CN106596669A - Device and method for nondestructive testing of sulfide inclusions in steel - Google Patents
Device and method for nondestructive testing of sulfide inclusions in steel Download PDFInfo
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- CN106596669A CN106596669A CN201611081676.3A CN201611081676A CN106596669A CN 106596669 A CN106596669 A CN 106596669A CN 201611081676 A CN201611081676 A CN 201611081676A CN 106596669 A CN106596669 A CN 106596669A
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Abstract
The invention discloses a device and a method for nondestructive testing of sulfide inclusions in steel. The device comprises an electrolytic cell, a low-temperature thermostatic control bath, a direct-current potentiostat, an argon bottle, a flowmeter, a pH meter, a computer and a plurality of cellulose acetate plastic bags 8. The method includes 1), making preparations for samples and preparing electrolyte by even mixing of anhydrous lithium chloride, gamma-butyrolactone, glycerol and absolute ethyl alcohol; 2), completing electrolysis preparations; 3), starting electrolysis, namely controlling a pH value of the electrolyte to be 7-9 by a citric acid solution, and electrolyzing for 12-36 hours; 4), washing the steel samples and the cellulose acetate plastic bags with the absolute ethyl alcohol, weighing the washed steel samples and subjecting washing liquid to magnetic separation; 5), conducting classified filtration under vacuum and separating out the sulfide inclusions. The device and the method have the advantages that Fe<2+> oxidization during filtration is avoided, filtering and collecting efficiency is improved, loss of the inclusions during filtration is reduced, and nondestructive extraction of tiny inclusions in the steel is achieved.
Description
Technical field
The invention belongs to Ferrous Metallurgy continuous casting quality testing field, and in particular to sulfide-based field trash in a kind of steel
The cannot-harm-detection device and its method.
Background technology
Although it is few that non-metallic inclusion is present in the quantity in steel, tremendous influence is then played to the quality of steel.
In order to improve the combination property of steel, the non-metallic inclusion in control steel must be just studied.Control nonmetallic inclusionsin steel
Form, quantity, size and composition, it has also become improve the inevitable approach of steel performance.And constantly improve non-in Study on Steel
The theoretical level and ability of experiment of metallic inclusion, the research that can just make field trash obtains bigger breakthrough.But the folder in steel
Debris are not of uniform size, and species is various, and according to different chemical compositions A class B class C classes and D type impurities are broadly divided into.So necessary
According to different field trashes, the attribute of itself takes different experimental techniques.Present invention is generally directed to the A for being easy to acid reaction in steel
Type impurity carries out lossless extracting and developing and sample preparation detection.
In the operation of rolling, the sulfide deflection in steel is big, and along rolling direction strip or lamellar, severe exacerbation are extended to
The non-anisotropy rolled mechanical property, aggravate steel of steel.Simultaneously the sulfide of dense distribution is easy to be linked as Jing after rolling
Integrally, it is to cause field trash exceeded or the main cause that do not conform to of flaw detection.So using Suitable assays means, by sulphide inculsion from
It is lossless in steel to extract, it is accurately to analyze sulfide primary morphology, before component distributing, size and formation mechenism
Put forward condition.
At present the conventional object detecting method that is mingled with has metallographic method, acid pasting and electrolysis.Wherein metallographic method has simple, straight
Sight, advantage in situ, in the past research steel inclusion was mainly using metallographic specimen method.But metallographic method can only observe field trash
Two-dimensional appearance, it is impossible to reflect the space three-dimensional pattern of field trash.And on the metallographic face of any grinding and polishing field trash appearance
With randomness, therefore easily there is detection leakage phenomenon in metallographic method.Further, since orientation of the field trash in space is different, it is same
Field trash is likely to present different pattern and size on metallographic face, thus metallographic method be often not easy to draw it is comprehensive and correct
Conclusion.Acid pasting can extract field trash from steel, and the three-dimensional appearance of field trash can be observed, but
In acid dissolution, part field trash is particularly readily dissolved in acidic electrolysis bath or tiny field trash and usually can react or quilt
Dissolve, therefore the use of the method is limited by certain condition.
