JP2690727B2 - Surface treatment method for amorphous alloy thin plate having difficult wettability surface - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention provides a method for surface treatment of an ultrathin amorphous alloy thin plate having a difficult wettability surface and the amorphous alloy thin plate By rubbing a rubbing body that has a sufficient hardness surface to scrape off the extreme surface while making the surface pressure in the plate width direction uniform, the reaction with the surface treatment liquid is promoted and the time is extremely short. In particular, the present invention relates to a surface treatment method for an amorphous alloy thin plate having a difficultly wettable surface to obtain a target surface treatment film. (Prior Art) The inventors of the present invention first applied a surface treatment apparatus provided with a sliding member made of a non-rotating rod state in order to form a surface treatment film on a hardly wettable metal. No. (Actual 60-6025)
No. 752) The specification (hereinafter referred to as the prior invention) was proposed. The present invention relates to the improvement of the uniformity of the surface pressure in the plate width direction, the prevention of local abrasion of the rubbing body, and the control of the adhered amount due to this. When applying a chromic acid, phosphate or chromic acid phosphate mixed treatment liquid to an amorphous magnetic alloy thin plate having a hard-to-wet surface, and drying or baking it, the applied treatment liquid is baked as it is. Need to be applied uniformly. In particular, the surface of the amorphous magnetic alloy thin plate is covered with dense silicon oxide or the like, and has poor wettability depending on the treatment liquid. Therefore, the ordinary aqueous treatment liquid cannot repel the treatment liquid to achieve a uniform surface treatment. Therefore, in order to improve the wettability, measures have been conventionally taken in terms of pretreatment of the steel sheet and treatment liquid. As a countermeasure, a method of lowering the surface tension of the treatment liquid,
There are a method of increasing the corrosiveness of the treatment liquid and a method of increasing the activity of the plate surface. Specifically, a method of using a bath to which a surfactant or an organic solvent is added, a method of increasing the concentration of an acid component to increase the corrosiveness after treatment, or a method of raising the temperature, a method of performing pickling as a pretreatment, etc. There is. However, although these methods have improved wettability, they have the drawback of shortening bath life and complicating the process. Of course, if there is oil on the surface,
It is necessary to thoroughly degrease beforehand. Rotating rubber rolls are usually used for applying or squeezing the treatment liquid, but the strip-shaped amorphous alloy thin plate with a plate thickness of 100 μm or less has edges like razor blades.
Easy to bite into the roll and scratch easily. Further, in the case of the squeeze roll method, the action of promoting the reaction between the treatment liquid and the plate is extremely small. However, in the process of the invention of the above-mentioned prior application, rods of glass, ceramics, stainless steel, superalloy, etc., which have a hard surface and are hard to be exposed to the treatment liquid due to their material, are pressed so as not to rotate, and the space between them is already treated. It has been found that the following effects can be obtained by passing the thin steel strip in contact with the liquid. (1) Before passing between the two pressed rods, the treatment liquid dropped only on the upper surface of the steel strip, no matter where it is dropped, due to the capillary phenomenon in the gap between the rod and the plate, Not only in the width direction of the upper surface but also on the back surface at the same time. (2) Like a phosphate or chromic acid phosphate mixed treatment solution,
When a film is formed by a chemical reaction with the surface of the steel sheet, the rubbing between the rod and the surface of the steel sheet facilitates the chemical reaction and facilitates the film formation. (3) The amount of coating can be appropriately controlled by changing the concentration of the treatment liquid to be coated. (Problems to be Solved by the Invention) In order to more uniformly form a surface-treated coating on an amorphous magnetic alloy thin plate having a difficultly wettable surface and to pass a large amount at high speed, the above-mentioned prior application is required. The device of the invention has been found to have the following problems. (1) When the rod-shaped body is rubbed against a thin plate, the rod-shaped body is pressed down and supported by the end of the rod-shaped body, and when the pressure is applied, the rod-shaped body bends, and high pressure is applied only to the end of the rod-shaped body, and the central part Weak surface pressure is applied. Therefore, adverse effects are exerted on the uniformity of the treatment film, the