CN101597693A - A kind of preparation method of industrial pure zirconium ingot - Google Patents
A kind of preparation method of industrial pure zirconium ingot Download PDFInfo
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- CN101597693A CN101597693A CNA2009100228159A CN200910022815A CN101597693A CN 101597693 A CN101597693 A CN 101597693A CN A2009100228159 A CNA2009100228159 A CN A2009100228159A CN 200910022815 A CN200910022815 A CN 200910022815A CN 101597693 A CN101597693 A CN 101597693A
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Abstract
The present invention relates to a kind of preparation method of industrial pure zirconium ingot, be used for nuclear power, metallurgy, field of petrochemical industry.Steps of the method are: the technical grade zirconium sponge that takes by weighing required weight, be pressed into electrode block, the electrode block of compacting is welded into electrode again, and the step that adopts once electron beam melting vacuum consumable electrode arc furnace at least to combine with electron beam melting then obtains purified industrial pure zirconium ingot.The zirconium ingot that the present invention produces, chemical ingredients is even, stable, and impurity contents such as Fe, Cr, O, H are low, are better than the ingot casting of vacuum consumable arc-melting, no ZrO
2Be mingled with the contour low density of WC; The present invention is applicable to and produces purified, the demanding pure zirconium ingot of metallurgical quality.
Description
Technical field
The present invention relates to a kind of preparation method of industrial pure zirconium ingot, belong to casting technology field, be mainly used in fields such as metallurgy, petrochemical complex, nuclear power.
Background technology
Zirconium is a kind of transition element, belongs to the IV-B family element in the periodic table of elements, and it is a kind of rare metal, is again a kind of strategy metal.It has hot strength height, solidity to corrosion good, can process, over-all properties such as performance is good and thermal neutron absorption cross section is low, zirconium also has good consistency with nuclear fuel, has minimum thermal neutron capture cross section (0.18 * 10-28m
2), its radiation-resistant property is also fine simultaneously, add that zirconium at high temperature has air-breathing preferably property and good erosion resistance and processing characteristics etc., zirconia material is widely used as the can material and the core structural material of water-cooled power reactor, be the important structure material of nuclear reactor, in nuclear industry, obtain to widely apply.In recent years, because its excellent corrosion resistance, also increase gradually in the application of chemical industry.Experimental study and typical example prove, zirconium has excellent solidity to corrosion in many acid commonly used, alkaline media, the characteristic of zirconium in these media is very unique, it can also use under acid, alkali exchange condition, be lower than 50% vitriolic as hydrochloric acid, nitric acid and the concentration of the anti-various concentration of zirconium ability when temperature is lower than 100 ℃ and corrode, zirconium is considered to be in all acetums noncorrosive materials.Therefore, zirconium is widely used in industries such as nuclear energy, space flight, aviation, naval vessel, electronics, machinery, metallurgy, chemical industry, weaving, papermaking, medical science, has wide future.
The major impurity element of industrial pure zirconium is iron, chromium, carbon, nitrogen, hydrogen, oxygen etc., studies show that in a large number, and the purity of material is very big to its solidity to corrosion influence, and wherein iron+chromium is very big for the influence of zirconium corrosion resisting property, affects zirconium equipment achieved reliability and work-ing life.Studies show that in depth iron+chromium content has disadvantageous effect for zirconium solidity to corrosion and the anti-hydrogen of inhaling, have only when iron level＜0.08% that just may avoid the zirconium welding zone preferentially to corrode, special-purpose acetic acid equipment is 0.15% with regulation iron+chromium upper content limit in the standard of zirconium.Simultaneously, hydrogen solid solubility in α-Zr is very low, hydrogen richness is greatly when 100～150ppm in the zirconium, just have needle-like or sheet hydride precipitated phase, in material, produce very big internal stress, because the fragility of hydride itself often just forms formation of crack, threshold limit value to hydrogen content in the zirconium in China's national standard is decided to be 0.005%, and is identical with U.S. ASTM standard.Therefore, reducing impurity contents such as iron+chromium and hydrogen is the important measures that prevent zirconium corrosion and hydrogen embrittlement.
