• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    1533487 Zirconium alloy SAES GETTERS SpA 9 April 1976 [10 April 1975] 14658/76 Heading C7A [Also in Divisions G6 and H1] Zr 2 Ni in particulate form, possibly pressed into porous blocks, is used as a getter for water vapour at 150-700‹C (20-700‹C if first activated at 800-900‹C for 5-50 seconds) which does not release free H 2 as much as prior art materials. It is particularly applicable to UO 2 nucleur fuel elements, HeZr alloy sheaths of which suffer from hydrogen embrittlement.
    公开号:SU862814A3
    申请号:SU762344051
    申请日:1976-04-09
    公开日:1981-09-07
    发明作者:Барози Альдо
    申请人:С.А.Е.С. Геттерс С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to water absorption methods for getter compounds and can be used to make a getter block of heat-generating elements of atomic reactors. During the long-term operation of the atomic reactor inside the fuel element (TVEL), water vapor is released, which can later be decomposed into oxygen and hydrogen. The release of hydrogen contributes to its combination with zirconium, which constitutes the main structural material (in pure form or in the form of alloys) of a fuel element, while the metal brittleness increases and this can lead to an emergency situation. To avoid this, fuel elements are equipped with a getter block capable of absorbing water vapor. A known method for the absorption of water vapor by a getter material consisting of strips made on the basis of a four-component alloy containing Zr g Ni-i Ti 1. The disadvantage of this method is the difficulty of fabricating a getter material and its low efficiency with respect to water vapor. The closest in technical essence and the achieved result to the proposed invention is a method of absorbing water vapor. A Hitter material based on a tertiary alloy Zr-Ti-Ni called Hipalloy 2 is used. The method is carried out by contacting water vapor with a getter material — at partial pressure of water vapor or a mixture of water vapor with helium 0.1 - 100 mm Hg. Art. and a temperature of 150-700 C, i.e. in the conditions of operation of the fuel elements of a nuclear reactor. The disadvantage of this. The method is a mara capacity of water vapor and the predominant absorption of oxygen from the vapor, which leads to the emergence of hydrogen embrittlement of fuel rod structural materials. The purpose of the invention is to ensure uniform extraction of oxygen and hydrogen in the process of absorbing water vapor to prevent brittleness and fragility of the fuel cladding material. This is achieved by the method of water vapor absorption by the getter material, in which binary zirconium and nickel co-Zr2Ni alloy is used, including their contact during partial vaporization of water vapor or a mixture of water vapor with helium in the range Oj1-100 mm Hg. Art. and a temperature of 150-70 ° C. A distinctive feature of the method is the use of getter material in quality to absorb the water vapor of a binary zirconium-nickel alloy of composition. The process method is as follows. The getter material is obtained from the pure compound by its mechanical grinding to sizes less than 60 µm and subsequent pressing of the powder to obtain a porous compact mass at a pressure of 3000–8000 kg / cm. The resulting getter block is placed in an argon stream saturated with water vapor at 15 ° C to a partial pressure of 23–80 mm Hg. After heating, the block is cooled and the hydrogen content is measured, which is a measure of water vapor absorption by known methods. Under these conditions, 1 mg of Zr2Ni absorbs about 0.5 cm 5 of hydrogen, which corresponds to 5% by weight of water. FIG. 1 is a diagram of a special installation for measuring the water sorption characteristics of getter materials. The installation consists of a closed topic 1, equipped with a microbalance 2, a manometric