Electrolysis includes aqueous solution electrolysises and nonaqueous solution electrolysis.Aqueous solution electrolysises method electrolytic efficiency is high, but in electrolysis
During aqueous solution be easily ionized out H+, electrolyte is often particularly tiny sulfide and causes in acidity to A type impurities
Destruction, affect steel in manganese sulfide inclusion thing collection, and aqueous solution electrolysises method be generally used for extract large scale, compared with stability property
Field trash, is difficult to obtain promising result, damage of the nonaqueous solution electrolysis to field trash to trickle field trash or unstable field trash
Wound is less, there is document (Xing Yang etc., electroextraction and the national steelmaking theory of the technique study the 17th for detecting trickle field trash in steel
Art proceedings) propose to go out steel inclusion by configuring AA non-aqueous eletrolyte electroextractions, and by Electronic Speculum to field trash
Pattern, composition etc. are analyzed.The composition of AA non-aqueous eletrolytes is：The acetylacetone,2,4-pentanedione of 1% tetramethyl ammonium chloride (conductive agent)+10%
(chelating agent)+absolute methanol, tetramethyl ammonium chloride, acetylacetone,2,4-pentanedione toxicity are larger, dangerous environmental protection, and tetramethyl ammonium chloride is low
Easily occur crystalline polamer under the conditions of temperature, have a strong impact on being collected by filtration for electrolytic efficiency and field trash, acetylacetone,2,4-pentanedione and Fe2+ from
Son forms a large amount of complex ferric acetyl acetonades, makes solution become very sticky, has a strong impact on filtration.2CH3COCHCOCH3+Fe2+→
Fe(CH3COCHCOCH3)2.The prolongation of filtration time causes the Fe2+ in electrolyte to aoxidize generation Fe2O3 in a large number, affects field trash
Collection and sample preparation observation.Novel electrolyte adopts lithium chloride for conductive agent, and lithium chloride can create conditions attraction opposite charges
Ion, it is electrically charged so as to reduce or neutralize original micelle institute, make colloid form bulky grain precipitation, electrolytic efficiency is improved, and adopt
Gamma-butyrolacton is chelating agent, and gamma-butyrolacton does not have a corrosivity, and in organic solvent viscosity is low for the complex of generation, dissolubility
Good, safety is good.Traditional nonaqueous electrolyte method can extract the field trash in steel, but in the field trash to extracting
Collection and sample preparation detection on but Shortcomings, especially in the sign to important informations such as the amount of inclusions, particle diameter distributions
Often representativeness is difficult to take into account with accuracy.
The content of the invention
The problem of trickle field trash in being difficult to complete extraction and detection steel for traditional method, the invention provides a kind of steel
In sulfide-based field trash the cannot-harm-detection device and its method, the present invention is a kind of lossless electrolysis of electrolyte of employing novel environment friendly
Extract and detect the method and device of fine foreign matter in steel.
Sulfide-based field trash the cannot-harm-detection device in the steel of the present invention, composition includes that electrolysis bath 1, cryogenic thermostat is controlled
Groove, direct current potentiostat, argon bottle, effusion meter, PH meters, computer and some cellulose acetate poly-bags；
Described electrolysis bath 1, composition comprising uncovered cylinder cell body, closure and central shaft and several be interconnected
Chamber；Uncovered cylinder cell body is provided with some through holes by seal cap sealing on closure, central shaft is vertically arranged in uncovered
The center of cylindrical cell body；Several chambers being interconnected are arranged in uncovered cylindrical groove body, and unit chamber composition is wrapped
Insulating barrier, support, catholyte plate are included, draw-in groove is provided with support, support level is arranged on central shaft top, and support phase
For central shaft has horizontal rotation degree of freedom；Catholyte plate is suspended on unit within the chamber by central shaft；
Described electrolysis bath is arranged on inside cryogenic thermostat control flume；
Described argon bottle, the chamber being interconnected with several through the through hole of closure by conduit, in argon
Effusion meter is provided between gas cylinder and the through hole of closure；
The test pen of described PH meters, is connected through the through hole of closure by wire with the chamber that several are interconnected
It is logical；PH meters are connected with computer；
Described direct current potentiostat, is connected through the through hole of closure by wire with catholyte plate；
The untapped through hole of closure, is provided with switchable through hole lid；
Described cellulose acetate poly-bag, for isolating sample and catholyte plate.
In above-mentioned steel in sulfide-based field trash the cannot-harm-detection device：
Described closure is sealing rubber plug.
The untapped through hole of described closure, for adjusting pH value by adding acid solution in electrolyte.
Described insulating barrier is electro-insulating rubber dividing plate.
Described catholyte plate is negative electrode stainless steel electrolytic plates.
The described chamber being interconnected is 8.
Upper part of the electrolytic cell closure sealing, be in order to prevent electrolytic process in electrolyte be oxidized.
Described support, distance that can be according to sample size adjusting sample away from catholyte plate.
PH meters are connected on computer the pH value that can in real time export electrolyte.
Under in working order, the wire of argon bottle passes through the through hole of closure, and the test pen of PH meters is through the logical of closure
Hole, direct current potentiostat is through some through holes of closure, and untapped through hole is provided with switchable through hole lid, so electric
Solution groove defines the working condition of a sealed chamber.
Sulfide-based field trash the cannot-harm-detection device in the steel of the present invention, electrolytic process is in the atmosphere protected with argon
Under carry out, electrolysis using 2～4V DC voltage, by adjusting electrode spacing to control suitable electric current density, it is ensured that sample
Uniformly electrolysis prevents bulk from coming off on surface.During cell reaction, along with the generation of the side reaction of the release of heat, electrolysis
The temperature and pH value of liquid can change, and the temperature and pH value of real time record electrolyte is counted with PH and it is regulated and controled, to carry
High its electrolytic efficiency, reduces the impact to the original appearance of field trash.
