CN115029701B - Zirconium alloy metal plate etching processing method and formed plate - Google Patents
Zirconium alloy metal plate etching processing method and formed plate Download PDFInfo
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- CN115029701B CN115029701B CN202210798108.4A CN202210798108A CN115029701B CN 115029701 B CN115029701 B CN 115029701B CN 202210798108 A CN202210798108 A CN 202210798108A CN 115029701 B CN115029701 B CN 115029701B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/02—Local etching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a zirconium alloy metal plate etching processing method and a formed plate, wherein the method comprises the following steps: pretreatment and etching treatment; specifically, the pretreatment comprises: processing the zirconium alloy metal plate to form a pre-etched working surface on the outer surface of the zirconium alloy metal plate; the etching process includes: and spraying an etching liquid medicine, etching the specific area of the pre-etched working surface by the etching liquid medicine, and drying after etching to form a plurality of micropores. According to the invention, the pre-etching working surface is arranged on the zirconium alloy metal plate, and then the nitric acid, the hydrogen chloride, the ferric trioxide, the caprolactam, the hydrogen peroxide and the purified water are mixed according to a certain proportion to prepare the etching liquid medicine, so that the etching liquid medicine is used for etching the zirconium alloy metal plate at the development round point on the pre-etching working surface, the zirconium alloy metal plate can be etched by the etching liquid medicine prepared by mixing according to a certain proportion, the etching effect is good, and the processing requirements on micropores with different specifications can be met by controlling the mixing proportion.
Description
Technical Field
The invention relates to the technical field of zirconium alloy processing, in particular to a zirconium alloy metal plate etching processing method and a formed plate.
Background
Zirconium alloys are solid solutions of zirconium or other metals. Zirconium has a very low thermal neutron absorption cross section, high hardness, ductility and corrosion resistance. The main use of zirconium alloys is in the field of nuclear technology, such as fuel rods in nuclear reactors and the like. The typical composition of nuclear grade zirconium alloys is over 95% zirconium and less than 2% tin, niobium, iron, chromium, nickel and other metals added to improve mechanical properties and corrosion resistance.
At present, the zirconium alloy plate is added with the other metals to enhance the corrosion resistance of the zirconium alloy plate, so that the zirconium alloy plate is particularly difficult to process. When the zirconium alloy metal plate is etched, the zirconium alloy metal plate is difficult to etch and is not etched in place due to the special properties of the zirconium alloy metal plate, so that the etched zirconium alloy metal plate cannot meet the actual use requirements, and the zirconium alloy plate is greatly wasted.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a zirconium alloy metal plate etching processing method and a formed plate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of processing a zirconium alloy metal plate by etching, the method comprising: pretreatment and etching
Engraving;
specifically, the pretreatment comprises the following steps: treating a zirconium alloy metal plate to form a zirconium alloy
The outer surface of the metal plate forms a pre-etching working surface;
the etching process includes:
spraying an etching liquid medicine, etching the specific area of the pre-etched working surface by the etching liquid medicine, and drying after etching to form a plurality of micropores;
the specific area is provided with a plurality of developing dots, and the developing dots are exposed areas of the zirconium alloy metal plate on the pre-etched working surface;
the etching liquid medicine can dissolve and corrode the zirconium alloy metal plate, and the etching liquid medicine cannot etch the positions of the pre-etched working surface except for the developing circular points;
the etching liquid comprises the following components: 12 to 13 weight percent of nitric acid, 6 to 7 weight percent of hydrogen chloride, 12 to 13 weight percent of ferric oxide, 6 to 7 weight percent of caprolactam, 12 to 13 weight percent of hydrogen peroxide and the balance of pure water solution.
Optionally, the etching temperature is 20 ℃, and the etching time is 2 minutes, 40 seconds to 3 minutes.
Optionally, the preprocessing includes:
step 1: removing oil stains on the surface of the zirconium alloy metal, finishing and leveling and cleaning;
step 2: spraying photosensitive etching-resistant ink on the outer surface of the zirconium alloy metal plate treated in the step (1), and drying the photosensitive etching-resistant ink to form a photosensitive ink layer;
and step 3: exposing the photosensitive ink layer;
and 4, step 4: developing and washing the exposed position, washing off photosensitive etching-resistant ink exposed by photopolymerization reaction, and forming a plurality of developing circular points on the zirconium alloy metal plate at the exposed position;
the photosensitive ink layer and the plurality of developing dots form a pre-etching working surface, and the plurality of developing dots are arranged in a rectangular array at the photosensitive ink layer;
in addition, the etching liquid medicine can not etch the photosensitive ink layer.