Zirconium at high temperature is easy to and element reactions such as oxygen, nitrogen, carbon, is combustible as fine dispersive zirconium powder, can be used in the flashbulb and as the getter (O in the valve tube
2And N
2Collecting agent), this is the advantage of zirconium, but its bad one side is also arranged, and especially seems particularly outstanding in the zirconium ingot melting.At present, traditional zirconium ingot melting method is the vacuum consumable arc-melting technology, generally adopts secondary or three meltings.The vacuum consumable arc-melting method is sophisticated smelting technique, can melt out the qualified zirconium of chemical ingredients, but because vacuum melting inherent molten bath superheating temperature is low, characteristics such as to hold time in liquid molten bath short, melting vacuum tightness is not high, problems such as existence can't effectively be removed high low density and is mingled with, and refining effect is limited.And zirconium at high temperature very easily with element reactions such as oxygen, nitrogen, carbon, generate ZrO respectively
2, ZrN and ZrC, its fusing point respectively up to 2700 ℃, 2980 ℃ and 3530 ℃, and ZrO
2Because chemical property is stable, coefficient of thermal expansion is less, is one of occurring in nature fire performance best material, often is used to make refractory brick and fire-clay crucible etc.If control is bad, very easily produce ZrO in zirconium sponge and the zirconium ingot production process
2, ZrN or ZrC defective, the vacuum consumable smelting process can't thoroughly be eliminated then can produce and be mingled with metallurgical imperfection, contain the ingot casting easy cracking in postorder processing that is mingled with metallurgical imperfection and produce tiny crack, this crackle can not thoroughly be found by technology such as non-destructive test(ing)(NDT)s, can cause accidents such as parts fatigue failure, fracture, leakage at the tiny crack place in the use, cause great financial loss.
Therefore, need take a kind of reliable smelting technique to carry out the purification of impurity and the elimination of metallurgical imperfection, produce tap a blast furnace, impurity contents such as chromium, hydrogen and oxygen are low, do not have a purified zirconium ingot that is mingled with.
Summary of the invention
The technical problem that solves
For fear of the deficiencies in the prior art part, the present invention proposes a kind of preparation method of industrial pure zirconium ingot, the impurity elements such as iron, chromium, hydrogen and oxygen of effectively purifying, and can remove ZrO in the zirconium effectively
2, ZrN, ZrC and W, Mo, Ta, Nb, the contour low density of WC be mingled with the pure industrial pure zirconium ingot production method of metallurgical imperfection.
Technical scheme
The inventive method is characterised in that step is as follows:
Step 1: will be pressed into electrode block after the zirconium sponge mixing:
Step 2: welding processs such as use plasma arc are welded into electrode with electrode block;
Step 3: ingot of vacuum consumable arc-melting melting, current control are at 5～40KA, and voltage control is at 28～42V, and melting vacuum tightness is lower than 5Pa, and leak rate is lower than 0.2Pam
3/ sec;
Step 4: electron beam melting secondary ingot, pump current is controlled at 0.5～10A, and speed of melting is controlled at 10～80kg/h, and melting vacuum tightness is lower than 5 * 10
-2Pa, leak rate is lower than 0.1Pam
3/ sec.
In the methods of the invention, can also adopt electron beam melting in step 3, current control is at 0.5～10A, and speed of melting is controlled at 10～80kg/h, and melting vacuum tightness is lower than 5 * 10
-2Pa, leak rate is lower than 0.1Pam
3/ sec.
Beneficial effect
The preparation method of a kind of industrial pure zirconium ingot of the present invention, compared with prior art have the following advantages: the zirconium ingot that the present invention produces, chemical ingredients is even, stable, and impurity contents such as Fe, Cr, H, O are low, the ingot casting that is better than vacuum consumable arc-melting, no ZrO
2Be mingled with the contour low density of WC; The present invention is applicable to the ingot casting that the production metallurgy specification of quality is high.
Embodiment
Now in conjunction with the embodiments the present invention is further described:
Embodiment 1:
Step 1: with technical pure zirconium sponge (oxygen: 0.10%; Iron: 0.15%; Chromium: 0.15%) be pressed into electrode block after the mixing:
Step 2: welding processs such as use plasma arc are welded into electrode with electrode block;
Step 3: the vacuum consumable arc-melting melting once becomes Ф 80mm ingot casting, and current control is at 10～20KA, and voltage control is at 31～36V, and melting vacuum tightness is 3.5Pa, and leak rate is 0.15Pam
3/ sec;
Step 4: the electron beam melting secondary forms Ф 125mm ingot casting, and pump current is controlled at 0.5～10A, and speed of melting is controlled at 15～30kg/h, and melting vacuum tightness is 1 * 10
-2Pa, leak rate is 0.05Pam
3/ sec.