Using sulfide-based field trash the cannot-harm-detection device in steel, the side of sulfide-based field trash Non-Destructive Testing in steel is carried out
Method, specifically includes following steps：
Step 1, carries out sample preparation and the preparation of electrolyte, and both are without sequencing：
Sample prepares：
By several steel curved beams, polish smooth and polish, be dried after ultrasonic cleaning, weigh standby；Wherein, steel curved beam is length
Cube, the number of the chamber of the number of steel curved beam≤be interconnected；
The preparation of electrolyte：
In mass ratio, anhydrous Lithium chloride: gamma-butyrolacton: glycerol: dehydrated alcohol=(1～3): (8～12): (2～5):
(80～89), by 4 kinds of raw material mix homogeneously, are obtained electrolyte, standby；
Step 2, is electrolysed preparation：
(1) electrolyte is poured in electrolysis bath, water is poured in cryogenic thermostat control flume；
(2) steel curved beam is mounted in cellulose acetate poly-bag, and is suspended on support, adjustment steel curved beam is electric with negative electrode
Horizontal range between solution plate is 1.5～3cm；
(3) connection is carried out according to the circuit theory diagrams of sulfide-based field trash the cannot-harm-detection device in steel；
(4) cryogenic thermostat control flume is started so as to which temperature is 0～5 DEG C；Noble gases are passed through in electrolyte, electricity is excluded
Air in solution liquid；
Step 3, electrolysis：
Direct current potentiostat is connected, electrolysis starts, start PH meter the real time measure and record the pH value and temperature of electrolyte, led to
Cross citric acid solution control electrolyte PH be 7～9, common-battery 12～36h of solution, electrolysis terminates；Wherein, electrolysis temperature is -5～5
DEG C, decomposition voltage is 1.6～2V；
Step 4, weighs and magnetic separation：
(1) steel curved beam and its cellulose acetate poly-bag are removed, with dehydrated alcohol steel curved beam and cellulose acetate is respectively washed
Poly-bag, obtains the cleanout fluid of steel curved beam and the cleanout fluid of cellulose acetate poly-bag；
(2) after the steel curved beam after cleaning is dried, weigh；
(3) cleanout fluid of the cleanout fluid of steel curved beam and cellulose acetate poly-bag is mixed, obtains solution electrode, electrode is molten
Liquid magnetic separation removes abrasive grit and FeC3；
Step 5, classified filtering：
By the solution electrode after magnetic separation, classified filtering, single filter aperture >=120 μm, screening are carried out under vacuum conditions
Fall the large granular impurity in solution electrode, cascade filtration aperture is 0.45～0.8 μm, isolates sulfide-based field trash.
In above-mentioned employing steel in the method for sulfide-based field trash Non-Destructive Testing：
In the step 1, described steel is one kind of potassium steel, mild steel or high-carbon steel grade.
In the step 1, the size of steel curved beam is (50～60) mm × (20～30) mm × (4～6) mm.
In the step 1, the method for polishing smooth is：Steel curved beam surface is used respectively 100#, 400#, 800# and 1200#
Sand paper wear into it is smooth.
In the step 1, using ultrasonoscope vibration washing.
In the step 2 (1), after steel curved beam is installed, electrolyte level height in a cell should not there be steel to try
Sample.
In described step 2 (3), the circuit theory diagrams connection of sulfide-based field trash the cannot-harm-detection device is in steel
It is no qualified, detect circuit to determine with universal meter.
In described step 2 (4), noble gases are argon.
In described step 2 (4), the flow for being passed through noble gases is 0.1～0.5L/min, be passed through the time for 5～
10min。
In the step 3, the concentration of citric acid solution is 0.1～0.15g/L.
In the step 3, the addition of citric acid dilute solution is completed by the through hole of closure.
In the step 3, electrolyte can 8～10h change once, to ensure electrolytic efficiency.
In the step 4 (3), magnetic separation adopts Magnet.
Described step 4 (3), by magnetic separation the magnetic unsulfided impurity of tool is removed.
In the step 5, cascade filtration adopts polyvinylidene fluoride film (PVDF).
The method of sulfide-based field trash Non-Destructive Testing in the employing steel of the present invention, the sulfide-based field trash that sub-argument goes out
Detect that preparation method is：Sulfide-based field trash is put in dehydrated alcohol, with ultrasonic cleaner ultrasonic disperse, the group for the treatment of are carried out
Poly- field trash is fully dispersed to be formed after suspension, is dropwise dropped in the suspension containing field trash for pressing from both sides with micropipette
On the carrier of debris surface sweeping electronic microscope photos, a drop of dripping again after a drip-dry, with to be detected.
In the inventive method operating process, operation will standardize, it should be noted that certain operations details, such as to prevent as far as possible
Liquid-to-air Long contact time, will also prevent having falling into accidentally for the impurity such as dust on filter membrane.
Sulfide-based field trash the cannot-harm-detection device and its method in a kind of steel of the present invention, compared with prior art, have
Beneficial effect is：
Apparatus of the present invention and method, are the nonaqueous electrolyte device and methods of a set of efficient and environment-friendly type electrolyte, basic to solve
Crystalline polamer that nonaqueous electrolyte method solution occurs, pH value excessively rapid growth, the interference of colloid, filter efficiency are low, Fe2O3Powder
The problems such as affecting the surface electrolysis non-uniform phenomenon of filter efficiency and sample preparation detection and anode sample, while sample is placed on
The exchange of ion is neither affected in cellulose acetate poly-bag, electrolytic efficiency is unaffected, and avoid Fe in filter process2+'s
Oxidation, increased the efficiency being collected by filtration, and reduce the loss of field trash in filter process, make the lossless of fine foreign matter in steel
Extraction is achieved, and improves electrolytic efficiency.
