steel are a variety of；
And/or the corrosion resistant alloy includes iron abros and/or abros.
6. method as claimed in claim 5, which is characterized in that the austenitic stainless steel is stainless including 316 stainless steels, 316L
One of steel, 304 stainless steels and 304L stainless steel are a variety of；
And/or the corrosion resistant alloy includes Inconel 800, Inconel 600, Inconel 617, Hastelloy C 276
With one of Hastelloy N or a variety of.
7. the method as described in claim 1, which is characterized in that the fluoride includes LiF, NaF, KF, BeF2、MgF2With
ZrF4One of or it is a variety of；
And/or the chloride includes NaCl, KCl, MgCl2And CaCl2One of or it is a variety of.
8. the method as described in claim 1, which is characterized in that the mixed operation and assembling process under inert atmosphere into
Row.
9. method according to claim 8, which is characterized in that the inert atmosphere is nitrogen and/or argon gas.
10. the method as described in claim 1, which is characterized in that the system is static state constant-temperature system or dynamic temperature difference system；
It and/or in the system further include carbon-based material.
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| CN107130242B (en) * | 2017-05-19 | 2019-03-26 | 中国科学院上海应用物理研究所 | The surface treatment method of the based high-temperature alloy containing ferrochrome and the part of based high-temperature alloy containing ferrochrome |
| CN108956744B (en) * | 2018-05-31 | 2020-07-31 | 中国科学院上海应用物理研究所 | Corrosion test method of redox buffer molten salt system |
| US10914293B2 (en) | 2018-06-20 | 2021-02-09 | David Alan McBay | Method, system and apparatus for extracting heat energy from geothermal briny fluid |
| AU2020378420A1 (en) | 2019-11-08 | 2022-06-02 | Abilene Christian University | Identifying and quantifying components in a high-melting-point liquid |
| CN113732294A (en) * | 2021-09-26 | 2021-12-03 | 中国科学院上海应用物理研究所 | Method for cheap large-scale synthesis of metal clusters through molten salt |
| CN114836712B (en) * | 2022-04-21 | 2023-08-11 | 中山大学 | In-situ magnesia forming method for inhibiting corrosiveness of chloride molten salt |
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| CN103776180B (en) * | 2014-01-24 | 2015-08-05 | 西安科技大学 | A kind of method reducing solar electrical energy generation heat accumulation fused salt corrosion performance |
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