Optionally, the exposure mode in step 3 is:
and (3) carrying out exposure treatment on the photosensitive ink layer by adopting an UV (ultraviolet) machine, wherein the aperture of a film image for exposure is set to be 0.10-0.3 mm.
Optionally, in step 2: spraying the photosensitive etching-resistant ink repeatedly until the photosensitive ink layer is smooth, uniform and evenly distributed on the outer surface of the zirconium alloy metal plate;
wherein the thickness of the photosensitive ink layer is 5-10 μm.
Optionally, the method further includes:
and cleaning the zirconium alloy metal plate after the etching treatment by using a film removing solution to remove the photosensitive ink layer.
Optionally, the membrane removing solution is an alkaline solution.
Optionally, the membrane removing solution is a sodium carbonate solution.
The invention also provides a formed plate, which adopts the zirconium alloy metal plate etching processing method, and the formed plate comprises the following steps:
the main board is made of a zirconium alloy metal plate;
the etching area is positioned on the outer surface of the main board and is distributed in a rectangular scattering mode in the center of the main board;
wherein, micropores in the etching area are distributed in a rectangular array, the diameter length d of the micropores is 300-301 μm, and the depth h of the micropores is 184-185 μm.
Optionally, the etching solution contains nitric acid, hydrogen chloride, ferric trioxide, caprolactam, hydrogen peroxide and purified water in a ratio of 1: 0.5: 1:4 is configured.
The invention has the beneficial effects that:
according to the invention, the pre-etching working surface is arranged on the zirconium alloy metal plate, and then the nitric acid, the hydrogen chloride, the ferric trioxide, the caprolactam, the hydrogen peroxide and the purified water are mixed according to a certain proportion to prepare the etching liquid medicine, so that the etching liquid medicine is used for etching the zirconium alloy metal plate at the development round point on the pre-etching working surface, the zirconium alloy metal plate can be etched by the etching liquid medicine prepared by mixing according to a certain proportion, the etching effect is good, and the processing requirements on micropores with different specifications can be met by controlling the mixing proportion.
Drawings
Fig. 1 is a process flow chart of a method for etching a zirconium alloy metal plate according to an embodiment of the present invention;
FIG. 2 is a flowchart illustrating an embodiment of a method for etching a zirconium alloy metal plate according to an embodiment of the present invention;
FIG. 3 is experimental data of a micro-via etching process performed in a method of etching a zirconium alloy metal plate according to an embodiment of the present invention;
fig. 4 is a schematic diagram illustrating an example of an etching process of forming a zirconium alloy metal plate according to an embodiment of the present invention;
FIG. 5 is a graph showing experimental two-hole etching data in a method for etching a zirconium alloy metal plate according to an embodiment of the present invention;
fig. 6 is a schematic diagram illustrating a second experimental etching process of forming a zirconium alloy metal plate according to an embodiment of the present invention;
FIG. 7 is a graph showing experimental three-hole etching data in a method for etching a zirconium alloy metal plate according to an embodiment of the present invention;
fig. 8 is a schematic diagram illustrating an experimental triple-etching formed zirconium alloy metal plate in the method for etching a zirconium alloy metal plate according to an embodiment of the present invention;
FIG. 9 is a graph showing experimental four-hole etching data in a method for etching a zirconium alloy metal plate according to an embodiment of the present invention;
fig. 10 is a schematic view of a zirconium alloy metal plate formed by an experimental four-etching process in a zirconium alloy metal plate etching processing method according to an embodiment of the present invention;
FIG. 11 is a graph showing experimental five-hole etching data in a method for etching a zirconium alloy metal plate according to an embodiment of the present invention;
fig. 12 is a schematic view of a zirconium alloy metal plate formed by an experimental five-stage etching in a method for etching a zirconium alloy metal plate according to an embodiment of the present invention;
fig. 13 is an overall structural view of a formed plate according to a first embodiment of the present invention;
FIG. 14 is a schematic plan view (in top view) of an overall structure of a formed plate according to one embodiment of the present invention;
FIG. 15 is a plan sectional view of an overall structure of a formed plate according to one embodiment of the present invention;
fig. 16 is an enlarged view of a portion a in fig. 14.
