TW209264B - - Google Patents

Description

Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 209264

BACKGROUND OF THE INVENTION The present invention relates to an anti-fouling structure that can effectively prevent pollutants in the ocean, such as tea lotus, mussels, and seaweed, and an anti-fouling method to protect certain structures from pollution. The structure of the sea surface is in contact with sea water, and it is always exposed to the pollution of pollutants in the ocean, causing surface damage or failure. For example, when a ship has multiple types of marine pollutants deposited on its bottom, it suffers from a drop in thrust, etc. When a power plant has various types of marine pollutants accumulated in its seawater inlet pool, it will be forced to stop Operation because of a serious problem in the circulation of seawater as a cooling medium. So far, in many studies to avoid the deposition of marine pollutants, there is a method to avoid the pollution of the sea surface structure, which is to coat the surface of the structure with the seawater-a coating material containing copper oxide or organic tin. However, there is a serious problem with this traditional method, that is, its coating material has a life cycle as short as one year, but if it is coated with a thick layer, it is very easy to peel off. Therefore, the coating material must be replaced every year, causing difficulties. The maintenance work 〇The use of coating materials containing organic tin, because of its toxicity and the risk of its accumulation in fish products, from the point of view of environmental protection, I do not want it. In recent years, 10% nickel to 90% copper wire has been put into practical use. Although it has a good service life (usability), its antifouling effect is far worse than the coating materials mentioned above. A main object of the present invention is to provide an anti-fouling structure, which can be free from the above-mentioned problems, or that it can be well protected against pollution, and has a long-term paper standard using the Chinese National Standard (CNS) specifications (210x297 Public; ¢) 5-

Outfit · (please read the note on the back &. ^ Item and then item | 1) line · 209264

Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. The validity of the invention description (2 ·) does not require any maintenance, nor does it have the problem of toxicity hazards. Another object of the present invention is to provide a method for protecting the structure against contamination. SUMMARY OF THE INVENTION According to an idea of the present invention, an antifouling structure is provided, which is characterized in that it is made of beryllium copper alloy. Preferably, the beryllium content of the wrinkled alloy is in the range of 02 to 2.8 weight percent. According to another concept of the present invention, there is provided an anti-fouling structure for a sea surface that is used on or in a place where it will contact seawater, and its special feature is that at least its surface is made of a beryllium copper alloy, and the beryllium (Be ) The content is between 0.2 and 2.8 weight percent. Preferably, cobalt (cobalt), nickel (nickel) and silicon (silicon) are selectively included in the beryllium copper alloy, and the content thereof is in the following range: cobalt (Co): 0.2 to 2.7% by weight ( % By weight) Nickel ("): 1.4 to 2.2% by weight Silicon (Si): 0.2 to 0.35% by weight The following will explain the purpose of adding the above elements and why they are limited to the above values. Beryllium (Be): 0, 2 to 2.8% by weight of the use of beryllium is due to (1) the use of free protection of beryllium ions immersed in the structure of seawater to prevent pollution, (2) to improve the strength and properties of beryllium copper alloy such as corrosion resistance Regularity, enhance the productivity of beryllium copper alloy, ⑷Improve the handleability and castability of beryllium copper alloy. This paper scale is easy to use the Chinese National Standard (CNS) A 4 specifications (210X297 public it) 6-(Please read the back Matters needing attention again ri wood R) installed-. Lsτ_ 209264

