TW524856B - Casting slab of shadow mask for braun tube, its heat treatment method and materials of shadow mask for braun tube - Google Patents

Abstract

Disclosed is to provide the relation between casting structure and constituent segregation when solidifized, and by discovering the heat treatment conditions conformed with their segregation states to provide the high degree segregation reducing technique that conventional art can't reach, i.e. to provide excellent stringe mottle grade materials of shadow mask for braun tube. Casing slab of casting structure over 99% by manufacturing shadow mask of Ni-Fe alloy containing 30 to 45% Ni can be used to form columnar crystal and/or chill crystalline. And preferably is casting slab without equiaxial crystalline, Without using electromagnetic stirring, and adopt the continuous casting method in accompany with keeping the temperature of the molten metal of non-solidification portion in the casting slab over liquidus line. Furthermore, adopt the obtained casting slab, heat treat is under the temperature of K-value over 150 μm and time to allow diffusing the Ni segregation.

Description

Ox

Mm — Revised 5. Description of the invention (1) The present invention relates to a stripe-spotted Ni-Fe 糸 alloy picture tube shielding screen used for etching. The picture tube shielding screen is superior in casting effect, especially a suitable film, and its heat treatment method Ni_Fef \ color TV picture tube or screen for cast screen for brain display. Casting β, its heat treatment method and screen use = screen tube masking. Known technology is known as a high-definition picture tube for large color appliances. The burial image or computer display shows that NbFe alloys (especially Fe—36% Ni alloys), " Invar alloys are sometimes called "striped spots"; this alloy money Disadvantages of engraved perforation showing a striped pattern. In the direction of such streaks, there will be X-causes in the material plate mainly used for etching, which is referred to as continuous casting of the material or a segregation of Fe and Fe. After segregation, the thermal elongation 丄 i = of r segregation will be stored in the final wear even after pre-combination. u Fire and other steps, the segregation of this component is also a residual circle: rolling 2 = stretching :::::; in the next step-the step becomes a flat shape in the line direction: L ::: Rolling has always been when carving the product plate ' In order to suppress this kind of insect pests, the Department of Technology has proposed the following: Gazetted No. 7-7827 0 adopted for the occurrence of streaked spots at the time of publication, Bulletin 4 Patent No. 2 1 30577 (Japanese Patent No. Warm production, continuous casting of 3 solidification structure, spot generation method.… Heat treatment above the interval to suppress streaks 89110318-1625TW-1625TYNYJP.ptc page 6 524856

Case No. 89110318 V. Description of the invention (2) It is also disclosed in Japanese Patent No. 2000 0 62 (Japanese Patent Fair 7_u〇34 $ ^ ^ is revealing the same high temperature long-term retreat for continuous casting pieces ^ fire again) In the Japanese Patent No. 195〇743 (Japanese Bent Fair 6-68128), the A newspaper is revealing whether there is a difference between continuous casting and ordinary ingots, in order to meet the conditions of a certain temperature and time relationship. A method of heat-treating a cast piece to suppress the occurrence of streaks. ^ The basic principle of the conventional technique is to use thermal diffusion to remove N existing inside the cast piece caused by a long-term heat treatment after reheating. Segregation of components such as, Ϊ, Cr, etc. is to be homogenized and to prevent the occurrence of 日本 spots. ^ Japanese Patent No. 2 1 30577 has mentioned solidification structure, but the meaning lies in the crystal orientation of the solidified structure on the product board. —The effect of ==, Xiao prevents the neodymium attributed to its crystal orientation., “The problem to be solved by the invention, the bite == ΐ Technical aspects.” As for the color TV image tube: "It is not beneficial to use the shadow tube for shielding Screen shaw Create enough special plates: Although annealing is possible, in recent years, the type has been reduced to 2 types, highly refined, and the mask is engraved. M = = to reduce the level of segregation to the extent that can be achieved with conventional techniques, two: The streaks that occur during the etching of the low Γ mask become insufficient, and it is expected that the phenomenon of low segregation will be even worse. 明 Ming is by discovering the structure of each structure and component segregation during solidification that should be considered in response to such requirements. Relationship, and match