The symbols in the figures are as follows:
1. a main board;
2. an etching region; 21 micro-pores.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that all directional indicators (such as up, down, left, right, front, back \8230;) in the embodiments of the present invention are only used to explain the relative positional relationship between the components, the motion situation, etc. in a specific posture (as shown in the attached drawings), and if the specific posture is changed, the directional indicator is changed accordingly.
In the present invention, unless otherwise expressly stated or limited, the terms "connected," "secured," and the like are to be construed broadly, and for example, "secured" may be a fixed connection, a removable connection, or an integral part; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In addition, if there is a description relating to "first", "second", etc. in the embodiments of the present invention, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The invention is between the production process of the zirconium alloy metal plate and improves the mechanical property and the corrosion resistance by adding other metals. The corrosion resistance of the zirconium alloy plate is greatly increased, the zirconium alloy plate is difficult to etch, common etching liquid almost hardly etches the zirconium alloy metal plate, even the zirconium alloy metal plate can be etched, the zirconium alloy metal plate is difficult to etch and not in place due to the special property of the zirconium alloy metal plate, the zirconium alloy metal plate after being etched cannot meet the actual use requirement, and the zirconium alloy plate is greatly wasted.
With reference to fig. 1 and 2, the present invention provides a zirconium alloy metal plate etching method, which aims at the above problems, and comprises: pretreatment, etching treatment and membrane removal treatment.
And (3) preprocessing, wherein the zirconium alloy metal plate is preprocessed in the preprocessing, so that a pre-etching working surface is formed on the outer surface of the metal plate, and the pre-etching working surface meets the requirement of etching processing. Namely, the pretreatment forms an area which is convenient for etching liquid medicine processing on the outer surface of the zirconium alloy metal plate. Specifically, the pretreatment comprises the following steps:
step 1: removing oil stains on the surface of the zirconium alloy metal plate, and meanwhile, finishing and flattening the surface of the zirconium alloy metal plate, and cleaning;
step 2: and (3) spraying photosensitive etching-resistant ink on the outer surface of the zirconium alloy metal plate treated in the step (1) by using an ink-jet machine, and drying the photosensitive etching-resistant ink to form a photosensitive ink layer. In this step, spraying can be repeated, and it is only necessary to ensure that the photosensitive ink layer is smoothly, uniformly and flatly arranged on the zirconium alloy metal plate. In this step, when the photosensitive etching-resistant ink is sprayed for the first time, the photosensitive etching-resistant ink can be manually checked after being placed into a dryer for drying. If the molding is flat and smooth, directly entering the following steps; if the molding is not smooth, even and flat, secondary spraying is needed, and the secondary spraying is performed at most. And (3) if the secondary spraying does not meet the requirement, removing the photosensitive ink layer on the metal plate, repeating the step (1), and continuously spraying the photosensitive etching-resistant ink until the photosensitive ink layer on the zirconium alloy metal plate is smooth, uniform and evenly distributed.
And 3, step 3: and exposing the photosensitive ink layer by using a UV (ultraviolet) machine, wherein the aperture of a film image for exposure can be set according to the actual processing requirement, and the value range of the aperture is 0.10-0.3 mm. That is, the aperture of the UV machine for exposing the photosensitive ink layer can be, but not limited to, 0.10mm, 0.11mm, 0.12mm, 0.13mm, 0.14mm, 0.15mm, 0.16mm, 0.17mm, 0.18mm, 0.19mm, 0.20mm, \ 8230 \ 8230;, 0.29mm, 0.3mm. And exposing the photosensitive ink layer, wherein the photosensitive ink layer is subjected to photopolymerization at an exposure position, and the exposure position in the photosensitive ink layer can be distributed through a program-controlled UV (ultraviolet) machine. The exposure positions may be distributed in a rectangular array at the photosensitive ink layer, or may be distributed in other shapes (for example, but not limited to, circular or triangular shapes, etc.), as long as the exposure positions do not adhere to each other and overlap each other, which is described herein as being distributed in a rectangular array.