Melting gained ingot casting any surface finish, no subsurface porosity, cold shut etc., at ingot casting head, two positions, bottom sampling carrying out chemical composition analysis, analytical results shows that chemical ingredients is even, conformance with standard requirement fully, and its principal element content is respectively: oxygen 0.04%, 0.038%, iron 0.06%, 0.065%, chromium: 0.04%, 0.045%, hydrogen: 0.001%, 0.0008%, impurity elements such as C, N are also controlled lowlyer simultaneously.Ingot casting is forged into Ф 30mm bar, and surperficial car light through 0.8mm flat-bottom hole ultrasonic inspection and vertically, the laterally multi-position high macroscopic examination of cutting into slices, does not find that all high low density is mingled with metallurgical imperfection.
Embodiment 2:
Step 1: with technical pure zirconium sponge (oxygen: 0.08%; Iron: 0.12%; Chromium: 0.2%) be pressed into electrode block after the mixing:
Step 2: welding processs such as use plasma arc are welded into electrode with electrode block;
Step 3: the vacuum consumable arc-melting melting once becomes Ф 100mm ingot casting, and current control is at 3KA, and voltage control is at 28～42V, and melting vacuum tightness is 2.5Pa, and leak rate is 0.11Pam
3/ sec;
Step 4: the electron beam melting secondary forms Ф 130mm ingot casting, and pump current is controlled at 0.5～10A, and speed of melting is controlled at 16～31kg/h, and melting vacuum tightness is 5 * 10
-2Pa, leak rate is 0.03Pam
3/ sec.
Melting gained ingot casting any surface finish, no subsurface porosity, cold shut etc., at ingot casting head, two positions, bottom sampling carrying out chemical composition analysis, analytical results shows that chemical ingredients is even, conformance with standard requirement fully, and its principal element content is respectively: oxygen 0.04%, 0.038%, iron 0.05%, 0.060%, chromium: 0.04%, 0.05%, hydrogen: 0.0007%, 0.0008%, impurity elements such as C, N are also controlled lowlyer simultaneously.Ingot casting is forged into Ф 30mm bar, and surperficial car light through 0.8mm flat-bottom hole ultrasonic inspection and vertically, the laterally multi-position high macroscopic examination of cutting into slices, does not find that all high low density is mingled with metallurgical imperfection.
Embodiment 3:
Step 1: with technical pure zirconium sponge (oxygen: 0.1%; Iron: 0.16%; Chromium: 0.18%) be pressed into electrode block after the mixing:
Step 2: welding processs such as use plasma arc are welded into electrode with electrode block;
Step 3: once become Ф 100mm ingot casting in electron beam melting, current control is at 0.5～10A, and speed of melting is controlled at 10～14kg/h, and melting vacuum tightness is 2.5 * 10
-2Pa, leak rate is 0.09Pam
3/ sec;
Step 4: the electron beam melting secondary forms Ф 130mm ingot casting, and pump current is controlled at 0.5～10A, and speed of melting is controlled at 16～31kg/h, and melting vacuum tightness is 5 * 10
-2Pa, leak rate is 0.03Pam
3/ sec.
Melting gained ingot casting any surface finish, no subsurface porosity, cold shut etc., at ingot casting head, two positions, bottom sampling carrying out chemical composition analysis, analytical results shows that chemical ingredients is even, conformance with standard requirement fully, and its principal element content is respectively: oxygen 0.035%, 0.04%, iron 0.065%, 0.072%, chromium: 0.04%, 0.045%, hydrogen: 0.0004%, 0.0005%, impurity elements such as C, N are also controlled lowlyer simultaneously.Ingot casting is forged into Ф 30mm bar, and surperficial car light through 0.8mm flat-bottom hole ultrasonic inspection and vertically, the laterally multi-position high macroscopic examination of cutting into slices, does not find that all high low density is mingled with metallurgical imperfection.
Claims (2)
1. the preparation method of an industrial pure zirconium ingot is characterized in that step is as follows:
Step 1: will be pressed into electrode block after the zirconium sponge mixing:
Step 2: welding processs such as use plasma arc are welded into electrode with electrode block;
Step 3: ingot of vacuum consumable arc-melting melting, current control are at 5～40KA, and voltage control is at 28～42V, and melting vacuum tightness is lower than 5Pa, and leak rate is lower than 0.2Pam
3/ sec;
Step 4: electron beam melting secondary ingot, pump current is controlled at 0.5～10A, and speed of melting is controlled at 10～80kg/h, and melting vacuum tightness is lower than 5 * 10
-2Pa, leak rate is lower than 0.1Pam
3/ sec.