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5. Description of the invention (3.) Printed and refuted by the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. When it is less than 0.2% by weight, the effects of (1) to (4) above cannot be achieved. When it is higher than 2.8% by weight, not only its metalizability (1 „61 ^ 116 ^ 丨 1 丨 4) decreases, but also the problem of cost effectiveness arises. Co (Co): 0.2 to 2.7% by weight A fine C〇Be compound, which is divided into the entire alloy mold and improves the mechanical properties and productivity of the beryllium copper alloy by heat treatment and regularity of particle size. If it is less than 0.02% by weight, it cannot be achieved The above good effect. If it is higher than 2.7% by weight, not only the flowability of the material is lowered but the substantial improvement of the above effect cannot be obtained. In addition, there are also problems of cost and effect. Nickel (11 丨): 1.4 to 2.2% by weight The medium is used to form a fine NiBe compound, which is dispersed throughout the alloy mold and improves the mechanical properties and productivity of the beryllium steel alloy by heat treatment and regularity of particle size. If less than 1.4% by weight , The above good effect cannot be achieved. If it is higher than 2.2% by weight, not only the flowability of the material is reduced, but there is no substantial improvement in the above effect. In addition, there is also a problem of cost effectiveness. Silicon (Si): 0.2 to 0.35 The amount of silicon is used to improve the material flowability of the beryllium copper alloy. If it is less than 0.2% by weight, the above-mentioned good effects cannot be obtained. If it is more than 0.35% by weight, the resulting alloy becomes brittle and the toughness decreases. The composition of the beryllium copper alloy forming the above antifouling structure may be, for example: (1) beryllium (Be) 0.2 to 1.0% by weight, cobalt (Co) 2.4 to 2.7% by weight, copper (Cu) for balance and inevitable Impurities; ⑵ beryllium (Be) 0.2 to 1.0% by weight, nickel (Ni) 1.4 to 2.2 This paper scale uses the Chinese HJ sample standard (CNS) T4 specification (210x297 male dung) f Please read the notes on the back Bian item #劈 巧 本 "} 装-定 _ 线 · 209264 Λ fi Π ϋ Printed by the Ministry of Economic Affairs Central Purification Bureau Beigongxiao F Cooperative V. Invention description (4 ·) Weight%, copper (Cu) for balance, And inevitable impurities; (3) beryllium (Be) 1.0 to 2.0% by weight, Cu (Co) 0.2 to 0.6% by weight, copper (Cu) for balance and inevitable impurities; and ⑷ beryllium (Be) 1.6 to 2.8 % By weight, 0.4% to 1.0% by weight (Co), 0.2% to 0.35% by weight, silicon (Si) Copper (Cu) and inevitable impurities. According to the third aspect of the present invention, a method for protecting a structure against pollution is provided, which is characterized by including two stages, or more specifically, the first stage is in contact A thin film of beryllium or copper oxide is formed on the surface layer of the wrinkled copper alloy main material of seawater, and beryllium or copper ions are released from the surface layer of the exposed beryllium copper alloy main material into the seawater. The second stage is to make the beryllium or copper The oxidized film is stripped from the beryllium copper alloy main material, wherein the first and second stages are repeated to ensure that beryllium or pin ions are continuously released from the surface layer of the exposed beryllium copper alloy main material into the seawater. BRIEF DESCRIPTION OF THE DRAWINGS The present invention will be referred to the attached 囷, but it is not limited to it, for explanation, where: & Specific Figure 1 shows a schematic diagram of an oxide film of an example of a beryllium copper alloy according to the present invention囷 2 represents a simple copper-nickel oxide film for comparison, and FIG. 3 includes a graph showing the change in the amount of steel ions released from beryllium copper and nickel-copper over time, and a circle showing when the wrinkle is used. The thickness of the corroded substances deposited with steel and nickel steel changes with time. Detailed description of the invention

