Remelting and ingot casting sample preparation and component detection method for ferroalloyTechnical Field
The invention relates to the technical field of alloy sample detection, in particular to a remelting ingot casting sample preparation and component detection method for ferroalloy.
Background
The ferroalloy is an intermediate alloy consisting of an iron element and one or more other elements, and is mainly used for removing oxygen, sulfur, nitrogen and the like in molten steel in the steel smelting process, or adding the alloy elements into the steel according to the component requirements of the steel to improve the structural performance of the steel, or adding the alloy elements into the molten iron before casting cast iron to improve the crystalline structure of a casting, or serving as a titanium alloy base material and the like. The ferroalloy products are various in types, and commonly used ferroalloys comprise ferrovanadium, sawtooth iron, ferrosilicon, silicomanganese, ferromanganese, ferromolybdenum, ferrotitanium and the like. The production and manufacture of ferroalloy products and the application in the fields of metallurgy and the like require analysis and determination of the content of element components, and at present, besides traditional chemical analysis methods such as titration method, gravimetric method and the like, X-ray fluorescence spectrometry is commonly used for determining the content of matrix, alloy and impurity element components in the ferroalloy.
The most commonly used sample preparation methods for X-ray fluorescence spectroscopy include both powder compression and fused glass. The powder tabletting method is characterized in that a sample is directly pressed into a sheet shape, the chemical form of the sample is not changed, the XRF determination is affected by the interference of sample matrixes such as granularity effect, mineral effect and the like due to the differences of particle size, mineral structure or coexisting components and the like between a sample to be detected and a calibration standard sample which are produced and manufactured by different processes or raw materials, and the precision and accuracy of the detection result are poor; the molten glass sheet is prepared by using lithium tetraborate, sodium tetraborate or lithium metaborate as sample digesting flux and vitrification reagent, or using lithium nitrate, sodium nitrate or ammonium nitrate as protecting agent, and ammonium iodide, potassium sulfonate or bromine water as demolding agent, and through the processes of melt digesting reaction at 1000 deg.c, crystallization and demolding. Because the element components in the iron alloy sample exist in the forms of metal simple substances or alloy components and the like, the metal components and the platinum crucible or the platinum yellow crucible generate alloying reaction in the high-temperature melting reaction process to seriously corrode the crucible, the digestion preparation effect of the sample is influenced, and the cost of the reagent and the platinum crucible is high.
In a word, the existing detection and analysis method for measuring the element components in various ferroalloy samples such as ferrovanadium, iron saw, ferrosilicon, silicomanganese, ferromanganese, ferromolybdenum, ferrotitanium and the like by the X-ray fluorescence spectrum analysis method has certain defects in both the powder tabletting method and the molten glass method. The requirement of accurately and quantitatively determining the content of the ferroalloy elements cannot be met by adopting a powder tabletting method; the method for preparing the glass sheet by melting also needs to carry out pyrogenic or wet pretreatment to convert the iron alloy into oxides or solid salts, and then carries out high-temperature melting digestion reaction, so that the preparation operation of the sample is complicated, the steps are increased, the error is increased, the melting operation is complicated and has high requirements, the used chemical reagents and crucibles have high cost and various types, and the sample needs to be melted and digested, and is effectively demoulded and crystallized to form a glassy crystal with a smooth and crackless surface.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a remelting ingot casting sample preparation and component detection method for ferroalloy, which can detect elements detected by the existing molten glass method, can also detect the contents of elements such as Si, P, B, S and the like in the ferroalloy, analyzes and detects an ingot casting sample by a direct-reading spectrometer and an X-ray fluorescence spectrometer, has wider application range, only needs to grind a sample when in detection, saves operation process and is more accurate in detection.
