CN109609873A - The preparation method of the iron-based austenitic alloy of anticorrosive wear-resistant - Google Patents
The preparation method of the iron-based austenitic alloy of anticorrosive wear-resistant Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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Abstract
The present invention relates to a kind of preparation method of the iron-based austenitic alloy of anticorrosive wear-resistant, prepare the proportion of each element selected by alloy be chromium 20%~30%, molybdenum 2.0%~5.0%, tungsten 1.0%~3.0%, vanadium 0.5%~3.0%, nickel 12%~20%, manganese 0.5%~1.5%, silicon 0.5%~2.0%, nitrogen 0.4%~0.9%, carbon 0.04%~0.15% and remaining be iron Fe；Alloy powder, specific steps are prepared by Mechanical Alloying are as follows: S1, the initial powder for obtaining each element, initial powder partial size is within 100um；Initial powder and abrading-ball are put into ball grinder by S2, the ratio for determining abrading-ball Yu initial powder quality；S3, the type for selecting inert gas, and initial powder is ground to nanometer grade powder.Nanometer grade powder is put into nitrogen pressure intermediate frequency furnace, inert gas is filled with after vacuumizing, and is successively powered under the power of 50Kw, 100Kw, 150Kw, 200Kw and 50kw.Aluminizing prepared by the present invention, roller resistance to corrosion is high with abrasive resistance, Preparation equipment application is mature and low cost, and preparation process is simple, and pollution is less.
Description
Technical field
The invention belongs to metal alloy preparation field, in particular to the system of the iron-based austenitic alloy of a kind of anticorrosive wear-resistant
Preparation Method.
Background technique
On face continuous hot aluminium-plated production line, be first steel strip surface be activated, subsequently into aluminum melting pot with movement
State reacts with liquid aluminium atom, generates aluminum-plated steel strip.Undertake the plating roller that steel band is aluminized, such as sinking roller, both resistance to liquid aluminiums
High temperature erosion, bear fretting wear of the steel band to roll surface again.The usually used rich chromium cast iron of previous roller of aluminizing or
The production of 2520 heat-resistance stainless steels.Temperature of aluminizing commonly reaches 680-720 DEG C, and active aluminium atom is easy to spread, cause aluminium atom with
Roller material matrix alloy reacts the corrosion product of generation, these corrosion products fall off from roll body surface, and roller surfaces is caused to damage
Wound.This rich chromium cast iron or the roller of aluminizing of 2520 heat-resistance stainless steels production, after 3-5 hour of general work, roller and its component
With regard to needing to remove repairing, then it greatly affected the working efficiency for production line of aluminizing.In general, general ferrous alloy and heat resisting steel
Operating temperature only have 600 DEG C hereinafter, only austenitic alloy could bear the elevated temperature strength under the operating condition of hot dip aluminium parts
With anti-corrosion environment.
Mechanical Alloying is to be homogenously mixed together different material powder by high-energy ball milling, in this course
Powder passes through repeated deformation, soldering and fracture, and each component atom phase counterdiffusion generates alloying and forms cenotype, finally obtains
The uniform alloy nano-powder of structural constituent, can greatly extend limit soluble, and many alloys is made to form over-saturation solid solution
Body.
Summary of the invention
By the present invention in that with the iron-based austenitic alloy of chromium, molybdenum, tungsten and vanadium reinforcing and dispersion hardening is carried out with vanadium nitride,
So that the operating temperature of alloy is reached 680-720 DEG C, there is good high-temperature corrosion-resistance ability and abrasive resistance.
The present invention provides a kind of preparation method of the iron-based austenitic alloy of anticorrosive wear-resistant, prepares each selected by alloy
Element proportion are as follows: chromium 20%~30%, molybdenum 2.0%~5.0%, tungsten 1.0%~3.0%, vanadium 0.5%~3.0%, nickel 12%~
20%, manganese 0.5%~1.5%, silicon 0.5%~2.0%, nitrogen 0.4%~0.9%, carbon 0.04%~0.15% and balance iron；It is logical
It crosses Mechanical Alloying and prepares the alloy, specific steps are as follows:
S1, according to the ratio table obtain the initial powder of each element, and the partial size of initial powder is within 100um；
Initial powder and abrading-ball are put into ball grinder by S2, the ratio for determining abrading-ball Yu initial powder quality；
Initial powder is ground to nanometer grade powder, by sample in vacuum glove box by S3, the type for determining inert gas
Seal taking-up up for safekeeping；
S4, by the sample place in air a period of time, made annealing treatment, carried out after mortar grinder observation and
Detection.