(Please read and read the notes first? Bian Xiang Zai Xiang-Write a copy) 装-线 · 209264 Printed by the Central Consumers ’Bureau of the Ministry of Economic Affairs Employee's Consumer Cooperative V. Description of the invention (5.) Zhan · present, known copper The structure can be protected against pollution, which is believed to be because the organisms in the ocean hate copper ions. However, using only copper on the sea surface structure, we found that it could not successfully provide a practical and effective anti-fouling effect. As a result of many years of research by the present inventors, a beryllium copper alloy has many more improved effects in protecting a sea surface structure against pollution, as will be understood from the example presented later. The reason is that the interaction of beryllium and copper ions produces an important effect of inhibiting the life in the ocean and avoiding the reproduction of life in the ocean from the structure approaching the sea surface. In other words, this copper-deficient alloy has the effect of avoiding contamination and maintaining a double merger of free copper ions. The antifouling effect and the continuous effect of free copper ions will be described in detail below. (1) The antifouling effect is well known in the literature. The order of ionization tendency of beryllium, copper and wire is as follows: Be> Ni> Cu In other words, beryllium ions are easier to dissociate than copper ions, and copper ions are less difficult than nickel ions. Yu free. In the mixed state of beryllium / copper, first, beryllium is ionized to form a local battery. Due to the effect of current, it has the effect of avoiding the deposition of marine / defective substances. At this time, beryllium ions are internally oxidized. Due to this internal oxidation, first a Be〇 film is produced, typically as shown in Figure i. The BeO film has pores, so that copper ions are free, forming a mixed oxide Cud + BeO on its surface. The dissipation of copper ions into the seawater produces an anti-fouling effect.

(Please read the note Bian item on the back first and then «this page) Binding · Order * Line · Printed by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs, Beigongxiao Cooperative Society $ 1 2〇9364 w Λ (»-_____no V. Description of the invention (6. ) ⑵ Performance of free copper ions The above-mentioned effect of avoiding pollution ⑴ provides another consistent contribution to the performance of free copper ions; that is, the lack of copper allows a function of anti-pollution to continue without stopping. When exposed to seawater, this beryllium copper forms an essential surface oxide (Cu2〇) on its surface, forming a porous BeO oxide film underneath, as shown in Figure 1. Therefore, when Oxidation of the film increases the volume, and free copper ions enter the seawater to be maintained. When this volume increase reaches a certain level, the surface oxide film peels from the porous oxide or Be 0 layer. This produces an electrochemical effect and copper Ion dissociation can be maintained for a long period of time. Refer to circle 3, which compares beryllium copper and copper nickel graphically. The continuous effect of free copper ions possessed by beryllium copper can be explained as follows. When the product of corrosion (oxidation) reaches A certain thickness As shown in Fig. 3, it is peeled from beryllium copper (BeCu). Then, the surface of this beryllium copper alloy is exposed to sea water again and corrodes or oxidizes to form an oxide film. When this film grows to a certain thickness, it is removed from beryllium Copper stripping. This process is repeated again and again. On the other hand, the release of copper ions will decrease with the increase of the thickness of the oxidation product. However, when the oxidation product strips, the beryllium copper alloy is exposed to the surface of the sea again, so the release of steel ions The amount is increased. Therefore, the increase and decrease of the free amount of feed ions occur alternately. According to the beryllium copper alloy of the present invention, the copper ions can be continuously released due to the peeling of the oxide film. As a result, there are no or few contaminants Deposited on the surface of the copper-deficient alloy. This is the opposite of the comparative copper-nickel (CuNi), see 囷 2. When one (please read the back first and pay attention to the Bian item and then 処? '5 wood Π ·) installation · wire ·