In order to achieve the purpose, the invention adopts the following technical scheme:
a remelting ingot casting sample preparation and component detection method of ferroalloy comprises the following steps:
a: remelting and casting an iron alloy sample to prepare a sample:
a1: weighing quantitative pure iron and an iron alloy sample to be detected, wherein the weight ratio of the pure iron to the iron alloy sample to be detected is 3-6: 1, placing the crucible in an alumina crucible;
a2: placing an alumina crucible containing pure iron and an iron alloy sample to be detected in a vacuum melting furnace, and carrying out remelting, ingot casting and sample preparation treatment to obtain an alloy sample;
b: detecting the components of the alloy sample:
and (3) cooling the alloy sample in a vacuum melting furnace to room temperature, taking out the alloy sample, grinding the surface of the alloy sample by a sample grinding machine, and analyzing by using a direct-reading spectrometer and/or an X-ray fluorescence spectrometer.
According to a further preferred scheme, the vacuum melting furnace comprises a case, a sample heating area and an equipment installation area are arranged inside the case, an ingot casting mold and a fixing seat are installed inside the sample heating area, and a heating assembly for installing an alumina crucible and a driving mechanism for driving the heating assembly to rotate are installed on the fixing seat.
Further preferred scheme, heating element includes roating seat, graphite crucible, protective sheath and electric heating coil, the roating seat rotates and installs on the fixing base, graphite crucible installs on the roating seat, the position at the inside just injectd protective sheath of graphite crucible is installed to the protective sheath, electric heating coil installs on the roating seat and covers the outside of establishing at graphite crucible, the external power that is located the equipment fixing zone of electric heating coil.
Further preferably, the driving mechanism comprises a first driving motor, a first driving disc and a second driving disc, the first driving motor is installed in the equipment installation area, the output end of the first driving disc extends to the sample heating area, the first driving disc is installed at the output end of the first driving motor, the second driving disc is installed on the rotating seat, and the first driving disc and the second driving disc are connected through a belt.
According to a further preferable scheme, a second driving motor is installed on the rotary seat, a driving gear is installed at the output end of the second driving motor, a base which is rotatably installed with the rotary seat is fixedly installed at the bottom of the graphite crucible, and a driven gear which is meshed with the driving gear is installed on the base.
Further preferred scheme, the top of machine case is for opening setting and installing the door, install observation window and exhaust duct, admission line on the door, all install the external argon gas bottle of valve and admission line on exhaust duct and the admission line.
Further preferably, a cooling channel is arranged inside the ingot casting mold, and water cooling equipment located inside the equipment installation area is externally connected to the cooling channel.
Further preferably, an insulating layer is arranged on the inner wall of the sample heating area.
Further preferably, in the step a2, the remelting ingot casting sample preparation process in the vacuum melting furnace specifically includes the steps of:
a21: opening a bin door, installing an alumina crucible containing pure iron and an iron alloy sample to be detected in a graphite crucible and a protective sleeve, placing an ingot casting mold, and closing the bin door;
a22: closing a valve of an exhaust pipeline, vacuumizing until the surface display is below 0.06MPa, opening a valve of an air inlet pipeline, filling argon into the sample heating area until the surface display is 0.03-0.04 MPa, and then closing the valve of the exhaust pipeline;
a23: supplying power to an electromagnetic heating coil, and melting and processing pure iron and an iron alloy sample to be detected in the alumina crucible through a graphite crucible;
a24: the driving motor II is started to drive the driving disc I to rotate, the driving disc II drives the driving disc II and the rotating seat to rotate for a certain angle through a belt, and the alloy melt in the alumina crucible is poured into the ingot casting mold;
a25: and finally, in a cooling stage, opening a valve on the exhaust pipeline until the surface shows to 0MPa, and opening a bin gate when the temperatures of the ingot casting mold and the sample heating area are reduced to the set temperature, so as to take out the alloy ingot casting in the ingot casting mold.
In a further preferable scheme, in the step a23, in the melting treatment process of pure iron and the ferroalloy sample to be detected, the driving motor two drives the driving gear to rotate and the driven gear to rotate, the base, the graphite crucible and the alumina crucible autorotate at a certain speed, and simultaneously the driving motor drives the driving disk one, the driving disk two and the rotating seat to do reciprocating rotation movement, and the range of the rotation angle is-45 degrees to +45 degrees.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the ferroalloy and the pure iron are uniformly mixed in a molten state, then the mixture is molded in an ingot mold to obtain a sample, the surface of the sample is ground by a sample grinder, and then the sample is analyzed by a direct-reading spectrometer and an X-ray fluorescence spectrometer, so that the defects of multiple types of reagents, high cost, environmental pollution and the like in the existing molten glass sheet method are eliminated, a platinum crucible which is high in price and easy to corrode is replaced by a cheap and durable alumina crucible, the detection cost is reduced, the alloy can be rapidly detected by the direct-reading spectrometer, the detection efficiency is greatly improved, and the uniformity of alloy sample preparation is greatly improved, so that the detection and analysis are facilitated.