reactivity of the treatment liquid with the thin plate, the sheet passing property of the thin plate, and the local wear of the rod-shaped plate. (2) The rod-shaped body pressed in the non-rotating state is abraded against the thin plate, so that the contact portion of the rod-shaped body is worn, which causes an increase in the amount of surface treatment film adhered and non-uniformity. Not suitable for passing. (3) Due to the capillary phenomenon in the gap between the rod-shaped body pressed in the non-rotating state and the thin plate, the surface treatment liquid dropped on the upper surface of the thin plate also spills over to the back surface, enabling simultaneous front and back coating. However, when a high-speed strip and a wide material are used, the difference in the amount of adhesion between the end portion and the central portion becomes large. Also, it may not completely wrap around the back surface. (Means for Solving the Problems) The essence of the present invention is that an amorphous alloy thin plate having a thickness of 100 μm or less, which has poor wettability, is contact-rubbed with an opposing rotatable rubbing body, A method of forming a surface treatment film on the amorphous alloy thin plate, comprising: (a) the rotatable rubbing body has a hardness sufficient to rub the extreme surface of the amorphous alloy thin plate; It is made of any one of glass, metal, non-ferrous metal, alloy, and ceramics having corrosion resistance to the surface treatment liquid, and (b) behind at least one of the opposed rotatable rubbing bodies that come into contact with the amorphous alloy thin plate. A backup device for holding the rotatable rubbing body, and (c) the surface of the amorphous alloy thin plate before the amorphous alloy thin plate and the rotatable rubbing body make contact with each other. Supply the surface treatment liquid to Is a surface treatment method for an amorphous alloy thin plate having a hardly wettable surface. Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 shows that the backup device 2 presses the rubbing body 1 so that the surface pressure in the plate width direction of the rubbing body 1 held in the metal frame 4 is evenly applied. An outline of an example of an apparatus for performing a surface treatment on an amorphous alloy thin plate having a hardly wettable surface by rubbing an extremely thin amorphous alloy thin plate 6 in contact therewith is shown. In this example, the amorphous alloy thin plate 6 horizontally moves from the left side to the right side, but before the amorphous alloy thin plate 6 comes into contact with the rubbing body 1, the amorphous alloy thin plate 6 looks like a mixed solution of phosphate or chromic acid phosphate. By dropping or spraying various surface treatment liquids,
If supplied to the surface of the amorphous alloy thin plate, the surface of the amorphous alloy thin plate is contact-rubbed with the rubbing body to renew the extremely wettable extreme surface, enhancing the surface reactivity and surface treatment. A film is formed. FIG. 1 shows an example of means for equalizing the surface pressure in the plate width direction by the backup device 2. In the case of FIG. 1 (a), the self-weight of the backup device 2 and the load type in which the weight 3 is placed on the backup device 2,
In the case of (b), a spring type in which the spring 9 presses down,
In the case of (c), an air cylinder type that is pressed down by the cylinder 10 is provided, and in the case of (d), a cylinder 10 is provided at the top and bottom to provide a quick open mechanism that facilitates the passage of the amorphous alloy thin plate at the time of starting the passage. In each case, the load is determined by the conditions such as the strip passing speed and the adhesion amount. FIG. 3 shows an example in which the surface treatment liquid leveling jig 7 is applied to the front surface of the rubbing body stand in order to apply it to high-speed strips and wide materials. (A) shows a simple structure in which flat plates are combined so as to give a minute clearance, and (b) shows one having a liquid supply port 8. The size of the clearance is adjusted so that the surface treatment liquid fills the liquid leveling jig. Further, FIG. 5 shows that only one of the upper and lower sides of the amorphous alloy thin plate is in contact with the rubbing body 1, and two sets of the sliding rubbing are arranged so that the rotating rolls 11 are arranged so as to sandwich the amorphous alloy thin plate 6 therebetween. An example in which a body stand is arranged is shown. As described above, according to the present invention, not only the rubbing members are arranged on both sides of the amorphous alloy thin plate, but also the one can be arranged on one side. The number of passes of the rubbing body is determined by looking at the passing conditions and the condition of the surface-treated film, but if two or more passes are used side by side instead of one pass, the effect is further enhanced. Usually, 3 passes will be enough to achieve the purpose. The shape of the rubbing body used in the present invention