TWI556896B - Manufacturing method of laser processing member and laser processing method - Google Patents

Description

Laser processing member manufacturing method and laser processing method

The present invention relates to a method of manufacturing a laser processed member and a laser processing method.

In recent years, the use of laser processing has progressed due to the high efficiency of the process and the demand for high quality and high precision of manufactured components. For example, it is used for hole processing for interlayer connection between a turbine member for power generation and a printed circuit board. However, in the case of processing by laser, there is a problem that welding slag and scum generated during processing adhere to the surface.

Therefore, in recent years, in order to suppress the adhesion to the surface at the time of hole processing of the turbine member for power generation, a method of applying a masking agent to the surface of the object to perform laser hole processing has been disclosed.

For example, in Patent Document 1, a method is disclosed in which a masking agent made of a paste of metal powder and cerium oxide is applied to a metal surface, and after performing hole processing by laser, the shielding agent is removed. This method uses a masking agent to protect the surface to obtain a surface of the cleaned portion.

Further, in Patent Document 2, a method is disclosed in which a decomposition product generated in laser processing is subjected to suction and removal while being irradiated and removed in the vicinity of an irradiation portion. In this method, the surface of the processed portion is obtained by suction after the decomposition product such as welding slag and scum adhere to the surface.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Invention Patent No. 4913297

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-121073

In the above-mentioned conventional method, for example, in the method of Patent Document 1, the masking agent is a ceramic coating layer, and therefore, it is necessary to perform a treatment such as blowing when it is removed.

Further, in the method of Patent Document 2, there is a possibility that the device becomes large-scale or interference with the device becomes a problem. In addition, in the processing of the laser hole, the gas is blown coaxially with the laser, but in this case, the suction effect may be weak, and the surface of the processed portion cannot be obtained.

Accordingly, the present invention is directed to obtaining a cleaned surface of a processed portion by simple laser processing.

In order to achieve the above object, the present invention is directed to a method of manufacturing a laser processing member having a protective layer for forming a protective layer on a surface of a member and a processing program for irradiating the protective layer with the processing of the member. The protective layer is an oxide glass containing P, and has a removal process in which the protective layer is dissolved in a liquid after the processing procedure.

Further, in the laser processing method including a protection program for forming a protective layer on the surface of the member and a processing program for irradiating the protective layer with the laser and processing the member, the protective layer is oxidized with P. The material glass has a removal process in which the protective layer is dissolved in a liquid after the processing procedure described above.

According to the present invention, the surface of the processed portion can be obtained by simple laser processing.

1‧‧‧Ni base alloy

2‧‧‧ basement

3‧‧‧ Thermal barrier coating

4‧‧‧Oxide glass layer

5‧‧‧Laser

6‧‧‧Processing residue

7‧‧‧ Hole Processing Department

8‧‧‧ glass epoxy resin

9‧‧‧ copper foil

10‧‧‧316 stainless steel

11‧‧‧cutting members

12‧‧‧Weld Department

Fig. 1 shows an example of a DTA curve obtained by differential thermal analysis of oxide glass.

[Fig. 2] Program diagram of hole processing of Ni-based alloy with thermal barrier coating

[Fig. 3] A program diagram of hole processing of a printed circuit board

[Fig. 4] Program diagram of cutting process of stainless steel

[Fig. 5] Program diagram of welding processing of stainless steel

In the present invention, when the surface of the member is processed using a laser, a protective layer containing P-containing oxide glass is provided on the surface of the member, and laser processing is performed thereon. After the laser processing, the protective layer is removed by liquid washing. A liquid system water or an aqueous solution containing water as a main solvent.

An oxide having a water-soluble characteristic containing P (phosphorus) is exemplified by P ₂ O ₅ and P ₂ O ₄ . The oxides herein do not substantially contain Pb (lead) and Bi (bismuth). According to the RoHS Directive (implemented on July 1, 2006), these substances are designated as banned substances, and substantially do not contain the banned substances in the RoHS Directive that do not contain the specified value or more. By adding V, Fe, Li, Na, K, Ba, Ca, and B to the oxide containing P, the water solubility and glass transition temperature can be adjusted.

