METHOD OF ION-PLASMA APPLICATION OF CORROSION-RESISTANT FILM COATINGS ON ARTICLES MADE FROM ZIRCONIUM ALLOYS

Abstract

A method of ion-plasma application of corrosion-resistant film coatings on articles made from zirconium alloys includes placing articles in a planetary carousel mechanism, heating the articles, and ion-beam etching and surface activation of the articles using water-cooled unbalanced magnetrons. In addition, the surface of the articles is activated using an ion source which generates gas ions with an accelerating voltage of up to 5000 V and with feeding of a bias voltage to the articles. The coating is applied by using unbalanced and balanced magnetrons simultaneously with a residual induction of the magnetic field from 0.03 T to 0.1 T. The coating is applied to articles which are made from zirconium alloys and are placed vertically in a planetary carousel mechanism. The articles are heated in the coating application process to a temperature of 150-600° C., wherein the heaters are accommodated along the entire length of the articles. This produces corrosion-resistant film coatings of uniform thickness along the outer surface of articles made from zirconium alloys and raises productivity due to an increase in the discharge power density of magnetrons.

Claims

1. A method of ion-plasma application of corrosion-resistant film coatings on articles made from zirconium alloys including placing articles in a planetary carousel mechanism, heating the articles, and ion-beam etching and surface activation of the articles surface using water-cooled unbalanced magnetrons, additional activation of the articles surface using an ion source which generates gas ions with an accelerating voltage of up to 5000 V while feeding of a bias voltage to the articles, application of the coating by using unbalanced and balanced magnetrons simultaneously with a residual induction of the magnetic field from 0.03 T to 0.1 T, characterized in that the coating is applied to articles which are placed vertically in a planetary carousel mechanism, and the articles are heated in the coating application process to a temperature of 150-600° C., wherein the heaters are accommodated along the entire length of the articles.

2. The method according to claim 1, wherein discharge power density of each of the unbalanced magnetrons is from 5 to 80 W/cm.sup.2.

3. The method according to claim 1, wherein discharge power density of each of the balanced magnetrons is from 40 to 600 W/cm.sup.2.

4. The method according to claim 1, wherein the applied coating is a chrome coating.

5. The method according to claim 1, wherein the applied coating is a chrome alloy coating comprising Cr: 0-75%, Al: 0-2.1%, Fe: 0-22%, Ni: 0-2.5%.

Description

[0024] The proposed invention is illustrated by the following functions:

[0025] FIG. 1 shows the structural diagram of a vacuum plant, where 1, 2—unbalanced magnetrons with sputtered water-cooled targets; 3—a vacuum chamber; 4—a planetary mechanism of carousel type, 5—articles from zirconium alloys; 6, 7—balanced magnetrons; 8—rigging for fixation of articles; 9—ion source, 10—sputtered target.

[0026] FIG. 2 shows the pattern of heater location, where 4—a planetary mechanism of rotary type; 5—articles of zirconium alloys; 11—heaters.

[0027] FIG. 3 shows a comparative diagram changing the weight gain depending on the test time in the samples made of zirconium alloy without or with a coating applied by ion-plasma method in superheated vapor.

[0028] FIG. 4 shows a photo of a microstructure in the cross section of the zirconium alloy article transverse fracture, where 12—a layer of chrome coating, 5—zirconium alloy articles.

[0029] The method of ion plasma application of corrosion resistant film coatings onto articles from zirconium alloys consists in the fact that articles 5, which are seamless cold rolled pipes made of E110 zirconium alloy with outer diameter from 6 to 15 mm, length of up to 5 in, are fixed in positions for rotation of the planetary carousel mechanism 4, the vacuum chamber 3 is pumped to pressure of (4-5)×10.sup.−3 Pa, the planetary carousel mechanism 4 rotation is activated, and articles 5 are heated using a heater 11 to temperature 150-600 ° C. For additional cleaning of surface in articles of zirconium alloys, ion etching and activation of surfaces shall be used with the help of water-cooled unbalanced magnetrons 1, 2, as well as additional activation of the articles surface using an ion source 9, generating gas ions, with accelerating voltage up to 5000 V. Activation of the surface in articles made of zirconium alloys 5 with argon ions is carried out at discharge current of 6-10 A and bias voltage of 100-200 V on the articles 5. Then targets 10 are sputtered using the ion-plasma method with the help of simultaneous use of unbalanced magnetrons 1, 2 and balanced magnetrons 6, 7, where targets of chrome are used, or its alloys with Cr. 0-75%, Al: 0-2.1%, Fe: 0-22%, Ni: 0-2.5%, at residual induction of the magnetic field from 0.03 T to 0.1 T using a complex based on the vacuum plant (FIG. 1). A coating 12 (FIG. 4) of chrome or its alloys with thickness of 5-25 μm is applied for 2-5 hours under operating pressure (1-3)×10.sup.−1 Pa. Then articles made of zirconium alloys 5 are cooled together with the vacuum chamber 3, air is injected into the vacuum chamber 3, and then the articles 5 are extracted from the vacuum chamber 3.