Description of the drawings
The structural representation of sulfide-based field trash the cannot-harm-detection device in the steel of Fig. 1 embodiment of the present invention 1～3；
The plan structure of the electrolysis bath of sulfide-based field trash the cannot-harm-detection device in the steel of Fig. 2 embodiment of the present invention 1～3
Figure；
The flow chart of the method for sulfide-based field trash Non-Destructive Testing in the steel of Fig. 3 embodiment of the present invention 1～3；
The secondary grading of the method for sulfide-based field trash Non-Destructive Testing filters dress in the steel of Fig. 4 embodiment of the present invention 1～3
Put schematic diagram；
The carrier structure that the detection of the sulfide-based field trash that Fig. 5 embodiment of the present invention 1～33 is isolated is adopted when preparing
Figure；
The method correspondence step 3 electrolysis 24h's of sulfide-based field trash Non-Destructive Testing in the steel of Fig. 6 embodiment of the present invention 1
Specimen surface photo；
The electron probe observation photo of three-dimensional manganese sulfide inclusion thing in the U75V heavy rail steel curved beams of Fig. 7 embodiment of the present invention 1；
The electron probe observation photo of three-dimensional manganese sulfide inclusion thing in the U75V heavy rail steel curved beams of Fig. 8 embodiment of the present invention 2；
The electron probe observation photo of three-dimensional manganese sulfide inclusion thing in the U75V heavy rail steel curved beams of Fig. 9 embodiment of the present invention 3；
Specific embodiment
The flow chart of the method for sulfide-based field trash Non-Destructive Testing is as shown in Figure 3 in the steel of example 1 below～3.
The method of sulfide-based field trash Non-Destructive Testing in the steel of example 1 below～3, the device that classified filtering is adopted is such as
Shown in Fig. 4.
When the detection of the sulfide-based field trash that example 1 below～3 are isolated prepares, the carrier structure figure of employing is as schemed
Shown in 5.
Embodiment 1
Sulfide-based field trash the cannot-harm-detection device in a kind of steel, its structural representation is as shown in figure 1, composition includes electrolysis
Groove 1, cryogenic thermostat control flume 2, direct current potentiostat 3, argon bottle 4, effusion meter 5, PH meter 6, computer 7 and 8 acetate fibers
Plain poly-bag 8；
Described electrolysis bath 1, its overlooking structure figure is as shown in Fig. 2 composition includes uncovered cylinder cell body 2-1, sealing rubber
The chamber 2-4 that plug 2-2 and central shaft 2-3 and 8 are interconnected；Uncovered cylinder cell body 2-1 is close by sealing rubber plug 2-2
Envelope, is provided with 4 through holes on sealing rubber plug 2-2, central shaft 2-3 is vertically arranged in the center of uncovered cylinder cell body；It is some
The individual chamber 2-4 being interconnected is arranged in uncovered cylinder cell body 2-1, and unit chamber composition includes electro-insulating rubber dividing plate 2-
5th, support 2-6, negative electrode stainless steel electrolytic plates 2-7, are provided with draw-in groove on support 2-6, and support 2-6 is horizontally arranged at central shaft 2-3
Top, and support 2-6 has horizontal rotation degree of freedom relative to central shaft 2-3；Negative electrode stainless steel electrolytic plates 2-7 passes through central shaft
2-3 is suspended on unit within the chamber；
Described electrolysis bath 1 is arranged on inside cryogenic thermostat control flume 2；
Described argon bottle 4, is connected by conduit through the through hole and 8 chamber 2-4 being interconnected of sealing rubber plug 2-2
It is logical, effusion meter 5 is provided between the through hole of argon bottle 4 and sealing rubber plug 2-2；
The test pen of described PH meters 6, the through hole through sealing rubber plug 2-2 and 8 chambers being interconnected by wire
Room 2-4 is connected；PH meters 6 are connected with computer 7；
Described direct current potentiostat 3, by wire the through hole and negative electrode stainless steel electrolytic plates of sealing rubber plug 2-2 are passed through
2-7 is connected；
1 untapped through hole of closure 2-2, is provided with switchable through hole lid, and for citric acid solution PH is adjusted
Value.
Described cellulose acetate poly-bag, for isolating sample and negative electrode stainless steel electrolytic plates 2-7.
Described support 2-6, distance that can be according to sample size adjusting sample away from catholyte plate.
PH meters 6 are connected on computer 8 pH value that can in real time export electrolyte.