And 4, step 4: developing and washing the exposed position by using an alkaline developing solution, washing off photosensitive etching-resistant ink exposed by photopolymerization, and exposing the zirconium alloy metal plate at the exposed position after the developing solution is washed at the exposed area to form a plurality of developing circular points; the photosensitive ink layer and the plurality of developing dots form a pre-etching working surface, and the plurality of developing dots are arranged on the photosensitive ink layer in a rectangular array; in addition, the etching liquid medicine can not etch the photosensitive ink layer. Namely, the photosensitive ink layer carries out anti-etching protection on the zirconium alloy metal plate in the unexposed area.
The etching process includes:
mixing nitric acid, hydrogen chloride, ferric trioxide, caprolactam, hydrogen peroxide and purified water according to a certain proportion to obtain a mixed aqueous solution of etching liquid medicine, uniformly spraying the etching liquid medicine on a pre-etched working surface, etching developing round points on the pre-etched working surface by the etching liquid medicine, after etching for a period of time, putting the etching liquid medicine into a dryer for drying, and forming a plurality of micropores on a zirconium alloy metal plate, wherein the etching time can be set according to actual requirements, the etching time is generally 2 minutes, 40 seconds and 3 minutes, the etching time can be specifically controlled according to an etching phenomenon, and the etching temperature is kept at 20 ℃. Wherein the etching liquid medicine is a water solution of 12-13 wt% of nitric acid, 6-7 wt% of hydrogen chloride, 12-13 wt% of ferric trioxide, 6-7 wt% of caprolactam, 12-13 wt% of hydrogen peroxide and the balance of purified water. The mixing ratio is described here, and the components are exemplified by 100g of etching solution. The etching solution comprises 100g of etching solution, 12g to 13g of nitric acid, 6g to 7g of hydrogen chloride, 12g to 13g of ferric trioxide, 6g to 7g of caprolactam, 12g to 13g of hydrogen peroxide and 52g to 47g of purified water. That is, the content of nitric acid in 100g of etching solution may be, but not limited to, 12g, 12.1g, 12.2g, 12.3g, 12.4g, \ 8230; \ 8230, 12.9g, 13g. The hydrogen chloride content, the ferric trioxide content, the hydrogen chloride content, the caprolactam content, the hydrogen peroxide content and the purified water content are prepared in the same way. Wherein the proportion of pure water is less, and the etching depth of etching liquid medicine is stronger, can carry out the etching according to actual processing requirement can.
The membrane removing treatment comprises the following steps:
and cleaning the zirconium alloy metal plate subjected to etching treatment by using a film removing solution to remove the photosensitive ink layer. In the film removing treatment, an alkaline solution can be selected to clean the redundant photosensitive ink layer, and simultaneously neutralize the acidic substances in the etching liquid, and then a large amount of purified water is used for cleaning so as to obtain the smoothness, flatness and uniformity of the etched zirconium alloy metal plate. In addition, preferably, the membrane removing solution is a sodium carbonate solution.
In order to highlight the influence of the etching solution formula and the proportion thereof disclosed by the invention on the etching effect, the applicant provides experimental data of four groups of etching solutions with other formulas (the total weight of the etching solution is 800g as an example, and the four groups of experimental variables are the same except for different etching solution formulas (wherein, the etching time is 2 minutes and 30 seconds, the etching temperature is 20 ℃, the other etching environments are the same, and the like), and the concrete steps are as follows:
experiment one: the formula and the proportion of the etching solution in the first experiment are as follows: 200g of nitric acid, 100g of caprolactam and 500g of purified water;
detailed experimental data referring to fig. 3 specifically, a zirconium alloy metal plate after etching is completed by using the etching solution in the first experiment referring to fig. 4;
the conclusion is drawn with reference to fig. 3 and 4: the highest depth value that etching liquid medicine in the experiment one etched out is 64.124um, does not reach the standard depth far away, and micropore's inner wall bottom is not slick and sly yet, still leads to sensitization printing ink layer to take place the part and drops, lets micropore top edge burr many. Therefore, the etching liquid medicine in the first experiment is difficult to etch the zirconium alloy metal plate, and the photosensitive ink layer is easy to separate due to the etching liquid medicine in the first experiment, so that the practical requirement is not met.
