TW201509580A - Laser-processed component manufacturing method and laser processing method - Google Patents

Laser-processed component manufacturing method and laser processing method Download PDF

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TW201509580A
TW201509580A TW103116713A TW103116713A TW201509580A TW 201509580 A TW201509580 A TW 201509580A TW 103116713 A TW103116713 A TW 103116713A TW 103116713 A TW103116713 A TW 103116713A TW 201509580 A TW201509580 A TW 201509580A
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laser
oxide glass
oxide
processing
laser processing
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TW103116713A
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TWI556896B (en
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Masanori Miyagi
Takuya Aoyagi
Takashi Naitou
Toshinori Kawamura
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Hitachi Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/16—Removal of by-products, e.g. particles or vapours produced during treatment of a workpiece
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/18—Working by laser beam, e.g. welding, cutting or boring using absorbing layers on the workpiece, e.g. for marking or protecting purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/20—Bonding
    • B23K26/21—Bonding by welding
    • B23K26/24—Seam welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/20—Bonding
    • B23K26/32—Bonding taking account of the properties of the material involved
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/38—Removing material by boring or cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/38—Removing material by boring or cutting
    • B23K26/382—Removing material by boring or cutting by boring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/40—Removing material taking account of the properties of the material involved
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/02—Iron or ferrous alloys
    • B23K2103/04—Steel or steel alloys
    • B23K2103/05—Stainless steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/16—Composite materials, e.g. fibre reinforced
    • B23K2103/166—Multilayered materials
    • B23K2103/172—Multilayered materials wherein at least one of the layers is non-metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/50—Inorganic material, e.g. metals, not provided for in B23K2103/02 – B23K2103/26

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Mechanical Engineering (AREA)
  • Glass Compositions (AREA)
  • Laser Beam Processing (AREA)

Abstract

This laser-processed component manufacturing method is provided with: a protecting step for forming a protection layer on a surface of a component; and a processing step for processing the component by irradiating the protection layer with a laser beam. The protection layer is formed of an oxide glass containing P, and the method is also provided with a removing step wherein the protection layer is melted using a liquid after the processing step.

Description

雷射加工構件之製造方法及雷射加工方法 Laser processing member manufacturing method and laser processing method

本發明，係有關於雷射加工構件之製造方法及雷射加工方法。 The present invention relates to a method of manufacturing a laser processed member and a laser processing method.

近年來，由於製程的高效化和製造構件的高品質化、高精密度化的要求之提升，已進展到雷射加工的利用。例如，利用於發電用渦輪構件和印刷電路板的層間連接用之孔加工等。然而，在以雷射而進行加工之情況下，係存在如下課題：在加工時產生之焊渣和浮渣等會附著於表面。 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.

於是近幾年，為了抑制在發電用渦輪構件的孔加工時之往表面的附著之目的，已揭露在對象物的表面塗佈遮蔽劑而進行雷射孔加工之方法。 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.

例如，在專利文獻1方面，係揭露如下方法：將由金屬粉末與二氧化矽的膏體所成之遮蔽劑塗佈於金屬表面，藉雷射而進行孔加工後，將遮蔽劑作除去。此手法係以遮蔽劑對於表面作保護而獲得清淨之加工部的表面者。 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.

另外在專利文獻2方面，係揭露如下方法：對於在雷射加工中所生成之分解物一邊在照射部分的近旁進行吸引除去，一邊進行加工。此手法，係在焊渣、浮渣這樣的分解物附著於表面之前藉進行吸引而獲得清淨之加工部的表面者。 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.

〔先前技術文獻〕 [Previous Technical Literature] 〔專利文獻〕 [Patent Document]

[專利文獻1]日本發明專利第4913297號公報 [Patent Document 1] Japanese Invention Patent No. 4913297

[專利文獻2]日本特開2012-121073號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-121073

在上述的歷來之方法中，例如在專利文獻1之方法中係遮蔽劑為陶瓷塗層，故要作除去時變得需要鼓風等的處理。 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.