2. The vacuum melting furnace adopts the rotatable rotating base, the rotating base is driven to rotate by the first driver, an alumina crucible on the heating assembly is conveniently heated, the melting treatment is favorable for mixing an internal alloy sample with pure iron, the internal molten liquid is cast into an ingot casting mold by the first driver, the internal ingot casting sample is formed by the ingot casting mold, the ingot casting mold is rapidly cooled by water washing equipment, the alloy sample is taken out and ground by a sample grinding machine, a direct-reading spectrometer and an X-ray fluorescence spectrometer can be directly used for detection and analysis treatment, and the finally obtained device
Drawings
FIG. 1 is a flow chart of the composition detection process of the present invention;
FIG. 2 is a schematic view showing the overall structure of the vacuum melting furnace of the present invention;
FIG. 3 is a top view of the vacuum melting furnace of the present invention;
FIG. 4 is a transverse cross-sectional view of the vacuum melting furnace of the present invention;
FIG. 5 is a schematic view of the overall structure of the rotary base according to the present invention;
FIG. 6 is a sectional view showing the entire structure of the ingot mold of the present invention.
In the figure: the casting machine comprises amachine case 1, aningot casting mold 2, a fixedseat 3, a rotatingseat 4, agraphite crucible 5, aprotective sleeve 6, anelectric heating coil 7, afirst driving motor 8, afirst driving disk 9, asecond driving disk 10, aheating zone 11, anequipment installation zone 12, asecond driving motor 13, abase 14, a drivengear 15, adriving gear 16 and a bin gate 17.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
Example 1:
as shown in fig. 1, a method for preparing a remelting ingot casting sample and detecting components of an iron alloy comprises the following steps:
a: remelting and casting an iron alloy sample to prepare a sample:
a1: weighing quantitative pure iron and an iron alloy sample to be detected, wherein the weight ratio of the pure iron to the iron alloy sample to be detected is 5: 1, placing the powder in an alumina crucible, uniformly mixing 40g of pure iron and 5g of an iron alloy sample to be detected in the alumina crucible in a powder state;
a2: placing an alumina crucible containing pure iron and an iron alloy sample to be detected in a vacuum melting furnace, and carrying out remelting, ingot casting and sample preparation treatment to obtain an alloy sample;
b: detecting the components of the alloy sample:
after the alloy sample is cooled to room temperature in a vacuum melting furnace, the alloy sample is taken out, the surface of the alloy sample is ground by a sample grinding machine (a working curve needs to be established by the alloy sample in advance), and finally, a direct-reading spectrometer and/or an X-ray fluorescence spectrometer are used for analysis.
1. The silicon-manganese alloy is used as a research object, the detection working curve attribute of the silicon-manganese alloy is established, and the parameters of the silicon-manganese working curve are shown in table 1.
Table 1: silicon manganese working curve parameter
2. Melt sample homogeneity experiment:
2.1 test for easy analysis of surface uniformity of molten sample
Selecting and selecting silicomanganese melting samples, and performing uniformity experiments on the same analysis surface by using a direct-reading spectrometer, wherein the results are shown in table 2. As can be seen from Table 2, the silicon-manganese molten sample has good uniformity on the same surface, and can meet the analysis requirements.
Table 2: same surface analysis result of silicon-manganese melt sample
| Element(s) | Measured value | Mean value | Extreme difference |
| Mn | 66.37;66.31;66.27 | 66.32 | 0.10 |
| Si | 17.28;17.41;17.34 | 17.34 | 0.13 |
| P | 0.182;0.184;0.181 | 0.182 | 0.003 |
2.2 testing of homogeneity at different depths of a melted sample
Homogeneity experiments were performed on the same sample (SP112955) at different depths using an X-ray fluorescence spectrometer and the results are shown in Table 3.