This paper standard mail + ea family quasi-ceramic iron 丨 _7 Gonglong f 4 6 2 9 20 66 V. Description of the invention (7 ·) Year after year, an essential nickel oxide (Ni〇) or copper oxide The (CUa 0) layer is formed on the surface of the copper wire, as shown in Fig. 2, and the dissociation of copper ions is reduced. According to the order of ionization trend (Be> Ni> Cu2), this is used for preferential ionization of nickel (Ni) to form a local battery, and an essential oxide is formed on the surface of copper nickel, as shown in Fig. 2. It can be understood from Fig. 3 that the thickness of the corrosion products on the copper wire initially increases with time, but its growth rate decreases as time passes. With this, the amount of free copper ions decreases. In addition, corrosion products are less susceptible to stripping from the copper wire than from copper deficiency. Therefore, the amount of free copper ions is low, resulting in a decrease in the anti-order effect. The beryllium copper alloy has a significant antifouling effect and provides continuous release of copper ions, which was first discovered by the inventors. As far as the inventors are concerned, there has never been an indication or explanation of this fact in the literature so far. There are many kinds of beryllium alloys in practice, including No. 1] L alloy having a beryllium content of 0.2 to 0.6% by weight, and No. 25 alloy having a beryllium content of 1.8 to 2.0% by weight, which are known in the art. However, from the viewpoint of the antifouling effect, it is preferable that the content of beryllium is at least% by weight. At a wrinkle content higher than 2.8% by weight, beryllium and copper will not form a solid solution, that is, the resulting alloy has excellent antifouling effect but its metallicity becomes poor. Therefore, if the beryllium copper alloy has a relatively high beryllium content, it is best to manufacture it by means of transformation. It has been confirmed that not only the beryllium alloy does not have any toxicity problems, but also that it has a long service life in seawater, just like aluminum is laid on copper or white brass. 0 In addition to being fragmented or tubular, the anti-fouling structure of the present invention The body can be used for casting · Order _ Line · Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

% 09:64 Λ 6 Η 6 Fifth, the description of the invention (8.) The method of making various required types depends on the purpose of its use. In addition, the antifouling structure of the present invention can be made entirely or partially of a beryllium copper alloy. In a later example, it can be made of plated or clad metal, and only the part that contacts the seawater is made of copper-deficient alloy. In the following description, the present invention will explain some embodiments in detail and by reference. Example 1 Each of the test samples 1 to 9 listed in Table 1 was made into a sheet with a thickness of about 0.1 to 0.5 nun, and then immersed in seawater. For comparison, a traditional anti-fouling and coating material was coated on the surface of the iron pieces, which were the 10th and 11th test samples, and were also immersed in seawater. After one year, the shellfish and seaweed were evaluated on the surface of the test samples. The evaluation criteria are as follows: ◎: few deposits are found 〇: limited deposits are found Φ: general deposits are found △: increased deposits are found X: a lot of deposits are found X: many deposits are found printed by the Ministry of Economic Affairs, Bureau of Economics, Employee and Consumer Cooperative Printed Back Note f. Re-wood η The corrosion condition of these test samples is also evaluated with five ranks. The durability of the test samples Nos. 10 and 11 was evaluated by observing the appearance of the coating material on it. In addition, the metallability, reproducibility and toxicity of these samples were also evaluated. The results and the overall evaluation results are listed in Table 1. The size of this paper is common to the Chinese National Standard (CNS) Yu 4 specifications (210x297 male dragon) -12-Lat 4 Table 1