In order to improve the water solubility of the oxide, it is preferred to add V or an alkali metal (Li, K, Na, etc.) or an alkaline earth metal (Ba, Ca, etc.). However, when V is contained in the oxide, when the alkali metal or the alkaline earth metal is excessively added, the water resistance is excessively increased. Therefore, the alkali metal is preferably 10 mol% or less, and the alkaline earth metal is preferably 5 mol% or less.

On the other hand, when the water resistance is increased, it becomes difficult to absorb moisture, so workability is improved. Since Fe and B have an effect of improving water resistance, it is preferable to appropriately add them from the viewpoint of workability. In addition, by adding Fe, the absorption of the laser will increase. In the case of processing an object having a low laser absorptivity, it is effective for improving the processing efficiency.

In addition, the oxide containing V is excellent in laser absorption. When the processing is performed on Cu (copper) or Al (aluminum) having a low absorption rate of the laser, the laser absorption rate can be increased by coating on the surface to improve the processing efficiency. Further, these oxides are easily dissolved in water, so that after laser processing, they can be washed away together with the slag and scum generated during processing. Even if it is an oxide containing no V, it can absorb a laser having a wavelength of about 10 μm. Therefore, by appropriately selecting the wavelength of the laser, good processing quality can be obtained.

The composition range of the effective oxide (oxide), based P-based system to the case where the composition of P ₂ O ₅ is 40 ~ 70mol%, Na ₂ O is preferably 25 ~ 50mol%. When B ₂ O ₃ contains 5 to 10 mol%, the glass transition point becomes low, and it becomes more preferable to form a protective layer. Not only P also contains V, and in the case where V is a main component, P ₂ O ₅ is 5 to 50 mol%, V ₂ O ₅ is 50 to 95 mol%, and P ₂ O ₅ + V ₂ O ₅ ≧ 68 mol% is preferable. The water solubility changes when P ₂ O ₅ +V ₂ O ₅ ≧ 90 mol%.

Further, by mixing the above oxides with metal or ceramic particles, the heat resistance of the oxide can be improved. It is not the case that the powder particles are removed together with the oxide after the processing, and it is not a metal or a ceramic. However, when it is likely to adhere and remain, it is preferable to have the same composition as the object to be processed. For example, in the case of processing a Ni-based superalloy, it is possible to impart heat resistance to an oxide by mixing metal particles of the same composition with the above-mentioned oxide. Further, in the case of processing of Cu, heat resistance can be imparted to the oxide by mixing the Cu particles with the above oxide.

The above oxides can be used after being pasteified using a solvent and a binder. Applying the paste to the surface of the sample and drying it so that An oxide glass layer can be formed that follows the surface of the sample. Alternatively, an oxide glass layer may be formed on the surface by thermal spraying or cold spraying. No matter how the oxide glass layer is formed, it does not affect the water solubility and the laser absorbability.

[Example 1]

In the present example, oxide glass having the composition shown in Table 1 was produced, and water solubility (detergency) and glass transition temperature were evaluated. The above oxide is prepared by using a reagent of V ₂ O ₅ , P ₂ O ₅ , Na ₂ O, Fe ₂ O ₃ , Li ₂ O, K ₂ O, BaO, CaO, or B ₂ O ₃ to obtain a total of 200 g. The method is to mix and mix into a quantitative amount and add platinum crucible, and heat it to 900 to 950 ° C at a heating rate of 5 to 10 ° C / min for melting. In order to make it uniform at this temperature, it is kept for 1 to 2 hours while stirring. Thereafter, the crucible was taken out and poured into a stainless steel plate which was previously heated to a temperature of about 150 °C. The oxide which flows into the stainless steel plate is pulverized until the average particle diameter (D ₅₀ ) becomes less than 20 μm. The differential thermal analysis (DTA) was carried out at a temperature elevation rate of 5 ° C / min for this oxide up to 550 ° C, thereby measuring the transfer point (T _g ), the yield point (M _g ), the softening point (T _s ), and the crystallization temperature. (T _cry ). Further, alumina (Al ₂ O ₃ ) powder was used as a standard sample.

A representative DTA curve for oxide glass is shown in FIG. As shown in Fig. 1, T _g is the starting temperature of the first endothermic peak, M _g is the peak temperature, T _s is the second endothermic peak temperature, and T _cry is the starting temperature of the exothermic peak due to crystallization. The T _g of the oxide glass of this example was 277 °C.