[0030] The following methods are used to apply the coating based on chrome or its alloys: preliminary vacuum <10.sup.−3 Pa; operating vacuum P=0.01-0.05 Pa; start voltage U=600-800 V; operating voltage U=350-700 V; charge capacity density 5-600 W/cm.sup.2.

EXERCISE OF INVENTION

Example 1

[0031] In particular case the coating of chrome is applied on the articles made of zirconium alloys 5, which represent seamless cold rolled pipes made of zirconium alloy E110 with the surface in the delivery condition with outer diameter of 9.1 and 9.5 mm, length of up to 4 in.

[0032] Chrome targets 10 are used in the magnetron sputtering system.

[0033] First the articles made of zirconium alloys 5 are fixed in positions for rotation of the planetary carousel mechanism 4, the vacuum chamber 3 is pumped to pressure of 4×10.sup.−3 Pa, the planetary carousel mechanism 4 rotation is activated, and articles 5 are heated using a heater 11 to temperature 250° C. For additional cleaning of surface in articles, ion etching and activation of surfaces shall be used with the help of water-cooled unbalanced magnetrons 1, 2, as well as additional activation of the articles surface using an ion source 9, generating gas ions, with accelerating voltage of 3000 V; activation of the surface in articles 5 with argon ions is carried out at discharge current 1.5 A and bias voltage of 100 V on the articles 5.

[0034] The chrome target 10 is sputtered by the ion-plasma method using simultaneously unbalanced magnetrons 1, 2 and balanced magnetrons 6, 7 with residual induction of the magnetic field of around 0.05 T using the complex based on the vacuum plant (FIG. 1). The chrome coating 12 with thickness of 7 and 15 μm is applied for 2 and 4 hours, accordingly, at operating pressure of 2×10.sup.−1 Pa.

[0035] Then the articles 5 are cooled in the vacuum chamber 3 under residual pressure of 4×10.sup.−3 Pa for 1.5-2 hours, and then air is injected into the vacuum chamber 3, then the articles 5 are removed from the vacuum chamber 3 and inspected for defects.

[0036] The structure and morphology of the corrosion resistant chrome coating 12 were tested by the method of scanning electronic microscopy in the cross sections of the transverse fracture of the chrome coating on the zirconium alloy article 5 (FIG. 4). The fracture plane is quite even and homogeneous. Pores, nonuniformities and flakes are unavailable. The coating is even along the thickness, the coating thickness is 8.748 μm. The chrome coating layer is tightly adjacent to the substrate made of alloy E110.

[0037] To test corrosion characteristics of the coatings, comparative high temperature corrosion tests were carried out on samples with or without a chrome coating.

[0038] Comparative corrosion tests of samples made of E110 alloy by the ion-plasma coating application method are carried out with the following parameters: medium—vapor, pressure—atmospheric, test type—double-sided oxidation, test temperature—1000-1200° C., vapor flowrate—25-90 g/hr (˜1.5-5.5 mg/cm.sup.2/s), heating speed of around 50°, cooling speed is 20° minimum per second, sample length—30 mm, test duration—4000 s.

[0039] FIG. 3 shows a comparative diagram changing the weight gain of samples depending on the test time in the samples made of zirconium alloy without or with a chrome-based coating applied by ion-plasma method in superheated vapor. Sample weight gain is a characteristic of corrosion properties of coatings under the conditions simulating a beyond design basis loss of coolant accident (LOCA).

[0040] During oxidation of the initial uncoated sample made of E110 alloy in vapor, after 770° C. there is a flaking oxide film being produced.

[0041] Oxidation of samples from E110 alloy with the applied chrome-based coating happened at a lower speed compared to the initial sample made of E110 alloy.

[0042] Comparatively high temperature tests in vapor at 1000-1200° C. demonstrated that speed of sample oxidation with a chrome coating was 5 times lower than in uncoated samples in the initial state.