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-Tired number Shan] 1 (1: training five, description of the invention (3) the method to solve the problem of reducing the height to achieve the problem to apply for the first scope of the patent scope of the stripe speck of the superior level of the shielding screen casting sheet, for manufacturing Made from 30% to 45% of cores ::: Casting sheet used to cover the screen, the casting sheet is made of more than 99% of the cast structure is columnar crystals and / or chilled fine crystals Features. The casting slabs in the scope of patent application No. 2 are characterized by the aforementioned casting with equiaxed crystals. Why not, the casting slabs in the scope of patent application No. 3 are not electromagnetically stirred and maintained. The temperature of the molten metal in the unsolidified part of the casting sheet is above the liquidus temperature, and the continuous casting method is used. The heat treatment method of the casting sheet for shielding screen in the scope of patent application No. 4 is based on the aforementioned casting. It is characterized by heat treatment at a temperature and time set to a κ value of 15Q㈣ or more. The material for the shielding screen in the scope of patent application No. 5 is based on the steps of hot rolling, cold rolling, and annealing using the aforementioned casting sheet. 4 main tender. Implementation of the V fishing invention Defects in the "striped spots" of Ni-Fe alloys used as shielding material for the screen can be understood as the main reason for the segregation of the components present in the casting sheet. Structured by columnar crystals and #

524856 __ Case number V. Description of the invention (4)

Fine crystals are best chilled. If the casting material whose casting structure is non-columnar crystal and / or chilled fine crystal is used as the starting material, the subsequent steps, such as the combination of hot rolling processing, cold rolling processing, and annealed casting chips, are used as starting materials. At the same time, the segregation of Ni components during casting is not eliminated, and even if processed into the final sheet of the shielding material, the "striped spots" defect will appear: The material used as the object of the present invention is Ni 30 Raw materials for shielding screens made of ~ 45% NI-Fe alloy. Many materials called 36% Ni, which are mainly made of Fe, and the remainder of which are essentially Fe, are used as the so-called steel alloys. In the composition of the present invention, if necessary, other materials such as Nb, Co, Cr and other added ingredients have no effect on the efficacy of the present invention, and the present invention contains these. The continuous praying makers who limited the casting sheet for shielding screens of the present invention to more than 99%, preferably 100% columnar crystals and / or chilled fine crystals, of the casting structure adopted the following reasons . That is, during the solidification process of the cast piece, due to the thermal diffusion of the next step, in the case of reducing the component segregation, it becomes the interval of the most dominant factor-based component segregation. The shorter the interval, the lower the heating temperature required to reduce segregation, and based on the general knowledge that a short heating time can be used, focusing on the relationship between component segregation and solidified structure of the cast piece, a detailed investigation is conducted. As a result, in the chilled fine crystal crystalline structure having a solidified morphology similar to that of the columnar crystal structure or the columnar aa structure produced in continuous casting, it was found that the interval between the segregation of the components was extremely shorter than that of other solidified structures. fact. It is also found that there is a dependency on the interval between the component segregation of these solidified tissues and the spacing of their primary (primary) dendritic crystal arms. Attributed to regeneration