2. the preparation method of industrial pure zirconium ingot according to claim 1, it is characterized in that: adopt electron beam melting in the step 3, current control is at 0.5～10A, and speed of melting is controlled at 10～80kg/h, and melting vacuum tightness is lower than 5 * 10
-2Pa, leak rate is lower than 0.1Pam
3/ sec.
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| CNA2009100228159A CN101597693A (en) | 2009-06-03 | 2009-06-03 | A kind of preparation method of industrial pure zirconium ingot |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049495A (en) * | 2010-12-20 | 2011-05-11 | 宝鸡钛业股份有限公司 | Production method of zirconium and zirconium alloy flat ingot |
| CN104195355A (en) * | 2014-08-13 | 2014-12-10 | 湖南稀土金属材料研究院 | Zirconium and method for preparing zirconium |
| CN105127677A (en) * | 2015-07-25 | 2015-12-09 | 宝鸡市富源通工贸有限责任公司 | Method for machining zirconium strip through sponge zirconium |
| CN107675004A (en) * | 2017-09-18 | 2018-02-09 | 国核宝钛锆业股份公司 | The preparation method of zircaloy ingot casting and based on zircaloy ingot casting made from this method |
| CN108265182A (en) * | 2018-01-19 | 2018-07-10 | 青海聚能钛业股份有限公司 | A kind of method using electron-beam cold bed furnace recycling melting zirconium defective material |
| CN110907243A (en) * | 2019-11-30 | 2020-03-24 | 西安诺博尔稀贵金属材料股份有限公司 | Hafnium corrosion plate type monitoring sample and preparation method thereof |
| CN111621642A (en) * | 2020-03-05 | 2020-09-04 | 国核宝钛锆业股份公司 | Method for recovering and purifying Nb sawdust residue |
| CN111961895A (en) * | 2020-09-03 | 2020-11-20 | 西部新锆核材料科技有限公司 | Preparation method of zirconium alloy ingot |
| CN114544905A (en) * | 2022-02-23 | 2022-05-27 | 国核宝钛锆业股份公司 | Assessment method for chemical components of nuclear-grade sponge zirconium |
-
2009
- 2009-06-03 CN CNA2009100228159A patent/CN101597693A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049495A (en) * | 2010-12-20 | 2011-05-11 | 宝鸡钛业股份有限公司 | Production method of zirconium and zirconium alloy flat ingot |
| CN102049495B (en) * | 2010-12-20 | 2012-08-29 | 宝鸡钛业股份有限公司 | Production method of zirconium and zirconium alloy flat ingot |
| CN104195355A (en) * | 2014-08-13 | 2014-12-10 | 湖南稀土金属材料研究院 | Zirconium and method for preparing zirconium |
| CN104195355B (en) * | 2014-08-13 | 2016-03-23 | 湖南稀土金属材料研究院 | Prepare the method for zirconium |
| CN105127677A (en) * | 2015-07-25 | 2015-12-09 | 宝鸡市富源通工贸有限责任公司 | Method for machining zirconium strip through sponge zirconium |
| CN107675004A (en) * | 2017-09-18 | 2018-02-09 | 国核宝钛锆业股份公司 | The preparation method of zircaloy ingot casting and based on zircaloy ingot casting made from this method |
| CN108265182A (en) * | 2018-01-19 | 2018-07-10 | 青海聚能钛业股份有限公司 | A kind of method using electron-beam cold bed furnace recycling melting zirconium defective material |
| CN108265182B (en) * | 2018-01-19 | 2020-04-17 | 青海聚能钛业股份有限公司 | Method for recycling smelting zirconium residues by using electron beam cold bed furnace |
| CN110907243A (en) * | 2019-11-30 | 2020-03-24 | 西安诺博尔稀贵金属材料股份有限公司 | Hafnium corrosion plate type monitoring sample and preparation method thereof |
| CN110907243B (en) * | 2019-11-30 | 2022-05-27 | 西安诺博尔稀贵金属材料股份有限公司 | Hafnium corrosion plate type monitoring sample and preparation method thereof |
| CN111621642A (en) * | 2020-03-05 | 2020-09-04 | 国核宝钛锆业股份公司 | Method for recovering and purifying Nb sawdust residue |
| CN111961895A (en) * | 2020-09-03 | 2020-11-20 | 西部新锆核材料科技有限公司 | Preparation method of zirconium alloy ingot |
| CN114544905A (en) * | 2022-02-23 | 2022-05-27 | 国核宝钛锆业股份公司 | Assessment method for chemical components of nuclear-grade sponge zirconium |
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Open date: 20091209 |