Experiment two: the formula and the proportion of the etching solution in the second experiment are as follows: 100g of nitric acid, 100g of caprolactam, 400g of purified water, 100g of hydrochloric acid and 100g of copper chloride;
detailed experimental data specifically refer to fig. 5, and refer to fig. 6, the zirconium alloy metal plate after etching by using the etching solution in experiment two is completed;
with reference to fig. 5 and 6, the conclusion is drawn: the highest depth value that etching liquid medicine in experiment two etched out is 167.414um, does not reach standard depth, and micropore inner wall bottom is slick and sly inadequately, still leads to the sensitization printing ink layer to take place to drop simultaneously, lets the phenomenon of the partial adhesion coincidence appear between the micropore top take place. Therefore, the etching liquid medicine in the second experiment does not etch the zirconium alloy metal plate in place, and the photosensitive ink layer is separated due to the etching liquid medicine in the second experiment, so that the processed micropores do not meet the actual processing requirements.
Experiment three: the formula and the proportion of the etching solution in the third experiment are as follows: 100g of nitric acid, 100g of hydrofluoric acid, 400g of purified water, 50g of hydrochloric acid, 100g of hydrogen peroxide and 50g of ferric trioxide;
detailed experimental data specifically refer to fig. 7, and refer to fig. 8, the zirconium alloy metal plate after etching by using the etching solution in experiment three is completed;
the conclusion is drawn with reference to fig. 7 and 8: the highest depth value etched by the etching liquid medicine in the third experiment is 168.659um, the etching liquid medicine is close to but not reach the standard depth, the tops of the micropores are irregular, and meanwhile the bottoms of the inner walls of the micropores are not smooth enough. Therefore, the etching effect of the etching liquid medicine in the third experiment on the zirconium alloy metal plate is close to the standard requirement but not achieved, so that the processed micropores do not meet the actual processing requirement.
Experiment four: the formula and the proportion of the etching solution in experiment four are as follows: 100g of nitric acid, 50g of caprolactam, 400g of purified water, 50g of hydrochloric acid, 100g of ferric trioxide and 100g of hydrogen peroxide;
detailed experimental data referring to fig. 9, a zirconium alloy metal plate after etching by using the etching solution in experiment four is referred to fig. 10;
the conclusion is drawn with reference to fig. 9 and 10: the highest depth value etched by the etching liquid medicine in the fourth experiment is 203.193um, reaches and exceeds the standard depth, and the whole micropore and the bottom are very smooth. Therefore, the etching liquid medicine in the fourth experiment has a good etching effect on the zirconium alloy metal plate, so that the processed micropores meet the actual processing requirements.
Overall conclusion: under the conditions of the same experimental environment, the same etching time and the same etching temperature,
the etching chemical formula in the first experiment is difficult to etch, and the photosensitive ink layer is easy to fall off;
the etching liquid medicine formula in the second experiment is not etched in place, and the photosensitive ink layer is separated due to the etching liquid medicine in the second experiment;
the etching of the formula of the etching solution in the third experiment is close to the etching requirement, but the tops of the micropores are irregular, and the bottoms of the inner walls of the micropores are not smooth enough;
the etching liquid medicine in the fourth experiment has a good etching effect on the zirconium alloy metal plate, and the processed micropores meet the actual processing requirements;
therefore, the etching solution formula proportion in the fourth experiment is considered for the corrosion resistance of the zirconium alloy metal plate, and the zirconium alloy metal plate is etched.
Meanwhile, in order to compare the influence factors of different temperatures on the formula proportion of the etching solution in experiment four, the applicant has adopted. Namely, the etching effect of the same etching liquid medicine proportion in the experiment IV is compared under different etching temperatures. In addition, a group of comparative experiments with the number of experiment five is provided, which specifically comprises the following steps:
experiment five: the formula and proportion of the etching solution in experiment five are the same as those in experiment four. Namely, the etching liquid medicine is: 100g of nitric acid, 50g of caprolactam, 400g of purified water, 50g of hydrochloric acid, 100g of ferric trioxide and 100g of hydrogen peroxide; the etching temperature is 26 ℃, and the rest is the same as the fourth experiment;
detailed experimental data referring to fig. 11 specifically, the etching solution in experiment five is used in an environment with an etching temperature of 26 ℃, and the zirconium alloy metal plate after etching is referred to fig. 12;
with reference to fig. 11 and 12, it is concluded that: the highest depth value etched by the etching liquid medicine in the fifth experiment is 184.521um, the standard depth is reached, the whole micropore is smooth, but the bottom of the inner wall of the micropore is not smooth, and the processing requirement is barely met. Therefore, in the same etching solution, the etching effect is better when the etching temperature is 20 ℃ than when the etching temperature is 26 ℃.