one; a sensor 3 and a gas analyzer 4, for example a gas chromatograph or a mass spectrometer. The gas analyzer is isolated from the system by valve 5. System 1 is connected to a vacuum pump by valve b, and is also equipped with valve 7. Outside system 1 is a heater 8, which is used to maintain the desired temperature of the getter unit 9, Getter unit 9, prepared from powder with a particle size less than 60 µm has a cylindrical shape with a diameter of 8.1 mm, a height of 2.2 mm, and a weight of 593 m. The system is also equipped with a tube 10 with some water 11. A tube 12 is surrounded by a bath 12 with an ice-cold mixture. Microbalances 2 have a magnet 13 with windings 14 connected to the indicator assembly 15, which converts the amount of current in the windings 14 to the difference in weight between the getter unit and the standard weight. Measurement of water sorption characteristics is performed as follows. Example. The water 11 in the tube 10 is frozen at the aid of the bath with liquid nitrogen, while the valves 6.7 are open and the valve 5 is closed. Pump 16 creates a vacuum. In the system up to 2 mm Hg, then valves 6, 7 are closed, water is brought up and a bath with an ice mixture is placed around the vessel with water, and the pressure in the system rises to 4.579 mm Hg. Art., which corresponds to the pressure of water var. In this case, the temperature of the nagfeater 8 is adjusted so that the temperature of the getter block 9 rises to 150-700 ° C, preferably up to 200-500 ° C, the pressure is controlled by the pressure gauge sensor 3 and the weight gain of the getter block 9 is measured at the indicator unit 15. The pressures and weight increments serve as characteristics of the activity of the getter block, which is presented graphically in Fig. 2, where the increase in weight in mg is plotted along the abscissa axis, and the total pressure in the system in mmHg along the ordinate axis. Art. Curve 17 presents the characteristic of the proposed getter material. The course of curve 17 indicates that the water vapor pressure increases from zero to slightly above equilibrium at and remains at or near this level until the getter block 9 gains a weight gain of about 30 mg. From this point on, the pressure in the system rises above a theoretical value of 4.579 mm Hg, which indicates that the getter device will no longer be able to absorb all of the hydrogen from the water. The analysis of gas in system 1 by gas analyzer 4 indicates the presence of hydrogen, and this confirms a decrease in the water adsorption capacity of the getter device. Example 2. Under the conditions of example 1, a test of the water sorption capacity of a tertiary alloy getter material is carried out, containing, wt%: nickel — 5.03, titanium — 9.30, and zirconium — 82.00 (the rest is insoluble zirconium oxides and titanium). The getter block is also prepared from a powder of less than 60 µm in size, weight. unit is 568 mg. Curve 18 presents the characteristic of a known getter block. The course of curve 18 shows that the phenomenon in the system immediately rises — above the theoretical and all the time remains above this value (segment 19), which indicates the presence of gas in the system that is different from water vapor. Analysis of the composition of this mixture in the system by means of a gas analyzer 4 shows that this gas is hydrogen. A comparison of the known and proposed methods of FIG. 2 allows us to conclude that the absorption efficiency of water vapor without hydrogen evolution by the proposed method is 6 times higher.
    Thus, the application of the proposed method allows water vapor to be adsorbed at high temperatures of hydrogen phases, which, in turn, makes it possible to reduce the hydrogen brittleness of fuel elements of atomic reactors.
    权利要求:
    Claims (1)
    [1]