[0043] The survey data confirm that chrome coating characteristics provide for high corrosion resistance of articles made of zirconium alloys in the superheated vapor.

Example 2

[0044] In another particular case the coating of chrome alloy is applied on the articles made of zirconium alloys 5, which represent seamless cold rolled pipes made of zirconium alloy E110 with the surface in the delivery condition with outer diameter of 9.1 and 9.5 mm, length of up to 4 in.

[0045] The magnetron sputtering system uses targets 10 made of chrome alloy containing Cr: 0-75%, Al: 0-2.1%, Fe: 0-22%, Ni: 0-2.5%.

[0046] First the articles 5 are fixed in positions for rotation of the planetary carousel mechanism 4, the vacuum chamber 3 is pumped to pressure of 4×10.sup.−3 Pa, the planetary carousel mechanism 4 rotation is activated, and articles 5 are heated using a heater 11 to temperature 150° C. For additional cleaning of surface in articles made of zirconium alloys, ion etching and activation of articles surfaces shall be used with the help of water-cooled unbalanced magnetrons 1, 2, as well as additional activation of the articles surface using an ion source 9, generating gas ions, with accelerating voltage of 2000 V; activation of the surface in articles 5 with argon ions is carried out at discharge current 1, 2 A and bias voltage of 150

[0047] V on the articles 5.

[0048] The chrome alloy target 10 is sputtered by the ion-plasma method using simultaneously unbalanced magnetrons 1, 2 and balanced magnetrons 6, 7 with residual induction of the magnetic field of around 0.05 T using the complex based on the vacuum plant (FIG. 1). The chrome alloy coating with thickness of 7 and 15 μm is applied for 2.5 and 4.5 hours, accordingly, at operating pressure of 2×10.sup.−1 Pa.

[0049] Then the articles made of zirconium alloy 5 are cooled in the vacuum chamber 3 under residual pressure of 4×10.sup.−3 Pa for 1.5-2 hours, and then air is injected into the vacuum chamber 3, then the articles 5 are removed from the vacuum chamber 3 and inspected for defects.

[0050] The structure of fracture in a corrosion-resistant coating made of a chrome-based alloy containing Cr: 0-75%, Al: 0-2.1%, Fe: 0-22%, Ni: 0-2.5% in the cross section of the coating on the article made of zirconium alloy 5 is smooth and homogeneous. There are no pores or flakes. The coating is even in thickness, coating thickness is 8.5 μm, it tightly adjoins the substrate made of E110 alloy.

[0051] To test corrosion characteristics of the coatings, comparative high temperature corrosion tests were carried out on samples with or without a chrome-based coating.

[0052] Corrosion tests are carried out with the following parameters: medium—vapor, pressure—atmospheric, test type—double-sided oxidation, test temperature—1000-1200° C., vapor flowrate—25-90 g/hr (˜1.5-5.5 mg/cm.sup.2/s), heating speed of around 50°, cooling speed is 20° minimum per second, sample length—30 mm, test duration—4000 s.

[0053] Weight gain depending on the time of testing samples made of zirconium alloy without or with a chrome-based coating applied by the ion-plasma method in the superheated vapor is 24 mg/dm.sup.2 and 11 mg/dm.sup.2 after 30 days, accordingly, and 30 mg/dm.sup.2 and 14 mg/dm.sup.2 after 60 days, accordingly. Sample weight gain is a characteristic of corrosion properties of coatings under the conditions simulating a beyond design basis loss of coolant accident (LOCA).

[0054] During oxidation of the initial uncoated sample made of E110 alloy in vapor, after 770° C. there is a flaking oxide film being produced.

[0055] Oxidation of samples from E110 alloy with the applied chrome-based alloy coating happened at a lower speed compared to the initial sample made of E110 alloy.

INDUSTRIAL APPLICABILITY

[0056] Comparative high temperature tests in vapor at 1000-1200° C. demonstrated that speed of sample oxidation with a chrome-based coating was 5 times lower than in uncoated samples in the initial state.

[0057] The survey data confirm that chrome-based coating characteristics provide for high corrosion resistance of articles made of zirconium alloys in the superheated vapor.

[0058] Therefore, the proposed invention makes it possible to obtain corrosion resistant film coatings of even thickness along the outer surface of the articles from zirconium alloys and improving quality of applied coatings through even heating of the entire surface of articles, as well as increasing efficiency of coating application process through higher density of magnetron charge capacity density.