may be circular or polygonal. When a polygonal rubbing body is used, the position of contact with the amorphous alloy thin plate may be the vertex or the side of the polygon. However, when used on the side, if the contact surface is large, the friction with the amorphous alloy thin plate increases, and the amorphous alloy thin plate may be cut.In that case, it is recommended to make contact at the apex of the polygon. preferable. The surface of the rubbing body may be a smooth surface. However, a slightly rough surface may be used in order to increase the adhesion amount, but too rough is not preferable for passing an ultrathin plate. When using a circular rubbing body, the diameter is preferably 5 to 20 mmφ. If it is less than 5 mmφ, the risk of breakage is high, and if it is 20 mmφ or more, the control accuracy of the adhered amount becomes poor. The arrangement position of the upper and lower rubbing members is the best when the center of the rubbing member is aligned with the upper and lower positions when viewed from around the surface treatment liquid. When it becomes necessary to control the reactivity between the amorphous alloy thin plate and the surface treatment solution, the centers may be shifted. FIG. 2 shows an example in which the rubbing body is connected to a rotating machine in order to rotate the rubbing body 1. The rotation speed and direction of the rubbing body are determined by the passing speed of the amorphous alloy thin plate, the uniformity of the surface treatment film, and the amount of adhesion. Further, the sliding member may be rotated on one side only, or both rotating machines may be independently operated to change the rotational speed, or the upper and lower sliding members may be simultaneously rotated, and the rotation may be continuous. It may be intermittent. (Operation) When applying a surface treatment film to an amorphous alloy thin plate having a surface with poor wettability, in order to equalize the surface pressure in the plate width direction of the rubbing body that makes contact with the surface of the amorphous alloy thin plate. , Use a backup device to hold the rubbing body from behind. As a result, the local wear of the rubbing body in contact with the amorphous alloy thin plate is made uniform, and as a result, the uniformity of the surface treatment film, the reactivity of the treatment liquid and the amorphous alloy thin plate, and the amorphous The passability of the thin alloy sheet is improved. Further, when the rubbing body is pressed in a non-rotating state to cause contact rubbing, only the contact surface is worn. However, by rotating the rubbing body, the contact surface is worn in the circumferential direction of the rubbing body evenly, the throughput of the plate passing increases, and it is suitable for high-speed and large-volume passing. (Examples) Example 1 An amorphous alloy sheet having a surface with poor wettability, which was produced by a single roll method, Fe; 60.5 Si; 6.5 B; 12 C; 1 (wt
%), An amorphous magnetic alloy thin plate having an average plate thickness of 30 μm and a plate width of 100 mm, as shown in FIG.
3 sets of glass sliding bodies were placed, and a weight of 400 g was placed on the upper portion of the upper sliding body so that the surface pressure was uniform in the plate width direction, and a load was applied. The surface treatment is performed by dropping the chromic acid phosphate mixed solution on the surface of the amorphous magnetic alloy thin plate before contacting and rubbing between the first set of upper and lower rubbing members, and a plate passing speed of 10 m / min. I went there. Since the rubbing body contacts and abrades the amorphous alloy thin plate, the contacting part is worn away, and the wear amount increases with the passing amount of the plate. Assuming that the amount of wear of the non-rotating rubbing body in contact with the amorphous alloy thin plate is F, the wear amount (F) = the wear of the rubbing body in the plate width direction as shown in FIG. It is represented by the length (L) × wear width (H) in the passing direction of the thin plate. Wear length (L)
Indicates a substantially constant value depending on the width of the plate to be passed and the meandering of the plate. However, the wear width (H) changes depending on the amount of passing of the plate, so by comparing the wear width (H), wear You can know the degree of. Therefore, Table 1 shows the wear width (H) and the adhesion amount of the rubbing body when passing the amorphous alloy thin plate having a length of 400 m as compared with the case where pressure is applied only to the end portions. The amount of adhesion was determined by peeling off the film and measuring the weight difference. According to Table 1, when pressure is applied to both ends of the rubbing body,
The rubbing body bends, high pressure is applied only to both ends of the amorphous alloy thin plate, and weak pressure is applied to the central part. Therefore, the amount of wear at both ends is larger than that at the center, and the amount of adhesion in the plate width direction becomes uneven. On the other hand, so that the surface pressure in the plate width direction of the rubbing body becomes uniform,