Using sulfide-based field trash the cannot-harm-detection device in steel, in the U75V Properties of Heavy Rail Steel for carrying out sulfide-based field trash without
The method for damaging detection, specifically includes following steps：
Step 1, carries out sample preparation and the preparation of electrolyte, and both are without sequencing：
Sample prepares：
By 8 sizes for 55mm × 25mm × 5mm U75V heavy rail steel curved beams, respectively with 100#, 400#, 800# and
The sand paper of 1200# is worn into smooth, then polishes, and is dried using after ultrasonoscope vibration washing, weighs standby；
The preparation of electrolyte：
In mass ratio, anhydrous Lithium chloride: gamma-butyrolacton: glycerol: dehydrated alcohol=1: 8: 2: 89,4 kinds of raw material mixing are equal
It is even, electrolyte is obtained, it is standby；
Step 2, is electrolysed preparation：
(1) electrolyte is poured in electrolysis bath, water is poured in cryogenic thermostat control flume；
(2) U75V heavy rail steel curved beams are mounted in cellulose acetate poly-bag, and are suspended on support, adjustment U75V weights
Horizontal range between rail steel sample and catholyte plate is 1.5；
(3) connection is carried out according to the circuit theory diagrams of sulfide-based field trash the cannot-harm-detection device in steel, with omnipotent
Table detection circuit guarantees to install errorless；
(4) cryogenic thermostat control flume is started so as to which temperature is 0～5 DEG C；Argon gas are passed through in electrolyte, electricity is excluded
Air in solution liquid；Wherein, the flow of noble gases is 0.1L/min, is passed through the time for 5min；
Step 3, electrolysis：
Direct current potentiostat is connected, electrolysis starts, start PH meter the real time measure and record the pH value and temperature of electrolyte, protected
Card electrolytic efficiency and steel inclusion are not damaged by, and the PH of electrolyte gradually rises with electrolysis time, by citric acid solution
The PH for controlling electrolyte is 7～9, common-battery solution 24h, is electrolysed the specimen surface photo of 24h as shown in fig. 6, electrolysis terminates；Wherein,
Electrolysis temperature is 0～5 DEG C, and decomposition voltage is 1.6V；In order to ensure electrolytic efficiency, electrolyte 8h is changed once；Citric acid is dilute molten
The addition of liquid is completed by the through hole of closure, and citric acid is a kind of organic acid, is soluble in ethanol, can be used to neutralize in solution
OH-But, how to add and add number, need it is accurate calculate, it is specific as follows：
The pH value of the electrolyte of 1000ml is reduced to 7, OH by hypothesis from 9-Ion concentration is reduced
Need the H+ of equivalent to neutralize.And 1mol citric acids
In the H+ containing 3mol, the relative molecular weight of citric acid is 192.14g/mol, and conversion can obtain citric acid quality and be：
Therefore, compound concentration is the ethanol solution of the citric acid of 0.1g/L as additive, according to electrolyte PH's
Change and add in electrolyte, it is ensured that pH value is between 7～9；
Step 4, weighs and magnetic separation：
(1) U75V heavy rails steel curved beam and its cellulose acetate poly-bag are removed, with dehydrated alcohol steel curved beam and second is respectively washed
Acid cellulose poly-bag, obtains the cleanout fluid of U75V heavy rail steel curved beams and the cleanout fluid of cellulose acetate poly-bag；
(2) after by the U75V Properties of Heavy Rail Steel samples drieds after cleaning, weigh；
(3) cleanout fluid of the cleanout fluid of U75V heavy rail steel curved beams and cellulose acetate poly-bag is mixed, obtains solution electrode,
Solution electrode is removed into abrasive grit and FeC3 with Magnet magnetic separation；
Step 5, classified filtering：
By the solution electrode after magnetic separation, classified filtering, single filter aperture >=120 μm, screening are carried out under vacuum conditions
Fall the large granular impurity in solution electrode, cascade filtration aperture is 0.45～0.8 μm of polyvinylidene fluoride film (PVDF), is isolated
Sulfide-based field trash.
The method that the present embodiment adopts sulfide-based field trash Non-Destructive Testing in U75V Properties of Heavy Rail Steel, that what is isolated is sulfide-based
The detection preparation method of field trash is：Sulfide-based field trash is put in dehydrated alcohol, with ultrasonic cleaner ultrasound is carried out
Dispersion, wait the field trash reunited it is fully dispersed formed suspension after, with micropipette by the suspension containing field trash dropwise
Drop in for the carrier of field trash surface sweeping electronic microscope photos, a drop of dripping again after a drip-dry, with to be detected.
Using electron probe it was observed that U75V heavy rail steel curved beams in three-dimensional manganese sulfide inclusion thing photo, as shown in fig. 7,
Clearly its composition, pattern and size can be analyzed.
Embodiment 2
Using steel in sulfide-based field trash the cannot-harm-detection device with embodiment 1.