89110318-1625TW-1625TYNYJP.ptc Page 9 V. Description of the invention (5) (person) and the secondary dendrite crystal arm of the eight-bar kL soil treatment will disappear, so it is not in the present invention: shorter here The thermal organization of time is the second shock of Ben Erming, Ben Zhe, and "Zhang ^ ^ .., a, V;" ^ ^ ^ 100, I, ^ is rapidly condensed and solidified, so almost = η is controlled by and solidified. The close product of the mold at that time only accounts for the whole of Λ in the continuous feed W of f, which is appropriate, and the operation control of the part other than the crystal to set the columnar crystal structure to m can be achieved. In order to avoid partial mixing of the components, it is not appropriate to simultaneously perform tungsten and sintering (EMS) and stir the metal dazzling liquid to obtain the Sic * crystal structure of the present invention. Therefore, ϊίΕ; λ metal solution flow The operation is necessary. Method: effective lambda electromagnetic brake and other metal splatter flow. The non-condensing factor in the film is that even if there is no metal melt flow, the casting, this, and r φ are combined. When the temperature of the molten metal is below the liquidus, I ’m unable to obtain the target because of the equiaxed crystal from the pillar of gold i1, the nucleation occurs and grows. State diagram = phase. Therefore, it is advisable to keep the temperature of the molten metal above 25 ° C or above, specifically, the deviation from the liquidus (A7) f. It is advisable. The upper limit of Αΐ The range of operating conditions is different in each continuous town machine, so there is no special feature / regulation in the present invention. 524856 Case No. 8911031ft Rev. V. Description of the Invention (6) The upper limit of the heating temperature of the casting sheet is not specified, but the negative i 0 ° (-i 〇〇c) of the melting point of the material is suitable. The diffusion distance K / U m (D · t) 0.5 X 106 (1) ^ Doexp (-Q / RT)

Do 1.63 x 1 0 " 4 / m2 · S_1 Q = 2 · 7 9 x 1 05 / J · mol-1 R = 8 · 31 / J · mol-1 · K-1 (D in the formula: diffusion coefficient [m2 / S] D .: Several terms of Ni diffusion obtained from experiments [m2 / S] Q: Activation energy of Ni diffusion obtained from experiments [J / m ο 1] Annealing temperature [K] Annealing time [S]-y gas constant [J / mol · K]%, good table: Ϊ: formula 'system segregation generated in the casting piece, by its two-distance H [Γ μ, heat treatment' shows that it can be used in The well-known relational expression of the diffusion distance of the diffusion in the casting piece. ^ In this formula (1), the temperature of the diffusion active energy of N i is set to 4, and the heat treatment time (immersion time) and heat treatment of the representative casting piece are performed. The K value obtained by substituting and calculating the temperature (immersion temperature) is shown in Table 1 below. 0

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Table 1 κ 値 temperature when substituting the immersion conditions. Heat treatment time 36 hours 48 hours 60 hours 72 hours 1280 ° C 93 108 121 132 1300 ° C 107 124 138 152 1320 ° C 123 142 158 173 1340 ° C 140 161 180 198 6 The figure shows the t value of κ and the rank of the streaks (rank) shown in Table 1.

Relationship. It can be seen from FIG. 7 that, in order to set the level of the streaks and spots to c or higher, it is appropriate to perform heat treatment under the condition that the K value is 1 5 0 // m or more, and to make the κ value 丨 when the level B or higher is desired. The heat treatment is preferably performed at a condition of 70 vm or more. Here, the streak level refers to a person who actually determines the level of the streaks to such an extent that a problem does not cause a problem when the mask is actually produced by the masking screen etching manufacturer. Grade A indicates that the streaks are not observed at all, and E indicates that the streaks are observed very clearly. The intensity of the streaks is used to divide the interval into 5 stages. As for the extent of the streaks, the conventional materials are used. From experience or actual results, it is clear that it is better to be above level C. So this

W4856 V. Description of the invention-L Xiu, Bu-Figure 5 is a diagram showing the relationship between the fabricated η μ ·. The "marked ^ = and streak speck step steps to make the masking screen material shown in Fig. 5: = the plate thickness is positive, and the streak specks on the facet of the manufacturing process are simulated. Figure 5, Λ spot intensity).