The detergency of the oxide glass was evaluated by immersion in water for 2 hours. In the evaluation sample, the oxide was pulverized in a jet mill until the average particle diameter (D ₅₀ ) was 2 μm or less, and a solvent in which 4% of the resin binder was dissolved was added to the oxide powder, and the mixture was mixed to prepare a printing paste. body. Here, ethyl cellulose is used for the resin binder, and diethylene glycol butyl ether acetate is used for the solvent. This paste was applied to a Ni-based alloy with a thermal barrier coating formed of ceramics, dried at 150 ° C, and baked at 500 ° C to 700 ° C for 10 minutes to be fired.

In the case where the oxide glass can be satisfactorily dissolved and removed, it is evaluated as "?", and when it is soluble, it is evaluated as "○", and when it is not dissolved, it is evaluated as "△". The case of dissolution is evaluated as "X". In the examples of the oxides Nos. 1 to 38, they are excellent in water solubility and can be easily removed from the test piece.

[Example 2]

Hole processing of a Ni-based alloy with a ceramic thermal barrier coating was carried out using the oxide glass paste produced in Example 1. The oxide glass composition was such that V ₂ O ₅ was 70 mol% and P ₂ O ₅ was 30 mol% (No. 4 of the examples). The oxide glass paste was applied to a ceramic thermal barrier coating and dried on a hot plate heated to 150 ° C for 10 minutes. After drying, the hole processing is performed by laser. Laser laser beam used. Aperture system 0.8mm and 1.4mm, the hole angle is taken at 90° and 45°. In the case of gas, Ar gas was used, and the gas pressure was 0.5 MPa. FIG. 2 shows a program diagram of laser hole processing. 1 is a Ni-based alloy, 2 is a base layer, 3 is a thermal barrier coating (ceramic layer), 4 is an oxide glass layer, 5 is a laser, and 6 is a processing residue (weld). It is a hole processing part.

A slag which is presumed to be a Ni-based alloy metal component adheres to the surface after the processing. The processed test piece was immersed in water, and the slag was removed together with the oxide glass. In the test piece after washing with water, the oxide glass was not confirmed by the naked eye and was almost removed. When compared with the case of the oxide-free glass layer, the appearance is such that no adhesion of the slag and the scum is obtained, and a hole-worked member excellent in surface cleanness is obtained.

A high-frequency inductively coupled plasma atomic emission spectrometer was used, and V was detected as a result of analysis in the vicinity of the laser processing section. Since the V component is not contained in the ceramic layer or the Ni-based alloy, it is considered to be a residue of the oxide glass. The ceramic layer is attached to the Ni-based alloy by thermal spraying, so it should be considered that there are fine irregularities on the surface, and the oxide glass intrudes into the unevenness. It was also confirmed that even a slight residual V component on the surface of the ceramic thermal barrier coating did not change in terms of heat insulating properties.

In the present embodiment, the fiber laser is used for the laser, but the hole processing is not limited thereto. Gas type and pressure This can be changed as appropriate, as in the following embodiments.

The same test as above was also carried out in the comparative example. The oxide glass composition was such that V ₂ O ₅ was 40 mol%, TeO ₂ was 40 mol%, and Ag ₂ O was 20 mol% (No. 4 of Comparative Example). Welding slag or scum is attached to the surface after processing. Although the test piece was immersed in water for 2 hours, the oxide glass was not water-soluble, and the weld slag, scum, and oxide glass were still attached to the thermal barrier coating.

[Example 3]

In Example 2, an oxide glass paste was used to form an oxide glass layer, but in the present embodiment, the oxide glass powder was cold-sprayed and blown onto the thermal barrier coating to form an oxide glass layer. For the difference. The particle size of the powder used is 10 to 30 μm. Other experimental conditions were as in Example 2.

A slag which is presumed to be a Ni-based alloy metal component adheres to the surface after the processing. The processed test piece was immersed in water, and the slag was removed together with the oxide glass. In the test piece after washing with water, the oxide glass was not confirmed by the naked eye and was almost removed. When compared with the case of the oxide-free glass layer, the appearance is such that no adhesion of the slag and the scum is obtained, and a hole-worked member excellent in surface cleanness is obtained.

A high-frequency inductively coupled plasma atomic emission spectrometer was used, and V was detected as a result of analysis in the vicinity of the laser processing section. Since the V component is not contained in the ceramic layer or the Ni-based alloy, it is considered to be a residue of the oxide glass.