Using steel in sulfide-based field trash Non-Destructive Testing, sulfide-based field trash in the U75V Properties of Heavy Rail Steel for being adopted
The method of Non-Destructive Testing, comprises the steps：
Step 1, carries out sample preparation and the preparation of electrolyte, and both are without sequencing：
Sample prepares：
By 8 sizes for 55mm × 25mm × 5mm U75V heavy rail steel curved beams, respectively with 100#, 400#, 800# and
The sand paper of 1200# is worn into smooth, then polishes, and is dried using after ultrasonoscope vibration washing, weighs standby；
The preparation of electrolyte：
In mass ratio, anhydrous Lithium chloride: gamma-butyrolacton: glycerol: dehydrated alcohol=2: 10: 3: 85,4 kinds of raw materials are mixed
Uniformly, electrolyte is obtained, it is standby；
Step 2, is electrolysed preparation：
(1) electrolyte is poured in electrolysis bath, water is poured in cryogenic thermostat control flume；
(2) U75V heavy rail steel curved beams are mounted in cellulose acetate poly-bag, and are suspended on support, adjust steel curved beam
It is 2cm with the horizontal range between catholyte plate；
(3) connection is carried out according to the circuit theory diagrams of sulfide-based field trash the cannot-harm-detection device in steel, with omnipotent
Table detection circuit guarantees to install errorless；
(4) cryogenic thermostat control flume is started so as to which temperature is 0～5 DEG C；Argon gas are passed through in electrolyte, electricity is excluded
Air in solution liquid；Wherein, the flow of noble gases is 0.3L/min, is passed through the time for 8min；
Step 3, electrolysis：
Direct current potentiostat is connected, electrolysis starts, start PH meter the real time measure and record the pH value and temperature of electrolyte, protected
Card electrolytic efficiency and steel inclusion are not damaged by, and the PH of electrolyte gradually rises with electrolysis time, by citric acid solution
The PH for controlling electrolyte is 7～9, and common-battery solution 12h, electrolysis terminates；Wherein, electrolysis temperature is 0～5 DEG C, and decomposition voltage is 2V；For
Guarantee electrolytic efficiency, electrolyte 8h is changed once；The addition of citric acid dilute solution is completed by the through hole of closure, Fructus Citri Limoniae
Acid is a kind of organic acid, is soluble in ethanol, can be used to neutralize the OH in solution-But, how to add and add number, need
Accurately to calculate, it is specific as follows：
The pH value of the electrolyte of 1000ml is reduced to 7, OH by hypothesis from 9-Ion concentration is reduced
Need the H+ of equivalent to neutralize.And 1mol citric acids
In the H+ containing 3mol, the relative molecular weight of citric acid is 192.14g/mol, and conversion can obtain citric acid quality and be：
Therefore, compound concentration is the ethanol solution of the citric acid of 0.1g/L as additive, according to electrolyte PH's
Change and add in electrolyte, it is ensured that pH value is between 7～9；
Step 4, weighs and magnetic separation：
(1) U75V heavy rails steel curved beam and its cellulose acetate poly-bag are removed, with dehydrated alcohol U75V Properties of Heavy Rail Steel is respectively washed
Sample and cellulose acetate poly-bag, obtain the cleanout fluid of U75V heavy rail steel curved beams and the cleanout fluid of cellulose acetate poly-bag；
(2) after the steel curved beam after cleaning is dried, weigh；
(3) cleanout fluid of the cleanout fluid of U75V heavy rail steel curved beams and cellulose acetate poly-bag is mixed, obtains solution electrode,
Solution electrode is removed into abrasive grit and FeC3 with Magnet magnetic separation；
Step 5, classified filtering：
By the solution electrode after magnetic separation, classified filtering, single filter aperture >=120 μm, screening are carried out under vacuum conditions
Fall the large granular impurity in solution electrode, cascade filtration aperture is 0.45～0.8 μm of polyvinylidene fluoride film (PVDF), is isolated
Sulfide-based field trash.
The method that the present embodiment adopts sulfide-based field trash Non-Destructive Testing in U75V Properties of Heavy Rail Steel, that what is isolated is sulfide-based
The detection preparation method of field trash is：Sulfide-based field trash is put in dehydrated alcohol, with ultrasonic cleaner ultrasound is carried out
Dispersion, wait the field trash reunited it is fully dispersed formed suspension after, with micropipette by the suspension containing field trash dropwise
Drop in for the carrier of field trash surface sweeping electronic microscope photos, a drop of dripping again after a drip-dry, with to be detected.
Using electron probe it was observed that U75V heavy rail steel curved beams in three-dimensional manganese sulfide inclusion thing photo, as shown in figure 8,
Clearly its composition, pattern and size can be analyzed.
Embodiment 3
Using steel in sulfide-based field trash the cannot-harm-detection device with embodiment 1.