The lower the level of the streaks (the higher the quality, the greater the ^ segregation & the quasi deviation, the longer the bar temperature will be heat treated for a long time. / 可 _, ::: From Figure 4, it is known that the cast film Mi will be segregated. The quasi-low = 1 analysis will reduce the tendency, when the value is set to 15G _ or more ^ quasi-difference ③ to G. G7niass% or less, K immersion 4 strokes are also dry-cast on the Λ horizontal axis of the film κ The conditions indicated by the values are the longest interval between the slabs and the spread of the center of the slab after the diffusion. What is the part of the nearby Ni segregation? The standard deviation of the state segregation of the slab. "2; , Refers to the position where the direction of drought is about, and the sampling is at this position. The picture shown in the figure is to set the value of the above to 15. ㈣ 上 使 使 χ-γ-z ,, Pu Yi from the T gauge ", f as shown in Figures 1 to 3, if the situation of diffusion. Y is the bar Λ shift Λ advance / hour ^ shows N1 when the divergence, it is more than the right Refined by "', the area where each piece is processed and the boundary of ^^ 1 and temperature conditions are sought to be ^, the area P is treated with heat treatment, and the area is treated with 孰It is appropriate. When the Nk diffusion is exceeded beyond the W boundary in FIG. 2 and the temperature conditions are processed, the processing time and temperature can be further advanced in the area exceeding the z boundary in FIG. 9 9 To heat ------ two and (when the cattle are processed, you can better seek the diffusion of N i II IWi W Sli tl Γ ΓΠΐ! ΙΏ? ΓίίίΚΙιΐίji.uj «— Page 13 89110318-1625TW-1625TYNYJP.plc 524856

V. Description of the invention (9) The respective fields represented by 0 in FIG. 1, p in FIG. 2, and Q in FIG. 3 indicate that the K value of the diffusion distance represented by the above-mentioned relationship (1) is 150 or more ( Corresponds to the 0 area in Figure 1), it should be 160 // m or more (corresponds to the P area in Figure 2), and then it should be set to 170 // m or more (corresponds to the q area in Figure 3) Realm. 7 And, in the process of the present invention, the Nim segregation for evaluating the characteristics of the material is measured under the following conditions completely, and the data processor is performed.

Measurement device: Microanalyzer JXA-8600MX manufactured by Nippon Denshi Co., Ltd. Measurement method: Line analysis Measurement conditions: Ni segregation measurement conditions are set as follows. Probe diameter irradiation current 100 ~ 300nm 5 · 0 X 1 〇-7 / Add the measured score data, quasi-deviation casting (Pomeranian, meter speed electrical timing fixed length fixed interval light junction pressure 20KV 〇 5 sec / Point 1 0 mm 2 / zm LiF 50 000 points measured by the above-mentioned measurement conditions according to the Li method: nT: the standard Ni deflection P of the data of 4992 points after the moving average four times. The index is expressed by the R axis quasi deviation shown in the vertical axis of Fig. 4. The etching of the masking screen material is performed in a 5Be ferrite chloride solution at a temperature of 20 ° C for 20 minutes to cause the occurrence of streaks. Degree interval