By adding a backup device that presses the rubbing body from behind, the rubbing body is evenly worn in the plate width direction, and the uniformity of the amount of adhesion in the plate width direction is also increased. Example 2 Under the conditions of Example 1, when a rubbing body was pressed in a non-rotating state and a plate having a length of 1.2 km was passed, the upper and lower rubbing bodies were perpendicular to the contact surface of the amorphous alloy thin plate. It was worn by 40 μm. For this reason, it becomes difficult for the amorphous alloy thin plate having a plate thickness of 30 μm to scrape off the difficult-to-wet surface only by passing it between the upper and lower rubbing bodies, and the reactivity between the liquid and the amorphous alloy thin plate becomes difficult. At the same time, the controllability of the adhered amount becomes worse at the same time as the effect of increasing On the other hand, when the rubbing body is passed through a plate having a length of 1.2 km while rotating the rubbing body at 1 rpm in the direction opposite to the passing direction, the diameters of the upper and lower rubbing bodies are each reduced by 2 μm. The reactivity between the crystalline alloy thin plate and the liquid and the controllability of the adhered amount were also good. Example 3 Under the conditions of Example 1, glass with a diameter of 8 mmφ, stainless steel,
Table 2 shows the wear width (H) and the amount of adhesion of the rubbing body when the amorphous alloy thin plate was passed through 400 m using hard stainless steel and zirconia. According to Table 2, there is a slight difference in the wear width depending on the material of the rubbing body, but if it has a hardness surface for scraping and removing the extremely wettable extreme surface, and has corrosion resistance to the surface treatment liquid, It can be seen that it has nothing to do with the adhesion amount. (Effect of the invention) As described above, by applying a load from the back of a rubbing body having a hardness surface sufficient to scrape and remove a hard-to-wet surface and having corrosion resistance to a treatment liquid, by a backup device. , The surface pressure in the plate width direction becomes uniform. Under such conditions, the surface treatment liquid is present between the amorphous alloy thin plate having a difficult-to-wet surface and the rubbing body, and the two are contact-rubbed with each other to obtain the uniformity and treatment of the treatment film. The reactivity between the liquid and the amorphous alloy thin plate and the passing property of the amorphous alloy thin plate are improved. Further, by rotating the rubbing member, high-speed mass passing can be performed.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a side view of the present invention, FIG. 2 is a front view (a) and a side view (b) of the present invention, and FIG. 3 is a side view of another example of the present invention. FIG. 4 is a schematic view showing a worn state of the rubbing body, and FIG. 5 is a side view of another example of the present invention. 1: Rubbing body, 2: Backup device 3: Weight, 4: Frame 6: Amorphous alloy thin plate, 10: Cylinder

Continuation of front page    (72) Inventor Hideo Kanno               1-1-1 Emitsu, Hachimanto-ku, Kitakyushu               Inside Steel Engineering Co., Ltd. (72) Inventor Osamu Mizutani               1-1-1 Emitsu, Hachimanto-ku, Kitakyushu               Inside Steel Engineering Co., Ltd.                (56) References JP-A-57-165115 (JP, A)                 JP-A-55-58962 (JP, A)                 JP-A-57-75767 (JP, A)                 JP-A-60-92483 (JP, A)                 JP-A-61-96084 (JP, A)

Claims (1)

(57) [Claims] A method of forming a surface-treated film on the amorphous alloy thin plate by contact-rubbing an amorphous alloy thin plate having a thickness of 100 μm or less, which has poor wettability, with an opposing rotatable rubbing member. (A) The rotatable rubbing body has sufficient hardness to rub the extreme surface of the amorphous alloy thin plate and has glass, metal, non-ferrous metal, alloy having corrosion resistance to a surface treatment liquid, (B) A backup device is provided behind at least one of the opposed rotatable slidable contact bodies that come into contact with the amorphous alloy thin plate, and holds the rotatable slidable friction body. And (c) the surface treatment liquid is supplied to the surface of the amorphous alloy thin plate before the amorphous alloy thin plate and the rotatable rubbing body contact and rub against each other. Amorphous alloy sheet with surface Surface treatment method. 2. The surface treatment method for an amorphous alloy thin plate having a hardly wettable surface according to claim 1, wherein the shape of the rotatable rubbing body is circular or polygonal. 3. The surface treatment method for an amorphous alloy thin plate having a hardly wettable surface according to claim 1 or 2, wherein the rotatable rubbing body has a smooth surface.