    1. The patent of FRG 2259570, cl. G 21 G 3/18, 1973.
    2, UK Patent
     1370208, class G 621 C 3/18, 1974 (prototype).
    / city center
    V--
    ff
    类似技术:
    公开号 | 公开日 | 专利标题
    SU862814A3|1981-09-07|Method of absoring water vapours by getter material
    Libowitz et al.1958|The system zirconium–nickel and hydrogen
    Vannice et al.1970|Determination of surface area by chemisorption: Unsupported platinum
    US2926981A|1960-03-01|Method of gettering using zirconiumtitanium alloy
    Cohen et al.1980|Degradation of Lani5 hydrogen-absorbing material by cycling
    US4119488A|1978-10-10|Nuclear reactor fuel element employing Zr2 Ni as a getter metal
    Flood et al.1954|Stresses and strains in adsorbent–adsorbate systems
    Aylmore et al.1961|Technique using 85Kr-labelled krypton for surface area measurements
    Ward1931|The sorption of hydrogen on copper. Part I.—Adsorption and the heat of adsorption
    Stern et al.1965|Cryosorption pumping of hydrogen and helium at 20 K
    Hut et al.1986|Fast and complete CO2-to-graphite conversion for 14C accelerator mass spectrometry
    Barton et al.1972|Surface studies on graphite: Immersional energetics
    Stakebake et al.1973|Water vapor adsorption on plutonium dioxide
    Acres et al.1965|γ Irradiation of alumina catalysts
    Stern et al.1967|The adsorption of atmospheric gases on molecular sieves at low pressures and temperatures. The effect of preadsorbed water
    Kawamura et al.1995|Adsorption characteristics of water vapor on Li2ZrO3
    Cadenhead et al.1971|Hydrogen sorption and exchange on reduced-oxide nickel and copper
    RU2056656C1|1996-03-20|Free neutron production process
    Pecora et al.1977|A magnetization-chemisorption study of hydrogen and sulfur dioxide on iron
    Spalaris1956|The micropore structure of artificial graphite
    Irmer et al.1972|Isotope Effect for Self‐Diffusion in Single Crystals of α Iron and Correlation Factor of Solute Diffusion in α Iron
    Karp et al.1972|Continuous flow measurement of desorption isotherms
    Gavra et al.1985|The EuNi5-H system
    Olander et al.1982|Retention and release of water by sintered uranium dioxide
    Grossman et al.1972|Microphysical, microchemical and adhesive properties of lunar material. 3: Gas interaction with lunar material
    同族专利:
    公开号 | 公开日
    JPS537599B2|1978-03-18|
    JPS51124795A|1976-10-30|
    GB1533487A|1978-11-29|
    FR2306735B1|1981-10-09|
    FR2306735A1|1976-11-05|
    US4071335A|1978-01-31|
    IT1037196B|1979-11-10|
    DE2615611A1|1976-10-14|
    DE2615611C2|1989-04-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US1151160A|1912-01-22|1915-08-24|Edward R Cooper|Alloy and process of producing the same.|
    NL41681C|1931-10-22|
    US3104049A|1959-12-30|1963-09-17|Ibm|High purity vacuum systems|
    US3620645A|1970-05-01|1971-11-16|Getters Spa|Getter device|
    CA962989A|1970-09-22|1975-02-18|Leonard N. Grossman|Alloys for gettering moisture and reactive gases|
    BE792373A|1971-12-08|1973-03-30|Gen Electric|NUCLEAR FUEL CARTRIDGE|
    BE792371A|1971-12-08|1973-03-30|Gen Electric|NUCLEAR FUEL CARTRIDGE|
    US3969185A|1973-05-09|1976-07-13|General Electric Company|Getter for nuclear fuel elements|AU497435B2|1975-10-14|1978-12-14|Westinghouse Electric Corporation|Tritium removal and retention device|
    IT1110271B|1979-02-05|1985-12-23|Getters Spa|NON-EVAPORABLE TERNARY GETTERING ALLOY AND METHOD OF ITS USE FOR THE ABSORPTION OF WATER, WATER VAPOR, OTHER GASES|
    IT1110295B|1979-02-05|1985-12-23|Getters Spa|NON-EVAPORABLE TERNARY GETTERING ALLOY PARTICULARLY FOR THE ABSORPTION OF WATER AND WATER VAPOR IN FUEL BARS OF NUCLEAR REACTORS|
    IT1115156B|1979-04-06|1986-02-03|Getters Spa|ZR-FE ALLOYS FOR HYDROGEN ABSORPTION AT LOW TEMPERATURES|
    US4360445A|1981-06-16|1982-11-23|The United States Of America As Represented By The United States Department Of Energy|Oxygen stabilized zirconium-vanadium-iron alloy|