Using steel in sulfide-based field trash Non-Destructive Testing, sulfide-based field trash in the U75V Properties of Heavy Rail Steel for being adopted
The method of Non-Destructive Testing, comprises the steps：
Step 1, carries out sample preparation and the preparation of electrolyte, and both are without sequencing：
Sample prepares：
By 8 sizes for 55mm × 25mm × 5mm U75V heavy rail steel curved beams, respectively with 100#, 400#, 800# and
The sand paper of 1200# is worn into smooth, then polishes, and is dried using after ultrasonoscope vibration washing, weighs standby；
The preparation of electrolyte：
In mass ratio, anhydrous Lithium chloride: gamma-butyrolacton: glycerol: dehydrated alcohol=3: 12: 5: 80,4 kinds of raw materials are mixed
Uniformly, electrolyte is obtained, it is standby；
Step 2, is electrolysed preparation：
(1) electrolyte is poured in electrolysis bath, water is poured in cryogenic thermostat control flume；
(2) U75V heavy rail steel curved beams are mounted in cellulose acetate poly-bag, and are suspended on support, adjustment U75V weights
Horizontal range between rail steel sample and catholyte plate is 3cm；
(3) connection is carried out according to the circuit theory diagrams of sulfide-based field trash the cannot-harm-detection device in steel, with omnipotent
Table detection circuit guarantees to install errorless；
(4) cryogenic thermostat control flume is started so as to which temperature is 0～5 DEG C；Argon gas are passed through in electrolyte, electricity is excluded
Air in solution liquid；Wherein, the flow of noble gases is 0.5L/min, is passed through the time for 10min；
Step 3, electrolysis：
Direct current potentiostat is connected, electrolysis starts, start PH meter the real time measure and record the pH value and temperature of electrolyte, protected
Card electrolytic efficiency and steel inclusion are not damaged by, and the PH of electrolyte gradually rises with electrolysis time, by citric acid solution
The PH for controlling electrolyte is 7～9, and common-battery solution 36h, electrolysis terminates；Wherein, electrolysis temperature is 0～5 DEG C, and decomposition voltage is 2V；For
Guarantee electrolytic efficiency, electrolyte 8h is changed once；The addition of citric acid dilute solution is completed by the through hole of closure, Fructus Citri Limoniae
Acid is a kind of organic acid, is soluble in ethanol, can be used to neutralize the OH in solution-But, how to add and add number, need
Accurately to calculate, it is specific as follows：
The pH value of the electrolyte of 1000ml is reduced to 7, OH by hypothesis from 9-Ion concentration is reduced
Need the H+ of equivalent to neutralize.And 1mol citric acids
In the H+ containing 3mol, the relative molecular weight of citric acid is 192.14g/mol, and conversion can obtain citric acid quality and be：
Therefore, compound concentration is the ethanol solution of the citric acid of 0.1g/L as additive, according to electrolyte PH's
Change and add in electrolyte, it is ensured that pH value is between 7～9；
Step 4, weighs and magnetic separation：
(1) U75V heavy rails steel curved beam and its cellulose acetate poly-bag are removed, with dehydrated alcohol steel curved beam and second is respectively washed
Acid cellulose poly-bag, obtains the cleanout fluid of U75V heavy rail steel curved beams and the cleanout fluid of cellulose acetate poly-bag；
(2) after the steel curved beam after cleaning is dried, weigh；
(3) cleanout fluid of the cleanout fluid of U75V heavy rail steel curved beams and cellulose acetate poly-bag is mixed, obtains solution electrode,
Solution electrode is removed into abrasive grit and FeC3 with Magnet magnetic separation；
Step 5, classified filtering：
By the solution electrode after magnetic separation, classified filtering, single filter aperture >=120 μm, screening are carried out under vacuum conditions
Fall the large granular impurity in solution electrode, cascade filtration aperture is 0.45～0.8 μm of polyvinylidene fluoride film (PVDF), is isolated
Sulfide-based field trash.
The method that the present embodiment adopts sulfide-based field trash Non-Destructive Testing in U75V Properties of Heavy Rail Steel, that what is isolated is sulfide-based
The detection preparation method of field trash is：Sulfide-based field trash is put in dehydrated alcohol, with ultrasonic cleaner ultrasound is carried out
Dispersion, wait the field trash reunited it is fully dispersed formed suspension after, with micropipette by the suspension containing field trash dropwise
Drop in for the carrier of field trash surface sweeping electronic microscope photos, a drop of dripping again after a drip-dry, with to be detected.
Using electron probe it was observed that U75V heavy rail steel curved beams in three-dimensional manganese sulfide inclusion thing photo, as shown in figure 9,
Clearly its composition, pattern and size can be analyzed.
Claims (10)
1. sulfide-based field trash the cannot-harm-detection device in a kind of steel, it is characterised in that described device composition include electrolysis bath,
Cryogenic thermostat control flume, direct current potentiostat, argon bottle, effusion meter, PH meters, computer and some cellulose acetate poly-bags；
Described electrolysis bath, composition includes uncovered cylinder cell body, closure and central shaft and several chambers for being interconnected；
Uncovered cylinder cell body is provided with some through holes by seal cap sealing on closure, central shaft is vertically arranged in uncovered cylinder
The center of shape cell body；Several chambers being interconnected are arranged in uncovered cylindrical groove body, and unit chamber composition includes exhausted
Edge dividing plate, support, catholyte plate, are provided with draw-in groove on support, support level is arranged on central shaft top, and support relative to
Central shaft has horizontal rotation degree of freedom；Catholyte plate is suspended on unit within the chamber by central shaft；
Described electrolysis bath is arranged on inside cryogenic thermostat control flume；
Described argon bottle, the chamber being interconnected with several through the through hole of closure by conduit, in argon bottle
Effusion meter is provided with and the through hole of closure between；
The test pen of described PH meters, is connected through the through hole of closure by wire with the chamber that several are interconnected；
PH meters are connected with computer；
Described direct current potentiostat, is connected through the through hole of closure by wire with catholyte plate；
The untapped through hole of closure, is provided with switchable through hole lid；
Described cellulose acetate poly-bag, for isolating sample and catholyte plate.