另外在專利文獻2的方法中，係有可能裝置成為大規模，或與該裝置的干涉成為問題。另外在雷射孔加工時係會以與雷射同軸而吹拂氣體，但在該情況下，係有可能吸引效果會變弱，無法獲得清淨之加工部表面。 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.

於是本發明，係目的在於：藉簡單之雷射加工，而獲得清淨之加工部表面。 Accordingly, the present invention is directed to obtaining a cleaned surface of a processed portion by simple laser processing.

為了達成上述目的，本發明，係在具備在構件的表面形成保護層之保護程序、及對於前述保護層照射雷射而對於前述構件進行加工之加工程序的雷射加工構件之製造方法中，特徵在於：前述保護層為含P之氧化物玻璃，具備在前述加工程序後將前述保護層以液體溶掉之除去程序。 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.

此外，在具備在構件的表面形成保護層之保護程序、及對於前述保護層照射雷射而對於前述構件進行加工之加工程序的雷射加工方法中，特徵在於：前述保護層為含P之氧化物玻璃，具備在前述加工程序後將前述保護層以液體溶掉之除去程序。 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.

依本發明，即可藉簡單之雷射加工，而獲得清淨之加工部表面。 According to the present invention, the surface of the processed portion can be obtained by simple laser processing.

1‧‧‧Ni基合金 1‧‧‧Ni base alloy

2‧‧‧底基層 2‧‧‧ basement

3‧‧‧熱障塗層 3‧‧‧ Thermal barrier coating

4‧‧‧氧化物玻璃層 4‧‧‧Oxide glass layer

5‧‧‧雷射 5‧‧‧Laser

6‧‧‧加工殘渣 6‧‧‧Processing residue

7‧‧‧孔加工部 7‧‧‧ Hole Processing Department

8‧‧‧玻璃環氧樹脂 8‧‧‧ glass epoxy resin

9‧‧‧銅箔 9‧‧‧ copper foil

10‧‧‧316不銹鋼 10‧‧‧316 stainless steel

11‧‧‧切斷構件 11‧‧‧cutting members

12‧‧‧焊接部 12‧‧‧Weld Department

[圖1]以氧化物玻璃的差熱分析而獲得之DTA曲線的1例。 Fig. 1 shows an example of a DTA curve obtained by differential thermal analysis of oxide glass.

[圖2]附熱障塗層Ni基合金的孔加工之程序圖 [Fig. 2] Program diagram of hole processing of Ni-based alloy with thermal barrier coating

[圖3]印刷電路板的孔加工之程序圖 [Fig. 3] A program diagram of hole processing of a printed circuit board

[圖4]不銹鋼的切斷加工之程序圖 [Fig. 4] Program diagram of cutting process of stainless steel

[圖5]不銹鋼的焊接加工之程序圖 [Fig. 5] Program diagram of welding processing of stainless steel

在本發明中，係使用雷射而進行構件的表面加工時，在構件的表面設置含P之氧化物玻璃的保護層，從其上進行雷射加工。雷射加工後，藉進行液體洗淨而將保護層作除去。液體係水、或以水為主溶劑之水溶液。 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.

具溶於水的特徵之氧化物，係含P(磷)舉例：P2O5和P2O4。於此等之氧化物係實質上不含Pb(鉛)與Bi(鉍)。根據RoHS指令(2006年7月1日施行)此等之物質係被指定為禁用物質，實質上不含係指在RoHS指令中之禁用物質不含有指定值以上的範圍。藉在含P之氧化物中加入V、Fe、Li、Na、K、Ba、Ca、B，使得可調整水溶性、玻璃轉移溫度。 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.

為了使氧化物的水溶性提升，加入V或鹼金屬(Li、K、Na等)、鹼土金屬(Ba、Ca等)較佳。但是，於氧化物中含有V之情況下，過度添加鹼金屬、鹼土金屬時，反而會過度提升耐水性，故鹼金屬係10mol%以下，鹼土金屬係5mol%以下較佳。 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.

另一方面，耐水性提升時會變得難以吸濕，故作業性會提升。Fe、B係具有使耐水性提升之效果，故從作業性的觀點而言作適當添加較佳。另外藉添加Fe，雷射吸收性會提升。在對於雷射吸收率為低之對象物進行加工的情況下，係有效於提升加工效率。 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.