When the cold spray method is employed in the present embodiment, the oxide glass layer can be formed efficiently in a large-scale apparatus such as a power plant, so that the processing time can be shortened.

[Example 4]

Hole processing of a Ni-based alloy with a ceramic thermal barrier coating was carried out by adding a Ni alloy powder to the oxide glass paste produced in Example 1. The particle size of the Ni-based alloy powder was 30 to 60 μm, and the content in the paste was 30% by volume. Other experimental conditions were as in Example 2.

A slag which is presumed to be a Ni-based alloy metal component adheres to the surface after the processing. The processed test piece was immersed in water, and the slag was removed together with the oxide glass. In the test piece after washing with water, the oxide glass was not confirmed by the naked eye and was almost removed. When compared with the case of the oxide-free glass layer, the appearance is such that no adhesion of the slag and the scum is obtained, and a hole-worked member excellent in surface cleanness is obtained.

A high-frequency inductively coupled plasma atomic emission spectrometer was used, and V was detected as a result of analysis in the vicinity of the laser processing section. Since the V component is not contained in the ceramic layer or the Ni-based alloy, it is considered to be a residue of the oxide glass.

[Example 5]

Using the oxide glass paste produced in Example 1, a copper foil-clad plate for a printed circuit board as shown in Fig. 3 was subjected to hole processing. 8 series means glass epoxy resin, 9 series means Copper foil.

The thickness of the copper foil was 18 μm. The oxide glass composition was such that V ₂ O ₅ was 70 mol% and P ₂ O ₅ was 30 mol%. The oxide glass paste was applied to a copper clad laminate by screen printing, and dried on a hot plate heated to 150 ° C for 10 minutes. After drying, the hole processing is performed by laser. The laser system used is a CO ₂ laser. Hole processing is performed by irradiating a CO ₂ laser from above the oxide glass layer. Aperture system 0.1mm, the hole angle is taken at 90°. Since the oxide glass layer absorbs the CO ₂ laser well, the copper foil can be subjected to hole processing. A processing residue estimated to be Cu adheres to the surface after processing. The processed test piece was immersed in water, and the processing residue was removed together with the oxide glass. In the test piece after washing with water, the oxide glass system was not confirmed by the naked eye and was almost removed. A high-frequency inductively coupled plasma atomic emission spectrometer was used, and no V was detected as a result of analysis in the vicinity of the laser processing section. It should be considered that the surface of the copper foil is very smooth, so the oxide glass is completely removed by washing with water.

When compared with the case of the oxide-free glass layer, the appearance is such that no adhesion of the slag and the scum is obtained, and a hole-worked member excellent in surface cleanness is obtained.

In the present embodiment, the oxide glass is screen printed for coating, but the same effect can be obtained by applying only to the hole processing portion by the dispenser.

The same test as above was also carried out in the comparative example. The oxide glass composition was such that V ₂ O ₅ was 40 mol%, TeO ₂ was 40 mol%, and Ag ₂ O was 20 mol% (No. 4 of Comparative Example). Welding slag or scum is attached to the surface after processing. Although the test piece was immersed in water for 2 hours, the oxide glass was not water-soluble, and the weld slag, the dross, and the oxide glass adhered to the copper foil, which was not effective.

[Example 6]

Using the oxide glass paste produced in Example 1, the 316 stainless steel was cut as shown in Fig. 4 . The 10 series indicates 316 stainless steel, and the 11 series indicates a cutting member.

The oxide glass composition was such that V ₂ O ₅ was 70 mol% and P ₂ O ₅ was 30 mol%. The oxide glass paste was applied to 316 stainless steel and dried on a hot plate heated to 150 ° C for 10 minutes. After drying, the 316 stainless steel was cut with a laser. Laser laser beam used. The thickness of the plate is 6 mm, and Ar gas is used for the gas for cutting. The gas system takes 0.5 MPa. The slag is attached to the surface after processing. The processed test piece was immersed in water, and the slag was removed together with the oxide glass. In the test piece after washing with water, the oxide glass was not confirmed by the naked eye and was removed. In comparison with the case of the oxide-free glass layer, the appearance is such that no adhesion of the slag and the scum is obtained, and a cut-off member excellent in surface cleanness is obtained.