2. sulfide-based field trash the cannot-harm-detection device in steel according to claim 1, it is characterised in that described sealing
Cover as sealing rubber plug；Described insulating barrier is electro-insulating rubber dividing plate；Described catholyte plate is negative electrode stainless steel electrolytic
Plate.
3. sulfide-based field trash the cannot-harm-detection device in steel according to claim 1, it is characterised in that described is mutual
The chamber of connection is 8.
4., using sulfide-based field trash the cannot-harm-detection device in the steel described in claim 1, sulfide-based in steel being mingled with is carried out
The method of thing Non-Destructive Testing, it is characterised in that specifically include following steps：
Step 1, carries out sample preparation and the preparation of electrolyte, and both are without sequencing：
Sample prepares：
By several steel curved beams, polish smooth and polish, be dried after ultrasonic cleaning, weigh standby；Wherein, steel curved beam is rectangular
Body, the number of the chamber of the number of steel curved beam≤be interconnected；
The preparation of electrolyte：
In mass ratio, anhydrous Lithium chloride: gamma-butyrolacton: glycerol: dehydrated alcohol=(1～3): (8～12): (2～5): (80～
89), by 4 kinds of raw material mix homogeneously, electrolyte is obtained, it is standby；
Step 2, is electrolysed preparation：
(1) electrolyte is poured in electrolysis bath, water is poured in cryogenic thermostat control flume；
(2) steel curved beam is mounted in cellulose acetate poly-bag, and is suspended on support, adjust steel curved beam and catholyte plate
Between horizontal range be 1.5～3cm；
(3) connection is carried out according to the circuit theory diagrams of sulfide-based field trash the cannot-harm-detection device in steel；
(4) cryogenic thermostat control flume is started so as to which temperature is 0～5 DEG C；Noble gases are passed through in electrolyte, electrolyte is excluded
In air；
Step 3, electrolysis：
Direct current potentiostat is connected, electrolysis starts, start PH meter the real time measure and record the pH value and temperature of electrolyte, by lemon
It is 7～9 that lemon acid solution controls the PH of electrolyte, and common-battery 12～36h of solution, electrolysis terminates；Wherein, electrolysis temperature is -5～5 DEG C, electricity
Solution voltage is 1.6～2V；
Step 4, weighs and magnetic separation：
(1) steel curved beam and its cellulose acetate poly-bag are removed, with dehydrated alcohol steel curved beam and cellulose acetate poly-bag are respectively washed,
Obtain the cleanout fluid of steel curved beam and the cleanout fluid of cellulose acetate poly-bag；
(2) after the steel curved beam after cleaning is dried, weigh；
(3) cleanout fluid of the cleanout fluid of steel curved beam and cellulose acetate poly-bag is mixed, solution electrode is obtained, by solution electrode magnetic
Choosing removes abrasive grit and FeC3；
Step 5, classified filtering：
By the solution electrode after magnetic separation, classified filtering is carried out under vacuum conditions, power down is screened in single filter aperture >=120 μm
Large granular impurity in the solution of pole, cascade filtration aperture is 0.45～0.8 μm, isolates sulfide-based field trash.
5. in steel according to claim 4 sulfide-based field trash Non-Destructive Testing method, it is characterised in that the step
In 1, described steel is one kind of potassium steel, mild steel or high-carbon steel grade.
6. in steel according to claim 4 sulfide-based field trash Non-Destructive Testing method, it is characterised in that the step
In 1, using ultrasonoscope vibration washing.
7. in steel according to claim 4 sulfide-based field trash Non-Destructive Testing method, it is characterised in that described step
In rapid 2 (4), the flow for being passed through noble gases is 0.1～0.5L/min, is passed through the time for 5～10min；Described step 2 (4)
In, noble gases are argon.
8. in steel according to claim 4 sulfide-based field trash Non-Destructive Testing method, it is characterised in that the step
In 3, the concentration of citric acid solution is 0.1～0.15g/L.
9. in steel according to claim 4 sulfide-based field trash Non-Destructive Testing method, it is characterised in that the step
In 3, electrolyte can 8～10h change once；In the step 4 (3), magnetic separation adopts Magnet.
10. in steel according to claim 4 sulfide-based field trash Non-Destructive Testing method, it is characterised in that the step
In rapid 5, cascade filtration adopts polyvinylidene fluoride film.
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| CN107621554A (en) * | 2017-09-22 | 2018-01-23 | 东北大学 | A kind of method of Oxide and sulfide extracting and developing in sulphur free-cutting steel |
| CN109883904A (en) * | 2019-03-06 | 2019-06-14 | 清华大学 | A method of it is distributed using non-metallic inclusion in electrolysis method characterization large-scale steel ingot |
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