    DE3316454A1|1983-05-05|1984-11-22|kabelmetal electro GmbH, 3000 Hannover|PIPE SYSTEM CONTAINING TWO OR SEVERAL CONCENTRIC TUBES|
    ES291691Y|1983-11-30|1987-01-16|Westinghouse Electric Corporation|AUXILIARY CONTROL ROD FOR FINE ADJUSTMENT OF THE REACTIVITY OF A NUCLEAR REACTOR|
    IT1173865B|1984-03-16|1987-06-24|Getters Spa|PERFECT METHOD FOR MANUFACTURING PORTABLE NON-EVAPORABLE GETTER DEVICES AND GETTER DEVICES SO PRODUCTS|
    IT1173866B|1984-03-16|1987-06-24|Getters Spa|PERFECT METHOD FOR MANUFACTURING NON-VARIABLE PORTABLE GETTER DEVICES AND GETTER DEVICES SO PRODUCED|
    US4664878A|1984-09-26|1987-05-12|Westinghouse Electric Corp.|Light water moderator filled rod for a nuclear reactor|
    DE3918190C2|1989-06-03|1991-06-06|Dornier Gmbh, 7990 Friedrichshafen, De|
    DE4003694A1|1990-02-07|1991-08-08|Linde Ag|METHOD AND DEVICE FOR REMOVING HYDROGEN FROM WATER CIRCUITS|
    US5238469A|1992-04-02|1993-08-24|Saes Pure Gas, Inc.|Method and apparatus for removing residual hydrogen from a purified gas|
    IT1255438B|1992-07-17|1995-10-31|Getters Spa|NON-EVAPORABLE GETTER PUMP|
    CA2117319A1|1993-07-12|1995-01-13|John D. Baker|Method for the purification of noble gases, nitrogen and hydrogen|
    JP3462562B2|1994-04-14|2003-11-05|日本原子力研究所|Method and apparatus for producing gel particles|
    US5972183A|1994-10-31|1999-10-26|Saes Getter S.P.A|Getter pump module and system|
    US6142742A|1994-10-31|2000-11-07|Saes Pure Gas, Inc.|Getter pump module and system|
    US6109880A|1994-10-31|2000-08-29|Saes Pure Gas, Inc.|Getter pump module and system including focus shields|
    US5911560A|1994-10-31|1999-06-15|Saes Pure Gas, Inc.|Getter pump module and system|
    US5685963A|1994-10-31|1997-11-11|Saes Pure Gas, Inc.|In situ getter pump system and method|
    US5610438A|1995-03-08|1997-03-11|Texas Instruments Incorporated|Micro-mechanical device with non-evaporable getter|
    IT1290451B1|1997-04-03|1998-12-03|Getters Spa|NON-EVAPORABLE GETTER ALLOYS|
    US6186849B1|1998-03-24|2001-02-13|Saes Getters S.P.A.|Process for the production of flat-screen grids coated with non-evaporable getter materials and grids thereby obtained|
    JP4662666B2|1999-06-02|2011-03-30|サエスゲッターズソチエタペルアツィオニ|Composite material and preparation method thereof|
    US6614039B2|1999-06-23|2003-09-02|Brad C. Hollander|Hermetically sealed ultraviolet light source|
    US6193894B1|1999-06-23|2001-02-27|Brad C. Hollander|Methods and apparatus for disinfecting and sterilizing water in water dispensers using ultraviolet radiation|
    US7081225B1|1999-07-20|2006-07-25|Hollander Brad C|Methods and apparatus for disinfecting and sterilizing fluid using ultraviolet radiation|
    US20050169766A1|2002-09-13|2005-08-04|Saes Getters S.P.A.|Getter compositions reactivatable at low temperature after exposure to reactive gases at higher temperature|
    ITMI20042271A1|2004-11-23|2005-02-23|Getters Spa|NON EVAPORABLE GETTER ALLOYS BY HYDROGEN ABSORPTION|
    KR101038240B1|2006-09-15|2011-05-31|사에스 게터스 에스.페.아.|Metal getter systems|
    ITMI20070301A1|2007-02-16|2008-08-17|Getters Spa|SUPPORTS INCLUDING GETTER MATERIALS AND ALKALINE OR ALKALINE-TERROSI METALS FOR THERMOREGULATION SYSTEMS BASED ON TUNNEL EFFECT|
    SE532185C2|2007-04-10|2009-11-10|Westinghouse Electric Sweden|Method of operating a reactor at a nuclear plant|
    ITMI20111870A1|2011-10-14|2013-04-15|Getters Spa|NON EVAPORABLE GETTER COMPOSITIONS THAT CAN BE REACTIVATED AT LOW TEMPERATURE AFTER EXPOSURE TO REACTIVE GASES AT A GREATER TEMPERATURE|
    ITMI20122092A1|2012-12-10|2014-06-11|Getters Spa|NON EVAPORABLE GETTER ALLOYS REACTIVATED AFTER EXPOSURE TO REACTIVE GASES|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT22211/75A|IT1037196B|1975-04-10|1975-04-10|FUEL ELEMENT FOR NUCLEAR REACTOR USING ZR2NI AS GETTERANT METAL|
    [返回顶部]