[Example 7]

Using the oxide glass paste produced in Example 1, the 316 stainless steel was welded as shown in FIG. The oxide glass composition was such that V ₂ O ₅ was 70 mol% and P ₂ O ₅ was 30 mol%. The oxide glass paste was applied to 316 stainless steel and dried on a hot plate heated to 150 ° C for 10 minutes. After drying, the 316 stainless steel was placed upside down and laser welded. Laser laser beam used. The thickness of the plate is 6 mm, and Ar gas is used for the shielding gas. The gas flow rate was taken at 30 L/min. The slag is attached to the surface after processing. The processed test piece was immersed in water, and the slag was removed together with the oxide glass. In the test piece after washing with water, the oxide glass was not confirmed by the naked eye and was removed. When compared with the case of the oxide-free glass layer, the appearance is such that no welding slag and scum adhere, and a welded workpiece having excellent surface cleanness is obtained.

According to the above, a protective layer is formed on the ceramic or the metal in the glass excellent in detergency as shown in Table 1, so that even if residue such as welding slag is generated during laser processing, it can be washed together with the glass. . Thereby, the laser processing is simpler than the prior art using a masking agent or the like, and a clean surface member is obtained. The laser processing system is not limited to the above-described hole processing, cutting, welding, or processing that does not penetrate the substrate.

1‧‧‧Ni base alloy

2‧‧‧ basement

3‧‧‧ Thermal barrier coating

4‧‧‧Oxide glass layer

5‧‧‧Laser

6‧‧‧Processing residue

7‧‧‧ Hole Processing Department

Claims (11)

A method for producing a laser processing member, comprising: a protection program for forming a protective layer on a surface of the member; and a processing program for processing the member by irradiating a laser beam to the protective layer, wherein the protective layer is oxidized by P The material glass includes a removal step of dissolving the protective layer in a liquid after the processing procedure, and the oxide glass system further contains V, and P ₂ O ₅ is 5 to 50 mol% in terms of oxide, and V ₂ O ₅ is 50 to 95 mol%, P ₂ O ₅ + V ₂ O ₅ ≧ 68 mol%. A method for producing a laser processing member, comprising: a protection program for forming a protective layer on a surface of the member; and a processing program for processing the member by irradiating a laser beam to the protective layer, wherein the protective layer is oxidized by P The material glass includes a removal step of dissolving the protective layer in a liquid after the processing procedure, and the oxide glass system further contains Na, and in the oxide conversion, P ₂ O ₅ is 40 to 70 mol%, and Na ₂ O is 25 ~50mol%. The method for producing a laser processing member according to claim 1 or 2, wherein the oxide glass system further comprises any one of Fe, Li, Na, K, Ba, Ca, and B. The method for producing a laser processing member according to the first or second aspect of the invention, wherein the protective layer is formed by blowing a powder of the oxide glass onto the member to form the protective layer. The method of manufacturing a laser processing member according to claim 1 or 2, wherein the protection program comprises the foregoing oxide glass. The paste is applied to the above member and dried to form the protective layer. The method for producing a laser processing member according to claim 1 or 2, wherein the liquid system is water. A laser processing method comprising: a protection program for forming a protective layer on a surface of a member; and a processing program for irradiating the protective layer with a laser to process the member, wherein the protective layer is an oxide glass containing P, A process for removing the protective layer by a liquid after the processing step, wherein the oxide glass system further contains V, and P ₂ O ₅ is 5 to 50 mol% in terms of oxide, and V ₂ O ₅ is 50 to 95 mol. %, P ₂ O ₅ + V ₂ O ₅ ≧ 68 mol%. A laser processing method comprising: a protection program for forming a protective layer on a surface of a member; and a processing program for irradiating the protective layer with a laser to process the member, wherein the protective layer is an oxide glass containing P, There is a removal procedure in which the protective layer is dissolved in a liquid after the processing procedure, and the oxide glass system further contains Na, and in the oxide conversion, P ₂ O ₅ is 40 to 70 mol%, and Na ₂ O is 25 to 50 mol%. . The laser processing method according to claim 7 or 8, wherein the protection step is to form the protective layer by blowing a powder of the oxide glass onto the member. The laser processing method according to claim 7 or 8, wherein the protective layer is formed by applying a paste containing the oxide glass to the member and drying the paste to form the protective layer. The laser processing method of claim 7 or 8, wherein the liquid system is water.