Table 3: results of different depth measurements of silicomanganese melt samples
From tables 2 and 3, it can be seen that the silicon-manganese molten sample has better uniformity at different depths, and can meet the analysis requirements.
2.3 sample melt consistency test
Selecting silicon-manganese alloy to respectively melt 3 samples (SP112955), carrying out melting consistency experiment, and comparing with wet detection results, wherein the results are shown in Table 4.
Table 4: silicon manganese melting consistency experimental result
From the above experimental results, it can be seen that the components of the sample obtained by melting the same sample for multiple times are consistent.
2.4 results control
Different standard samples and production samples were selected and the results of the analysis obtained by this method were compared with standard values or values determined by chemical methods and are shown in Table 5.
As is clear from Table 5, the analytical deviations between the measured values and the standard values and the values measured by the chemical method were within the allowable differences of the standard requirements, and the analytical requirements were satisfied.
Table 5: silicon-manganese alloy measuring result comparison table
The silicon-manganese alloy obtained by the method has excellent experimental results. The alloy sample prepared by the vacuum melting method has good uniformity, the massive sample obtained by melting the same silicon-manganese alloy sample for multiple times has good consistency, the accuracy of the analysis result reaches the standard requirement, and meanwhile, the melting method for analyzing the iron alloy has the advantages of simplicity, convenience and quickness, and can improve the analysis speed of the silicon-manganese alloy. The detection device can detect the content of elements such as Si, P, B and S in the iron alloy besides the elements detected by the existing molten glass method, and can analyze and detect the ingot sample through a direct-reading spectrometer and an X-ray fluorescence spectrometer, so that the application range is wider, only a sample needs to be ground when the detection is needed, the operation process is saved, and the detection is more accurate.
Example 2:
as shown in fig. 2 to 6, on the basis ofembodiment 1, the vacuum melting furnace is improved as follows, the vacuum melting furnace includes acase 1, asample heating area 11 and anequipment installation area 12 are arranged inside thecase 1, aningot casting mold 2 and a fixingseat 3 are installed inside thesample heating area 11, and a heating assembly for installing an alumina crucible and a driving mechanism for driving the heating assembly to rotate are installed on the fixingseat 3. Can also swing the aluminium oxide crucible when will drive heating element and aluminium oxide crucible through actuating mechanism and heat the melting and handle to inside pure iron with wait to detect the ferroalloy sample and carry out intensive mixing so that guarantee the homogeneity, do benefit to the composition detection analysis in later stage.
Further preferred scheme, heating element includesroating seat 4,graphite crucible 5,protective sheath 6 andelectric heating coil 7,roating seat 4 rotates and installs on fixingbase 3,graphite crucible 5 installs onroating seat 4,protective sheath 6 is installed insidegraphite crucible 5 and is injectd the position ofprotective sheath 6,electric heating coil 7 installs onroating seat 4 and covers the outside of establishing atgraphite crucible 5, the external power that is locatedequipment installing zone 12 ofelectric heating coil 7.Electric heating coil 7 can rotate 180 degrees, and figure 4 releases, andelectric heating coil 7 is provided with the sealing ring and can rotate 180 degrees along with the coil between sample zone ofheating 11 andequipment installing zone 12, and heat treatment is carried out tographite crucible 5 after circular telegram throughelectric heating coil 7, and insidegraphite crucible 5 shifted high temperature to inside aluminium oxide crucible, carries out melting treatment with inside pure iron and the ferroalloy sample that awaits measuring.
Further preferably, the driving mechanism comprises afirst driving motor 8, afirst driving disk 9 and asecond driving disk 10, thefirst driving motor 8 is installed inside theequipment installation area 12, the output end of thefirst driving disk 9 extends to thesample heating area 11, thesecond driving disk 10 is installed on the rotatingbase 4, and thefirst driving disk 9 and thesecond driving disk 10 are connected through a belt. The driving motor I8 drives the driving disc I and the driving disc II to rotate, so that pure iron and the ferroalloy sample to be detected are uniformly mixed in the melting process, the uniformity of the alloy sample is ensured, and the later-stage component detection is facilitated. Thefirst driving motor 8 can rotate therotating seat 4 by 180 degrees, so that all the melt in the alumina crucible is poured into theingot casting mold 2.