Preferably, the nanometer grade powder is put into pressure intermediate frequency furnace, inert gas is filled with after vacuumizing, and
The nanometer grade powder is obtained after being successively powered under the power of 50Kw, 100Kw, 150Kw, 200Kw and 50kw.
Preferably, the heating time under 50Kw, 100Kw, 150Kw and 200Kw power is respectively 20min.
Preferably, the annealing temperature for carrying out the annealing is 550 DEG C, and keeps the temperature 90min.
The invention has the following advantages over the prior art:
1, by changing alloying component, with when preparation process, improve the heat-resisting quantity of alloy, resistance to corrosion with it is resistance to
Mill ability；
2, Preparation equipment application is mature and low cost, preparation process are simple；
3, during the preparation process, by way of improving and being operated in ball milling kinetic energy shortening Ball-milling Time and vacuum sealing hand case
Reduce the pollution in preparation process.
Detailed description of the invention
Fig. 1 is the preparation flow block diagram of iron-based austenitic alloy of the invention.
Specific embodiment
By the technology contents of the detailed present invention, structure feature, reach purpose and efficacy, below with reference to Figure of description
It is described in detail.
The preparation method of the iron-based austenitic alloy of anticorrosive wear-resistant proposed by the present invention, using Mechanical Alloying,
I.e. by kind of a high-energy ball-milling process, synthesis balance phase, non-equilibrium phase or mixed phase under solid-state are realized, so as to reach between element
The alloying of atom level level.
In the present invention, meet hot-dip aluminizing production line for preparation to aluminize resistance to corrosion needed for roller and abrasive resistance, press
Each element proportion: chromium Cr is 20%~30%, molybdenum Mo is 2.0%~5.0%, tungsten W is 1.0%~3.0%, vanadium V be 0.5%~
3.0%, nickel N is i12%~20%, manganese M is 0.5%~1.5%, silicon Si is 0.5%~2.0%, nitrogen N be 0.4%~
0.9%, carbon C be 0.04%~0.15% and remaining be iron Fe.It is matched according to mentioned component and carries out alloying, in Fe-Ni-Cr base
Mo+W+V etc. and the substantially nonwettable alloying element of liquid aluminium are added on alloy substrate, are reduced by the erosion journey of high temperature molten aluminum
Degree, these elements have good high temperature wear resistant performance simultaneously, and the vanadium nitride and boride especially generated can be well
Strengthen matrix and crystal boundary.
The reasons why using and adding each element is as follows: C takes 0.14-0.15%, C and Fe, Cr, Mo, W, V etc. that can be combined shape
At a certain number of carbide, so that the wearability of alloy be made to increase, while the infiltration of Al atom pair matrix alloy is also inhibited
Property, to reduce aluminium (Al) to the corrosivity of plating roller.The upper limit of C is 0.15%, and excessive carbide is solid-solution in Fe-Ni-Cr base
Anti-corrosion element in body reduces.
Si takes 0.5%~2.0%, Si that Fe atom in alloy can be made to stablize, so that Fe atom be inhibited to dissolve in the expansion in Al liquid
Dissipate speed.Si amount at least 0.5% is added, to guarantee the mobility of alloy solution, addition Si amount is more than 2.0% easy to make cast sturcture
Embrittlement occurs.
Mn takes 0.5-1.5%, due to S in conjunction with Mn MnS easily generated, to reduce the illeffects of S, the timeliness of Mn < 0.5%
Fruit is unobvious, the strengthening effect decline of Mn when Mn > 1.5%, and causes alloy embrittlement.
Ni takes 15-20%, Ni not to generate carbide, is dissolved only in matrix to guarantee to form austenite, plays High-Temperature Strengthening.
Complete austenitizing is difficult to when Ni<15%, Ni>20% item can improve cost of alloy.
Cr takes 20-30%, Cr to be not only dissolved in matrix, but also is that carbide generates element, it is often more important that inhibits liquid Al to base
The etch of body.But excessive Cr, Fe carbide, influences the ability of the matrix alloy aluminium of resistance to liquid corrosion, while also influencing to the aluminium of resistance to liquid corruption
The precipitation of inhibiting effect vanadium nitride (VN) is lost.
Mo takes 2.0-5.0%, and still carbide does not generate element to Mo, and plays solution strengthening effect, improves alloy
High temperature hardness and wearability.Its effect is insufficient when Mo<2.0%, when Mo>5.0%, excessive Mo2C is generated, and material is brittle.
W takes 1.0-3.0%, and WC carbide generates, and reduces to the wellability of liquid aluminium.The presence of WC can also improve the height of matrix
Warm hardness, thus improve wearability.Effect is unobvious when W<1.0%, when W>3.0%, the macroscopic view group as caused by centrifugal casting
Knitting segregation makes material embrittlement.
