Patent Application
20130236349
1. Field of the Invention
The present invention pertains to the field of metallic material, and belongs to the category of oxide dispersion strengthened materials. Particularly, there is provided a process in which powders of mixed oxides of yttrium oxide and ferric oxide are industrially fabricated at low cost and on a large scale by utilizing the recovery procedure of pickling liquors of industrial hydrochloric acid, and then are subjected to reduction and a densification process to fabricate an iron-based dispersion strengthened material.
Due to its low cost and good performance, the oxide dispersion strengthened iron-based material according to the present invention can be used on the occasions when excellent high-temperature strength and creep strength are required, such as material for the first wall of a nuclear fusion reactor, etc., and can be used to fabricate powder metallurgy parts of low cost and high performance besides.
2. Description of the Related Art
With the rapid development of science and technology, various thermal mechanics (gas turbines, jet engines, rockets), the aerospace industry, and the atomic energy industry have increasingly high requirements on high-temperature strength and corrosion-resistant property of heat-resistant materials. Currently, as regards a conventional heat-resistant metallic material, solid solution strengthening and precipitation hardening of precipitated phases are usually adopted as its main strengthening means. However, the precipitated phases will be aggregated and grow up at a high temperature or be solid-solved in the matrix again, so that the strengthening function is lost and its usage temperature is limited; and on the other hand, elements for solid solution strengthening each enormously reduce the anti-oxidation corrosion resistance. While for an iron-based oxide dispersion strengthened material, a metal is strengthened by a stable dispersed phase of an oxide, and accordingly, it is possible that the above limitations are overcome, the high-temperature properties and mechanical properties of general metals are improved, and the thermal stability, hardness and strength of high-temperature alloys are enhanced more effectively.
Dispersion strengthening is such a method: in a metal, second phase particles that are usually relatively stable are added or formed, so as to strengthen the alloy. The second phase particles are added into the matrix material artificially, and they are uniform, fine, and capable of pinning dislocations, particle boundaries, subparticle boundaries and impeding movement of dislocations, and have good thermal stability and chemical stability, to thereby strengthen the material. Moreover, they will not be dissolved any more when the alloy is heated to a higher temperature, and the strengthening effect can be maintained until it approximates the melting point of the alloy (0.8-0.9 Tmelting point), so that the dispersion strengthened material still has a quite high strength, creep property and anti-oxidation property at temperatures close to the melting point. As such, it is possible that potentials of the material are exploited to a great extent, and the metallic material is fully used. The second phase particles for bringing out the strengthening effect in the metallic material have to be fine particles that are dispersed in the metal by way of being relatively uniform. It is generally thought that the finer the oxide particles are, the more uniform the distribution is, and the improvement in properties of the material is more remarkable.
At present, for the preparation of iron-based oxide dispersion materials, what is mainly adopted is the mechanical alloying technology, in which they are fabricated through a mechanical alloying process, taking Fe as original powders, Cr, Al, Ti and Mo as intermediate alloy powders, and Y2O3 as second-phase particles for dispersion strengthening. This method suffers from the following drawbacks: it has a high cost and a long production cycle, is not easy to control, tends to introduce impurities to pollute the alloy, etc. It is difficult to achieve large-scale industrial production and to assure nonexistence of coarse dispersed-phase particles by this method. The high production cost limits the scope of use of iron-based dispersion strengthened materials, which are merely used in the high-end industry at present. Therefore, to develop a fabricating process of iron-based oxide dispersion strengthened bulk materials of low cost has an important meaning in reality and a great market potential.
An object of the present invention is to provide a powder metallurgy fabrication method of a dispersion strengthened iron-based material, which has industrial application value and a low cost, namely, a process in which, powders of mixed oxides of yttrium oxide and ferric oxide are industrially fabricated at low cost and on a large scale by utilizing the recovery procedure of pickling liquors of industrial hydrochloric acid, and then they are subjected to reduction and two different densification processes so as to fabricate iron-based dispersion strengthened materials for servicing different needs. Drawbacks of an existing method that it has a high cost and a long production cycle, is not easy to control, etc. are solved.
Hot rolled strip steel can be subjected to cold rolling only if hydrochloric acid pickling has been performed on it. Upon pickling, iron and an oxide skin at surfaces of the strip steel are washed away by hydrochloric acid, and the consumed hydrochloric acid turns into chlorides that are mostly FeCl2 and dissolved in the hydrochloric acid solution. The chemical equations for its main reactions are:
Fe+2HCl═FeCl2+H2O
FeO+2HCl═FeCl2+H2O
At present, pickling waste liquors are basically treated by a spray roasting technological process at home and abroad, and a large amount of by-products of Fe2O3 are obtained simultaneous with hydrochloric acid regeneration.