89110318-1625TW-1625TYNY.IP.ptc Page 14 524856 n 卞 5. The level of invention description. FIG. 7 shows a continuous casting sheet made of 99% or more of columnar crystals and / or excited fine crystals, which is an essential part of the present invention, and about 30% of netting crystals are formed in the casting sheet as a comparative example. At the same time, the continuous prayer sheet was attached to the center of the casting sheet, and the results of the Ni segregation after heat treatment at 1300 ° C-72hr were determined. The horizontal axis in Fig. 7 is the measurement distance analyzed by the X-ray microanalyzer line, and the vertical axis is the weight% of Ni. It can also be clearly seen from Fig. 7 that the period of segregation on the equiaxed crystal is 1000 // 111 to 2000 // 111, which can be increased to 2 4 compared with the columnar crystal. As a result, it becomes difficult to reduce segregation by heat treatment. From a cast piece having an equiaxed crystal ratio of 30%, a thin plate sample manufactured by laboratory rolling was subjected to a cut and a streak spot was determined, and the result was grade E. Therefore, the cast sheet of the / equiaxed crystal structure is not suitable as a shielding screen material. In addition, No. 8 is a photomicrograph showing the structure of the casting sheet of the present invention. Fig. 9 is a photograph of the structure of a cast piece of a comparative example. The second etching strip of this photograph is sprayed with a vaporized iron solution (45. Be, 50. 0 etch for 1 minute. Also, the ratio of the casting structure is expressed by the ratio of the vertical cross-sectional area to the casting direction. Or the production of heat-treated strips is ready and 'in terms of inter-operation, taking into account the capabilities of the heat-treating furnace, the cast pieces used to obtain the desired κ value are selected from Table 1 and each garment has a stripe at any time when it is etched The speckled grade is possible. &Quot; Washing Mw said that the cast piece is a 2.5 mm hot-rolled steel sheet, and then proceed to the following: the processing rate in the cold rolling step is approximately 20% to 95%. / ¾ Annealing is in the range of 700 ~ 1000t when using a continuous furnace ^ 疒

524856 _Case No.11 is like 18 _Pingyueri__ V. Description of the invention (11) It is advisable to perform cold rolling in the range of 1 to 50%. After such steps, masking screen materials with different thicknesses in the range of 0.1 to 0.39 mm were manufactured. The masking screen materials were etched and the streak specks were investigated. The results are in the grade A, In the fields of B and C. The effect of the invention is as described above. The masking screen material using the casting sheet for masking screens of the present invention has a level of streaks and speckles that meets the requirements of conventional etching manufacturers. There is no streaks after etching. It is possible to make a streak-speck grade material that meets the requirements of those who use ultra-fine precision.

89110318-1625TW-1625TYNYJP.ptc Page 16 524856 The figure of the K value at the time when the description of the pattern is changed is shown as the graph showing the immersion condition of the casting sheet, and … 一 # ～ 间 3 is a graph showing the value of 1 () when the reading of the casting piece is changed. Figure 4 is a graph of # -necki and the κ value when the conditions are changed. Figure 1 shows the relationship between the segregation standard deviation of k 1 and the immersion strip 1 of the cast piece. Figure 5 shows the relationship between the standard deviation of the segregation N i of the cast piece and the grade of the streaks. Figure 6 shows the value of K and the streak. The relationship between spots. Fig. 7 is a graph showing the results of measuring N i segregation between the casting sheet of the present invention and the casting sheet of the comparative example. Fig. 8 is a photograph of the structure of the casting sheet of the present invention. Comparative photograph of the structure of a cast piece.

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Claims (1)

The cast iron sheet for the Ni alloy tube gold masking screen is used for manufacturing a masking sheet containing 30 to 45% of a masking screen woven by the casting group 7 and 991, and the casting sheet is a system. Above ° is made of columnar crystals and / or chilled fine crystals. For example, those in the scope of the patent of Shenyang include equiaxed crystals. The casting sheet of which the above-mentioned rusty sheet is not 3 · As in the scope of the patent application, the casting sheet is not electromagnetically stirred, and the casting sheet of the member, wherein the liquid temperature of the aforementioned casting sheet is above the liquidus line, = keep the casting sheet Metal melting in the unsolidified part. Twisting operation of continuous casting method to obtain 4 · A kind of heat treatment method for the two-piece film used for the kinescope shielding screen & patent scope No. 1 to 3, which uses the above-mentioned application temperature and time , K is set to 1 5 0 // m for heat treatment. 5 · —The cast sheet of any one of 7 to 3 of the materials used for the shielding tube of the picture tube is manufactured by adopting the first step of the scope of patent application. After having hot rolling, cold rolling, and annealing 89110318-1625TW.1625TYNYJP.ptc Page 18 524856 Γ ......:, male fLirnw * " ** · * 4 i Λ. I cr charge, gas 5, Λ type esms 100 1000 Immersion time / hour Figure 1 Page 1