V takes 0.5-3.0, and vanadium and C, N etc. combine and form vanadium carbide nitride, declines the wellability of alloy and liquid aluminium, simultaneously
The high temperature hardness that can maintain matrix, improves wearability, and effect is unobvious when V<0.5%, and when V>3.0% holds in centrifugal casting
Easily form gross segregation.
Guarantee that the impurity such as phosphorus P and sulphur S are below 0.05% simultaneously.
The technique for preparing alloy powder are as follows: (1) obtain the initial powder of constituent material, initial powder partial size generally exists
100um or less；(2) according to the property of constituent material, grinding ball material such as steel ball, corundum ball or the ball of other materials, abrading-ball are selected
Size should also configure by a certain percentage, and the effective ratio of general abrading-ball and powder quality is 5~10, but also with processing raw material
Difference and different from；(3) initial powder and abrading-ball are put into ball grinder by a certain percentage (ratio of grinding media to material)；(4) as needed
Protective atmosphere is selected, high vacuum is in most cases selected, the inert gases such as argon, helium also can be selected；(5) in ball milling ball with
Ball, ball and ball milling tank skin make it by cold welding-crushing-cold welding repetitive process the collision of initial powder, through enough time
The uniform nanometer grade powder of structural constituent is formed after grinding.The variation of particle size, ingredient and structure is not by mechanical milling process
With the X-ray diffraction of the obtained powder of Ball-milling Time, electron microscope observation etc. is monitored.
It seals vacuum glove box of the sample under protective atmosphere up for safekeeping taking-up, is then placed within a period of time in air, due to
Sealing can not be got to completely tightly, had a small amount of oxygen and reacted with metal powder, play passivation, reduce the table of alloyed powder
Face activity, need to carry out subsequent anneal processing.Annealing uses tube type resistance furnace, and annealing temperature is 550 DEG C, soaking time difference
For 30min and 60min.Annealed treated alloyed powder after being grinded with a mortar, using scanning electron microscopic observation and X-ray diffractometer
It is observed and is detected.Next step technique is carried out after sample detection is qualified.
Production hot-dip aluminizing production line is aluminized the technique of roller test specimen:
Alloy sample is put into pressure intermediate frequency furnace, is first vacuumized, evacuation valve is then shut off, is filled with protection
Gas, and test specimen is obtained after being successively powered at 50Kw, 100Kw, 150Kw, 200Kw and 50kw.
The embodiment of the present invention is as follows:
The technique for preparing alloy powder specifically: select corundum ball, according to the ratio of grinding media to material of 10:1, be addedWith 2 kinds of different-diameters to ball mill carries out abrading-ball, prepares five classes alloy powder as shown in Table 1 in batches, adds suitable
Ethyl alcohol utilizes continuous ball milling 30h of the QM-3SP4 planetary ball mill under the revolving speed of 500r/min.
The main method that pollution is reduced in preparation process includes: to shorten Ball-milling Time by improving ball milling kinetic energy；To synthesis
Material uses the metal powder pure, ductility is good in composition design, because so abrading-ball can be by these powder
Material cladding is got up, to greatly reduce the pollution of iron；It is operated using vacuum-packed method and in vacuum sealing hand case
Method；Using the method for Controlled Atmosphere Protect.
1 ball milling sample primitive component of table matches table
Example 1, example 2, example 3 are self-control alloy proportion ingredient, compare 1 for 2520 heat-resistance stainless steels, compare 2 for Gao Ge
Cast iron is successively prepared by same process.
Since the powder after long-time high-energy ball milling can achieve Nano grade, exposure is easily oxidized in air
Burning, or even explode；And the trial of wet ball grinding, the height that ball milling generates are carried out as grinding aid using dehydrated alcohol
Energy expands dehydrated alcohol sharply, it is also possible to explode, so sampling process is the vacuum hand under argon atmosphere
It is carried out in casing, sample is first sealed up for safekeeping taking-up by when sampling, is then placed within a period of time in air, due to poorly sealed close, meeting
There is a small amount of oxygen to react with metal powder, reduces the surface-active of alloyed powder, play passivation, to subsequent anneal
Reason and scanning electron microscopic observation and X-ray diffraction analysis.
Annealing uses tube type resistance furnace, and annealing temperature is 550 DEG C, and soaking time is respectively 30min and 60min, argon
Gas shielded.It is annealed that treated that alloyed powder is observed and detected after being grinded with a mortar.It is further to the qualified sample of detection
Test specimen is carried out to manufacture.