The principle of the present invention is: based on the selective reduction of a salt mixture subjected to spray roasting, yttrium chloride is added into a pickling waste liquor, and metal oxide mixed powders containing a dispersed phase of yttrium oxide are fabricated by utilizing a spray roasting process in the recovery procedure of the pickling waste liquor. After yttrium chloride is added into the picking waste liquor, a solution containing ferric chloride, ferrous chloride and yttrium chloride is attained, and the solution is atomized to be tiny droplets in the spray roasting process, so that the droplets contact with a gas and are dried to become powders, the powders being heated in the air to become metal oxides.
The chemical equations for its main reactions are:
4FeCl2+4H2O+O2═2Fe2O3+8HCl ↑
2FeCl3+3H2O═Fe2O3+6HCl ↑
2YCl3+3H2O═Y2O3+6HCl ↑
The resultant superfine mixed powders of metal oxide are subjected to a selective reduction in a flow of hydrogen gas to thereby obtain yttrium oxide dispersion strengthened iron powders, and then a densification process is carried out. Oxide particles that are dispersedly distributed in the matrix can inhibit grain growth, so that a stable grain size is attained easily. Thus, a higher sintering temperature can be used upon cold-pressing sintering so as to attain high density.
Specific processing steps are as follows:
a. yttrium chloride is added into a hydrochloric acid pickling waste liquor containing iron (concentration of iron in the pickling waste liquor is in the range of 50-150 g/L), so as to obtain a pickling waste liquor containing matrix metal ions, by which, a metal elementary substance is finally generated, and dispersed-phase metal ions, by which, an oxide as a dispersed phase is finally generated. When raw materials are converted into quality of the oxide as the dispersed phase and the matrix metal, mass fraction of the oxide as the dispersed phase in the total alloy is in the range of 0.1-2%.
b. Let the pickling waste liquor containing matrix metal ions and dispersed-phase metal ions get into a preconcentrator, so as to concentrate the waste acid, and the concentration of iron after concentrating is in the range of 600-1500 g/L;
c. The concentrated waste acid is atomized and sprayed to be tiny droplets by a nozzle on the top of a roasting furnace, a mixture of particles of ferric chloride and ferrous chloride in the concentrated acid is roasted into free hydrogen chloride and iron oxide in a burning gas, and yttrium chloride is roasted into free hydrogen chloride and yttrium oxide.
d. Mixed oxides are reduced in H2 atmosphere at 900-1000° C., with a reduction time of 60-90 minutes, so as to get dispersion strengthened iron powders with yttrium oxide as the dispersed phase.
e. The dispersion strengthened iron powders are densified by using a cold-pressing sintering process or a hot extrusion process, so as to get an iron-based dispersion strengthened material.
The cold-pressing sintering process is: the dispersion strengthened iron powders are molded by cold pressing, and in the course of molding by cold pressing, a mold pressing or a cold isostatic pressing is adopted. Pressure of the mold pressing is: 600-1200 Mpa, pressure of the cold isostatic pressing is in the 200-300 MPa range, pressure holding time is in the range of 30-90 minutes, and a vacuum sintering process is adopted, the sintering process being carried out at 1300-1400° C. under a vacuum degree of 0.1-0.01 Pa, the temperature being maintained for 60-120 minutes. The hot extrusion process is: the dispersion strengthened iron powders are loaded into a canning, which is vacuumized under a vacuum degree of 10−1-10−2 pa for 1-2 hours firstly, and heated to 1150-1250° C. for hot extrusion, so that the dispersion strengthened iron powders are solidified.
The ferric chloride particles in the step 3 are replaced by ferrous chloride particles or a mixture of particles of ferric chloride and ferrous chloride.
The spray speed of the concentrated waste acid in the step 3 is: 200-4000 L/h; and the temperature in the spray roasting furnace is in the range of 300-700° C. Dispersed-phase Y2O3 particles are rapidly generated by reaction in situ owing to an extremely quick evaporation speed in the spray roasting process, and thus, in the prepared iron-based dispersion strengthened material, dispersed-phase Y2O3 particles are more fine and homogeneous, and no coarse Y2O3 particle is mingled with them. Further, the spray speed of the concentrated waste acid is: 1000-3000 L/h.