Example one
Referring to fig. 13, 14, 15, and 16, a formed plate material using one of the above-described zirconium alloy metal plate etching methods includes: a main plate 1 and an etched area 2. Mainboard 1, mainboard 1 is zirconium alloy metal sheet material. Wherein, the etching area is located on the outer surface of the main board 1, and the etching area 2 is in rectangular scattering distribution at the center of the main board 1. Namely, the center line of the etching area 2 coincides with the center line of the main board 1, the etching area 2 can be distributed along the periphery of the surface of the main board 1, the etching area 2 can be completely coincided with the surface of the main board 1, and the zirconium alloy metal plate is utilized to a great extent to meet the actual processing requirement.
In this embodiment, the etching area 2 (representing the same position as the pre-etching working surface in the above description) is etched by the etching solution to obtain a plurality of micro-holes. Wherein the micropores 21 of the etching region 2 are distributed in a rectangular array, the diameter length d of the micropores 21 is 300 μm-301 μm, and the depth h of the micropores 21 is 184 μm-185 μm. That is, the diameter length d of the micro-holes 21 may be 300.00 μm, 300.01 μm, 300.02 μm, 300.03 μm, 300.04 μm, 300.05 μm, 8230301.00. Mu.m, but not limited thereto. Wherein the diameter of the micro-holes 21 can be set according to the exposure aperture. The depth h of the micropores 21 can be obtained similarly, and the value of h can be 184.00 μm, 184.01 μm, 184.02 μm, 184.03 μm, 184.04 μm, 184.05 μm, 823070 and 185.00 μm.
In this embodiment, the etching solution contains nitric acid, hydrogen chloride, ferric trioxide, caprolactam, hydrogen peroxide and purified water in a ratio of 1: 0.5: 1:4 is configured. For example, the total weight of the etching solution is 100g, wherein the total weight of the etching solution is 12.5g of nitric acid, 6.25g of hydrogen chloride, 12.5g of ferric oxide, 6.25g of caprolactam, 12.5g of hydrogen peroxide and 50g of purified water. In this example, the etching was performed at a temperature of 20 ℃ for 2 minutes and 30 seconds.
Referring to fig. 16, in the present embodiment, in order to prevent interference between the plurality of minute holes 21 in the formed plate material at the time of use or processing. A plurality of micropore 21 is the rectangle distribution between, and every two sets of perpendicular parallel micropore group that is close to each other between misplace the setting each other. Namely, one micropore 21 in one micropore group and two micropores 21 close to each other in the other micropore group, the circle centers of the three are connected to form a triangle, and the three inner angles of the triangle are all a. I.e. a is 60. I.e. the triangle is an equilateral triangle. Through the setting of misplacing each other between every two sets of micropore group that are close to each other vertical parallel to realize reducing micropore 21 and appear disturbing when processing and using, make full use of the usable floor area of zirconium alloy metal sheet simultaneously, to a great extent practices thrift the material of zirconium alloy metal sheet.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A zirconium alloy metal plate etching processing method is characterized by comprising the following steps: pretreatment and etching treatment; specifically, the pretreatment comprises the following steps: processing the zirconium alloy metal plate to form a pre-etched working surface on the outer surface of the zirconium alloy metal plate;
the etching process includes:
spraying an etching liquid medicine, etching the specific area of the pre-etched working surface by the etching liquid medicine, and drying after etching to form a plurality of micropores;
the specific area is provided with a plurality of developing dots, and the developing dots are exposed areas of the zirconium alloy metal plate on the pre-etched working surface;
the etching liquid medicine can dissolve and corrode the zirconium alloy metal plate, and the etching liquid medicine cannot etch the positions of the pre-etched working surface except for the developing circular points;
the etching liquid comprises the following components: 12 to 13 weight percent of nitric acid, 6 to 7 weight percent of hydrogen chloride, 12 to 13 weight percent of ferric oxide, 6 to 7 weight percent of caprolactam, 12 to 13 weight percent of hydrogen peroxide and the balance of purified water.