Production hot-dip aluminizing production line is aluminized the technique of roller test specimen:
Alloy sample is put into nitrogen pressure intermediate frequency furnace, first vacuumizes, is extracted into 10Pa, be then shut off evacuation valve
Door is filled with nitrogen, and nitrogen pressure is in 2 atm highers, by following technique table 2 to electricity:
2 test specimen processing technology of table
| 50Kw | 20min |
| 100Kw | 20min |
| 150Kw | 20min |
| 200Kw | 20min fusing |
| 50kw | Temperature adjustment casting |
Surface of test piece hardness HRC and 680 DEG C of aluminum melting corrosion test are tested, continuously keeps 48h in graphite crucible, sample takes
Its surface damage degree is measured after out, the results are shown in Table 3:
Each test specimen testing result of table 3
Table 3 is invention alloy and contrast material in 680 DEG C of liquid aluminiums, pair of corrosion depth and room temperature hardness through 48h
Than data, the maximum corrosion depth of alloy of the present invention is below 0.1mm, the invention alloy aluminium of resistance to liquid corrosive power be 2520 it is heat-resisting not
15 times of rust steel anti-corrosion capability, are as many as 30 times of rich chromium cast iron.
The above is the preferred embodiment of the application, is not limited the scope of protection of the present invention with this, it is noted that right
For those skilled in the art, under the premise of not departing from this technology principle, can also make it is several improvement and
Retouching, these improvements and modifications also should be regarded as the protection scope of the application.
Claims (4)
1. a kind of preparation method of the iron-based austenitic alloy of anticorrosive wear-resistant, which is characterized in that prepare each selected by alloy
Element proportion are as follows: chromium 20%~30%, molybdenum 2.0%~5.0%, tungsten 1.0%~3.0%, vanadium 0.5%~3.0%, nickel 12%~
20%, manganese 0.5%~1.5%, silicon 0.5%~2.0%, nitrogen 0.4%~0.9%, carbon 0.04%~0.15% and balance iron；It is logical
It crosses Mechanical Alloying and prepares the alloy, specific steps are as follows:
S1, according to the ratio table obtain the initial powder of each element, and the partial size of initial powder is within 100um；
Initial powder and abrading-ball are put into ball grinder by S2, the ratio for determining abrading-ball Yu initial powder quality；
Initial powder is ground to nanometer grade powder, seals sample up for safekeeping in vacuum glove box by S3, the type for determining inert gas
It takes out；
S4, the sample is placed into a period of time in air, is made annealing treatment, is observed and examined after mortar grinder
It surveys.
2. the preparation method of the iron-based austenitic alloy of anticorrosive wear-resistant according to claim 1, which is characterized in that by institute
State nanometer grade powder to put into pressure intermediate frequency furnace, inert gas be filled with after vacuumizing, and successively 50Kw, 100Kw,
The nanometer grade powder is obtained after being powered under the power of 150Kw, 200Kw and 50kw.
3. the preparation method of the iron-based austenitic alloy of anticorrosive wear-resistant according to claim 2, which is characterized in that
Heating time under 50Kw, 100Kw, 150Kw and 200Kw power is respectively 20min.
4. the preparation method of the iron-based austenitic alloy of anticorrosive wear-resistant according to claim 1, which is characterized in that carry out
The annealing temperature of the annealing is 550 DEG C, and keeps the temperature 90min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070007A (en) * | 1991-08-28 | 1993-03-17 | 株式会社日立制作所 | Heat-resistant nitride dispersion strengthened alloys |
| CN101784687A (en) * | 2007-10-03 | 2010-07-21 | 住友金属工业株式会社 | Austenitic stainless steel |
| JP2012528943A (en) * | 2009-06-05 | 2012-11-15 | エドロ・スペシャルティ・スティールズ・インコーポレーテッド | Low carbon martensitic stainless steel plastic injection mold |
-
2019
- 2019-01-07 CN CN201910012637.5A patent/CN109609873A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070007A (en) * | 1991-08-28 | 1993-03-17 | 株式会社日立制作所 | Heat-resistant nitride dispersion strengthened alloys |
| CN101784687A (en) * | 2007-10-03 | 2010-07-21 | 住友金属工业株式会社 | Austenitic stainless steel |
| JP2012528943A (en) * | 2009-06-05 | 2012-11-15 | エドロ・スペシャルティ・スティールズ・インコーポレーテッド | Low carbon martensitic stainless steel plastic injection mold |
Non-Patent Citations (1)
| Title |
|---|
| 机械制造工艺材料技术手册编写组: "《机械制造工艺材料技术手册（下册）》", 31 December 1993 * |
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Application publication date: 20190412 |
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