Advantages of the present invention are:
Dispersed-phase Y2O3 particles are rapidly generated by reaction in situ owing to an extremely quick evaporation speed in the spray roasting process of the present invention. Thus, in the iron-based dispersion strengthened material prepared by the invention, dispersed-phase Y2O3 particles are more fine and homogeneous, and no coarse Y2O3 particle is mingled with them. As compared to other process for fabricating iron-based dispersion strengthened materials in prior art (such as co-precipitation, EDTA complexing method, microemulsion method, etc.), the material has more excellent material properties and a good processability. It is possible that the dispersion strengthened powders are taken as raw material to fabricate filaments of the iron-based dispersion strengthened material with a size smaller than 0.2 mm.
An existing production process for recovering industrial hydrochloric acid pickling liquors is utilized by the invention to prepare dispersion iron powders of low cost. Upon preparation of powders of mixed oxides, an existing pickling waste liquor is used as raw material, and besides the cost of yttrium chloride as raw material for the dispersed phase being added, an additional cost is not required basically. Moreover, according to requirements of different usage situations, there are provided two corresponding densification processes, among which, the cold-pressing sintering has a relatively low cost, and the hot extrusion process has a relatively high cost, but has a better performance relative to the cold-pressing sintering. The present patent makes full use of accompanying regenerants in the production process of steel, and it is a typical energy-saving, emission-reduction and circular-economy technology, and is also a typical production technology of green materials.
Regarding the iron-based dispersion strengthened powders prepared by using the present invention, the pressing properties are excellent, and the material properties are excellent. The average density in the cold-pressing sintering process can be over 97%, and tensile strength at room temperature for a material containing 1% of a Y2O3 dispersed phase is larger than or equal to 400 MPa, being one times higher than pure iron; the average density with the hot extrusion process can be over 99%, and tensile strength at room temperature for a material containing 1% of a Y2O3 dispersed phase is larger than or equal to 600 MPa.
yttrium chloride is added into a hydrochloric acid pickling waste liquor (concentration of iron in the pickling waste liquor is 50 g/L), so as to obtain a pickling waste liquor containing matrix metal ions, by which, a metal elementary substance is finally generated, and dispersed-phase metal ions, by which, an oxide as a dispersed phase is finally generated. When raw materials are converted into quality of the oxide as the dispersed phase and the matrix metal, mass fraction of the oxide as the dispersed phase in the total alloy is 0.1%;
Let the pickling waste liquor containing matrix metal ions and dispersed-phase metal ions get into a preconcentrator, so as to concentrate the waste acid, and the concentration of iron after concentrating is 600 g/L;
The concentrated waste acid is atomized and sprayed to be tiny droplets by a nozzle on the top of a roasting furnace, the spray speed of the concentrated waste acid being 600 L/h, the temperature in the spray roasting furnace being 400° C. A mixture of particles of ferric chloride and ferrous chloride in the concentrated acid is roasted into free hydrogen chloride and iron oxide in a burning gas, and yttrium chloride is roasted into free hydrogen chloride and yttrium oxide;
Mixed oxides are reduced in H2 atmosphere at 900° C., with a reduction time of 90 minutes, so as to get dispersion strengthened iron powders with yttrium oxide as the dispersed phase;
The dispersion strengthened iron powders are molded by mold pressing, with a pressing pressure of 600 Mpa, and a vacuum sintering process is used, the sintering temperature being 1300° C. and maintained for 120 minutes.
As for the prepared dispersion strengthened iron material, the relative density is 97.5%, the tensile strength at room temperature is 363 MPa, and the HRB hardness is 70.
yttrium chloride is added into a hydrochloric acid pickling waste liquor (concentration of iron in the pickling waste liquor is 90 g/L), so as to obtain a pickling waste liquor containing matrix metal ions, by which, a metal elementary substance is finally generated, and dispersed-phase metal ions, by which, an oxide as a dispersed phase is finally generated. When raw materials are converted into quality of the oxide as the dispersed phase and the matrix metal, mass fraction of the oxide as the dispersed phase in the total alloy is 0.5%;
Let the pickling waste liquor containing matrix metal ions and dispersed-phase metal ions get into a preconcentrator, so as to concentrate the waste acid, and the concentration of iron after concentrating is 900 g/L;
The concentrated waste acid is atomized and sprayed to be tiny droplets by a nozzle on the top of a roasting furnace, the spray speed of the concentrated waste acid being 2000 L/h, the temperature in the spray roasting furnace being 700° C. A mixture of particles of ferric chloride and ferrous chloride in the concentrated acid is roasted into free hydrogen chloride and iron oxide in a burning gas, and yttrium chloride is roasted into free hydrogen chloride and yttrium oxide;
Mixed oxides are reduced in H2 atmosphere at 900° C., with a reduction time of 90 minutes, so as to get dispersion strengthened iron powders with yttrium oxide as the dispersed phase;
The dispersion strengthened iron powders are loaded into a canning, which is vacuumized under a vacuum degree of 10−2 pa for 2 hours firstly, and heated to 1200° C. for hot extrusion, so that the dispersion strengthened iron powders are densified.