Further preferably, asecond driving motor 13 is installed on the rotatingbase 4, adriving gear 16 is installed at an output end of thesecond driving motor 13, a base 14 rotatably installed on the rotatingbase 4 is fixedly installed at the bottom of thegraphite crucible 5, and a drivengear 15 meshed with thedriving gear 16 is installed on thebase 14. Thebase 14, the drivengear 15 and thedriving gear 16 are made of high-temperature-resistant non-heat-conducting materials, thedriving gear 16 is driven to rotate by the drivingmotor II 13, thedriving gear 16 drives the drivengear 15 and the base 14 to rotate together, the uniformity heating of the alumina crucible during melting treatment is guaranteed, and the inner molten liquid can be uniformly and fully mixed by combining the swing during melting.
Further preferred scheme, the top ofmachine case 1 is for opening setting and install door 17, install observation window and exhaust duct, admission line on the door 17, all install the external argon gas bottle of valve and admission line on exhaust duct and the admission line. After the furnace is vacuumized, argon is filled into the furnace to protect the internal melting treatment, and meanwhile, the furnace can be in a state of being lower than the atmospheric pressure.
Further preferably, a cooling channel is arranged inside theingot casting mold 2, and the cooling channel is externally connected with a water cooling device located inside thedevice installation area 12. The cooling channel inside the ingot casting mold is utilized to carry out quenching on the ingot casting mold under the action of water cooling equipment, and the ingot casting mold adopts a copper mold, so that the cooling treatment is facilitated.
Further preferably, an insulating layer is installed on the inner wall of thesample heating area 11. The inner heat-insulating layer is utilized to save energy.
Example 3:
based on example 2, the method for preparing the remelting ingot and detecting the components is described in detail as follows: in the step A2, the remelting, ingot casting and sample preparation treatment process of the vacuum melting furnace comprises the following specific steps:
a21: opening a bin door 17, installing an alumina crucible containing pure iron and an iron alloy sample to be detected in agraphite crucible 5 and aprotective sleeve 6, placing aningot casting mold 2, and closing the bin door 17;
a22: closing a valve of an exhaust pipeline, vacuumizing until the surface display is below 0.06MPa, opening a valve of an air inlet pipeline, filling argon into thesample heating area 11 until the surface display is 0.03MPa to 0.04MPa, and then closing the valve of the air inlet pipeline;
a23: supplying power to an electromagnetic heating coil, and melting and processing pure iron and an iron alloy sample to be detected in the alumina crucible through agraphite crucible 5;
a24: asecond driving motor 13 is started to drive afirst driving disc 9 to rotate, asecond driving disc 10 drives asecond driving disc 10 and arotating seat 4 to rotate for a certain angle through a belt, and the molten alloy in the alumina crucible is poured into theingot casting mold 2;
a25: and finally, in the cooling stage, opening a valve on the exhaust pipeline until the pressure is 0MPa, and opening a bin gate 17 when the temperature of theingot casting mold 2 and thesample heating area 11 is reduced to the set temperature, so as to take out the alloy ingot in theingot casting mold 2.
In a further preferable scheme, in the step a23, in the melting treatment process of pure iron and the iron alloy sample to be detected, the drivingmotor II 13 drives thedriving gear 16 to rotate and the drivengear 15 to rotate, thebase 14, thegraphite crucible 5 and the alumina crucible autorotate at a certain speed, and the driving motor I8 drives the driving disc I9, thedriving disc II 10 and therotating base 4 to do reciprocating rotation motion, wherein the rotation angle range is-45 degrees to +45 degrees.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto. The substitution may be of partial structures, devices, method steps, or may be a complete solution. The technical solution and the inventive concept thereof according to the present invention should be equally replaced or changed within the protection scope of the present invention.