2. The method of claim 1, wherein the etching temperature is 20 ℃ and the etching time is 2 minutes and 30 seconds.
3. The method of claim 2, wherein the pre-treating comprises:
step 1: removing oil stains on the surface of the zirconium alloy metal, finishing and leveling and cleaning;
step 2: spraying photosensitive etching-resistant ink on the outer surface of the zirconium alloy metal plate treated in the step (1), and drying the photosensitive etching-resistant ink to form a photosensitive ink layer;
and step 3: exposing the photosensitive ink layer;
and 4, step 4: developing and washing the exposed position, washing off photosensitive etching-resistant ink exposed by photopolymerization reaction, and forming a plurality of developing circular points on the zirconium alloy metal plate at the exposed position;
the photosensitive ink layer and the plurality of developing dots form a pre-etching working surface, and the plurality of developing dots are arranged in a rectangular array at the photosensitive ink layer;
in addition, the etching liquid medicine can not etch the photosensitive ink layer.
4. The method of claim 3, wherein the exposure in step 3 is:
and (3) carrying out exposure treatment on the photosensitive ink layer by adopting an UV (ultraviolet) machine, wherein the aperture of a film image for exposure is set to be 0.10-0.3 mm.
5. The method of claim 4, wherein in step 2: spraying photosensitive etching-resistant ink repeatedly until the photosensitive ink layer is smooth, uniform and evenly distributed on the outer surface of the zirconium alloy metal plate;
wherein the thickness of the photosensitive ink layer is 5-10 μm.
6. The method of etching a zirconium alloy metal plate according to any one of claims 1 to 5, further comprising:
and cleaning the zirconium alloy metal plate after the etching treatment by using a film removing solution to remove the photosensitive ink layer.
7. The method according to claim 6, wherein the film removing solution is an alkaline solution.
8. The method of claim 7, wherein the film removing solution is a sodium carbonate solution.
9. A formed plate material obtained by the method for etching a zirconium alloy metal plate according to any one of claims 1 to 8, said formed plate material comprising:
the main board is made of a zirconium alloy metal plate;
the etching area is positioned on the outer surface of the main plate, and the etching area is in rectangular scattering distribution at the center of the main plate;
the micropores in the etching area are distributed in a rectangular array, the diameter length d of each micropore is 300-301 μm, and the depth h of each micropore is 184-185 μm.
10. The formed sheet according to claim 9, wherein the etching solution contains nitric acid, hydrogen chloride, ferric trioxide, caprolactam, hydrogen peroxide and purified water in a ratio of 1: 0.5: 1:4 is configured.
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US4059678A (en) * | 1973-02-02 | 1977-11-22 | Fmc Corporation | Stabilization of iron-containing acidic hydrogen peroxide solutions |
US4927492A (en) * | 1987-08-31 | 1990-05-22 | Westinghouse Electric Corp. | Etching process for zirconium metallic objects |
JP2016211058A (en) * | 2015-05-12 | 2016-12-15 | 三愛プラント工業株式会社 | Porous metal plate and manufacturing method therefor |
CN114231986A (en) * | 2021-12-17 | 2022-03-25 | 中国核动力研究设计院 | Method for etching crystal grains of zirconium alloy after irradiation |
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GB0324947D0 (en) * | 2003-10-25 | 2003-11-26 | Avecia Ltd | Process |
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US4059678A (en) * | 1973-02-02 | 1977-11-22 | Fmc Corporation | Stabilization of iron-containing acidic hydrogen peroxide solutions |
US4927492A (en) * | 1987-08-31 | 1990-05-22 | Westinghouse Electric Corp. | Etching process for zirconium metallic objects |
JP2016211058A (en) * | 2015-05-12 | 2016-12-15 | 三愛プラント工業株式会社 | Porous metal plate and manufacturing method therefor |
CN114231986A (en) * | 2021-12-17 | 2022-03-25 | 中国核动力研究设计院 | Method for etching crystal grains of zirconium alloy after irradiation |
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