As for the prepared dispersion strengthened iron material, the relative density is 99%, the tensile strength at room temperature is 540 MPa, and the HRB hardness is 92.
yttrium chloride is added into a hydrochloric acid pickling waste liquor (concentration of iron in the pickling waste liquor is 100 g/L), so as to obtain a pickling waste liquor containing matrix metal ions, by which, a metal elementary substance is finally generated, and dispersed-phase metal ions, by which, an oxide as a dispersed phase is finally generated. When raw materials are converted into quality of the oxide as the dispersed phase and the matrix metal, mass fraction of the oxide as the dispersed phase in the total alloy is 1%;
Let the pickling waste liquor containing matrix metal ions and dispersed-phase metal ions get into a preconcentrator, so as to concentrate the waste acid, and the concentration of iron after concentrating is 1000 g/L;
The concentrated waste acid is atomized and sprayed to be tiny droplets by a nozzle on the top of a roasting furnace, the spray speed of the concentrated waste acid being 3000 L/h, the temperature in the spray roasting furnace being 600° C. A mixture of particles of ferric chloride and ferrous chloride in the concentrated acid is roasted into free hydrogen chloride and iron oxide in a burning gas, and yttrium chloride is roasted into free hydrogen chloride and yttrium oxide;
Mixed oxides are reduced in H2 atmosphere at 950° C., with a reduction time of 75 minutes, so as to get dispersion strengthened iron powders with yttrium oxide as the dispersed phase;
The dispersion strengthened iron powders are molded by cold isostatic pressing, the pressing pressure being 200 Mpa, the pressure holding time being 60 minutes, and a vacuum sintering process is used, the sintering temperature being 1400° C. and being maintained for 120 minutes.
As for the prepared dispersion strengthened iron material, the relative density is 98%, the tensile strength at room temperature is 430 MPa, and the HRB hardness is 86.
yttrium chloride is added into a hydrochloric acid pickling waste liquor (concentration of iron in the pickling waste liquor is 150 g/L), so as to obtain a pickling waste liquor containing matrix metal ions, by which, a metal elementary substance is finally generated, and dispersed-phase metal ions, by which, an oxide as a dispersed phase is finally generated. When raw materials are converted into quality of the oxide as the dispersed phase and the matrix metal, mass fraction of the oxide as the dispersed phase in the total alloy is 2%;
Let the pickling waste liquor containing matrix metal ions and dispersed-phase metal ions get into a preconcentrator, so as to concentrate the waste acid, and the concentration of iron after concentrating is 1500 g/L;
The concentrated waste acid is atomized and sprayed to be tiny droplets by a nozzle on the top of a roasting furnace, the spray speed of the concentrated waste acid being 4000 L/h, the temperature in the spray roasting furnace being 700° C. A mixture of particles of ferric chloride and ferrous chloride in the concentrated acid is roasted into free hydrogen chloride and iron oxide in a burning gas, and yttrium chloride is roasted into free hydrogen chloride and yttrium oxide;
Mixed oxides are reduced in H2 atmosphere at 1000° C., with a reduction time of 60 minutes, so as to get dispersion strengthened iron powders with yttrium oxide as the dispersed phase;
The dispersion strengthened iron powders are loaded into a canning, which is vacuumized under a vacuum degree of 10−2 pa for 2 hours firstly, and heated to 1250° C. for hot extrusion, so that the dispersion strengthened iron powders are densified.
As for the prepared dispersion strengthened iron material, the relative density is 99%, the tensile strength at room temperature is 710 MPa, and the HRB hardness is 103.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201010562535.X | Nov 2010 | CN | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/CN11/76644 | 6/30/2011 | WO | 00 | 5/23/2013 |