Item material AE (S) AE (SW) SA τχ MA CA ARE 1 Be-Cu 11 alloy 0 · 2-0 · 6% Be 0 ® © not found ©-0 2 Be-Cu 1S5 alloy 1.6-1.8% Be ® Θ Θ Not found @-Θ 3 Be-Cu 25 alloy Χ * 8 * 2.0% Βθ Θ © © No present Θ-0 4 Be-Cu alloy 0 ·!% Be 0 0 0 No Θ-0 5 found Be-Cu alloy 2 · 2% Βθ © Θ Θ X was not found @ 〇6 Be-Cu alloy 2.75% Be Θ © © not found X © 0 7 Pure copper 0 0 0 No hair extension • 0-〇8. Copper Town 10% Ni 0 • © No found Θ •. 9 Copper Town 30% Ni 0 Xin Θ No Θ found-• 10 Stainless steel sus XX • No Θ-X 11 Fe + Cii2〇 * Traditional coating © Θ X Not found Θ-〇12 Fe + Organic tin traditional coating Θ Θ X Found ©-X linshu 4 AE: Antifouling effect S: Shellfish SW: Haidan SA: Usability (use period) TX: Toxicity MA: Metallicity CA: Sharpenability ARE: Overall technology evaluation symbol antifouling effect C amount of pollutants) Usability C lifespan? Gen) Disposability overall random evaluation @ 冲 常 好 和 常 好 补 常 好Excellent 0 Gen's good • General 'General General General Δ Increased bad bad bad bad X Increased a lot of Park Chang bad Park Chang bad Zhong Chang bad Central Ministry of Economics Printed by the employee consumer cooperative of the bureau. 〇92 ^ 4 Λ 6 ______ Π6__ V. Description of the invention (9.), Example 2 A beryllium copper alloy (number 165 alloy) containing 1.6 to 1.8% by weight of beryllium, made to a thickness of 0.1lmra Sheet, and then combine it on the surface of a fiberglass boat outer panel. Even after two or more years have passed, there is no noticeable deposit of marine life. In other words, the boat can be used continuously without any cleaning. Example 3 A beryllium copper alloy (No. 25 alloy) containing 1.8 to 2.0% by weight of beryllium was formed into a sheet with a thickness of 0.5 mm and then bonded to the concrete surface of a thermal power plant water inlet pool. Even after two or more years have passed, there are no noticeable deposits of marine life. In other words, this pool does not require any cleaning. I noticed that when the concrete is not protected, it needs to be decontaminated every three months. Example 4 A high beryllium material manufactured by casting. A tube with an outer diameter of 120 mm, a thickness of 10 mm and a length of 300 mm, was immersed in seawater to observe changes over a long period of time. The first tube used was made of beryllium (Be) 2.2% by weight and caramel (Co) 0.72% by weight and silicon (Si) 0.29% by weight as well as balanced copper (Cu) and inevitable impurities. The second tube is made of beryllium (Be) 2.7 wt% and cobalt (Co) 0.80 wt% and silicon (Si) 0.28 wt% as well as balanced copper (Cu) and inevitable impurities. After two years, no noticeable marine deposits were found in each tube. From the understanding that will be obtained from the above description, the present invention has created a breakthrough: that is, if it is applied to a boat, its propulsion energy can be reduced, and if it should be (please «| read the note on the back and read the mustard before dying. 1 £: 0 Packing < Ordering & Threading-This paper scale is printed in China ’s “Family Standard (CNS) > F4 specification (210x297 _ 15 _ Printed by the Ministry of Economic Affairs Central Bureau of Employee Consumers’ Cooperative Fifth) 10.) The water inlet pool used in thermal power plants can be operated without interruption. The technology of the present invention will obviously make a lot of contributions to the breeding industry. For example, the anti-fouling structure and method of the present invention can be applied to The outer layer of a submarine, a power plant by the sea, a fish reef protected by fish, a raft for marine farming, and a cooler or other equipment of a thermal power plant. The anti-fouling structure and method of the present invention as described above have many advantages, including To avoid the deposition of marine life for a long time, effective use for a long time without maintenance, and there is no problem of toxicity, so it also contributes to environmental protection. (Please read the back to the notes No matter how hard it is to write a book R)-Line-This paper uses Chinese B standard (CNS) Grade 4 specifications (210x297 public I)-16-

Claims (1)

Report this repair〗 Έ 命 年 ΙΜΙβ Α7 Β7 C7 D7 VI. Apply for a patent Fan Yuan 1. An antifouling structure made of a beryllium copper alloy, some of which have a beryllium content ranging from 0.2 to 2.8 weight percent 2. The anti-fouling structure as described in item 1 of the patent application, gold has a cobalt content between 0.2 and 2.7 weight percent 3. As the anti-fouling structure as described in item 1 of the patent application, gold has The line content is between 14 and 2.2 weight percent. 4. As described in the second patent application, the antifouling structure has gold with a silicon content between 0.2 and 0.35 weight percent. 5. Kind used in contact with seawater Above or within the local area, at least the surface layer of which is made of corrugated copper alloy with a beryllium content of 0.2%. Copper deficiency alloy park. The scope of lack of sales. Among them is the fan garden of beryllium copper. Among them the range of copper beryllium. Anti-fouling structure up to 2.8 weight (please read "Precautions on the back and then Qiqiang the goods"). The printed version of the paper is printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Cl > -17