另外含V之氧化物係在雷射吸收性方面優 異，故在對於雷射的吸收率為低之Cu(銅)或Al(鋁)等進行加工之情況下，可藉在表面作塗佈而使雷射吸收率增加，改善加工效率。另外此等之氧化物係容易溶於水，故雷射加工後，可與在加工時所生成之焊渣和浮渣等一起沖走。即使為不含V之氧化物，仍可吸收10μm程度之波長的雷射，故藉適當選擇雷射的波長，可獲得良好之加工品質。 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.

氧化物的有效之組成範圍(氧化物換算)，係以P為主成分之情況下係P2O5為40~70mol%，Na2O為25~50mol%較佳。B2O3含有5~10mol%時玻璃轉移點會變低，變得容易形成保護層故更佳。不僅P亦含V，以V為主成分之情況下係P2O5為5~50mol%，V2O5為50~95mol%，P2O5+V2O5≧68mol%較佳。P2O5+V2O5≧90mol%時水溶性會變更佳。 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%.

另外藉對於上述之氧化物，以金屬或陶瓷顆粒作混合，可使氧化物的耐熱性提升。粉末粒子係在加工後與前述氧化物一起被除去故是金屬還是陶瓷都沒關係，但考量有可能附著而殘存時，與加工對象物為同組成較佳。例如，在對於Ni基超合金進行加工之情況下，係可藉對於上述的氧化物混入同組成的金屬粒子，而對於氧化物賦予耐熱性。另外在Cu的加工情形下係可藉對於上述氧化物以Cu粒子作混合，而對於氧化物賦予耐熱性。 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.

上述之氧化物係可使用溶劑及黏合劑，而膏體化後作使用。將膏體塗佈於樣品表面，予以乾燥，使得 可形成接著於樣品表面之氧化物玻璃層。另外亦可藉熱噴塗或冷噴塗等，在表面形成氧化物玻璃層。無論以何種方法形成氧化物玻璃層，皆對於水溶性和雷射吸收性不會產生影響。 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.

〔實施例1〕 [Example 1]

在本實施例中，係製作示於表1之組成的氧化物玻璃，對於水溶性(洗淨性)與玻璃轉移溫度進行了評估。上述氧化物的製作，係使用V2O5、P2O5、Na2O、Fe2O3、Li2O、K2O、BaO、CaO、B2O3的試劑，以成為合計200g的方式，調配、混合成既定量而加入白金坩堝，藉電爐以5~10℃/分鐘之升溫速度加熱至900~950℃，作熔化。為了在此溫度下作成均勻而一邊攪拌一邊保持1~2小時。之後，將坩堝取出，流入預先加熱至150℃程度之不銹鋼板上。流入不銹鋼板上之氧化物，係進行粉碎直到平均粒徑(D50)成為不足20μm為止。對於此氧化物以5℃/分鐘的升溫速度進行差熱分析(DTA)直到550℃，從而測定了轉移點(Tg)、屈服點(Mg)、軟化點(Ts)及結晶化溫度(Tcry)。另外，作為標準樣品採用礬土(Al2O3)粉末。 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.

於圖1繪示氧化物玻璃之具代表性的DTA曲線。如圖1所示，Tg係第一吸熱峰之開始溫度，Mg係其峰值溫度，Ts係第二吸熱峰溫度，Tcry係因結晶化之顯著的放熱峰之開始溫度。本實施例之氧化物玻璃的Tg係 277℃。 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.

藉浸漬於水2h，對於氧化物玻璃的洗淨性進行了評估。評估樣品，係對於氧化物以噴射磨機進行粉碎直到平均粒徑(D50)成為2μm以下，於該氧化物粉末加入溶解了樹脂黏合劑4%之溶劑，進行混合，從而製作了印刷用膏體。於此，在樹脂黏合劑方面係採用乙基纖維素，在溶劑方面係採用二甘醇丁醚醋酸酯。將此膏體塗佈於以陶瓷而形成之附熱障塗層的Ni基合金，在150℃下予以乾燥，500℃~700℃程度保持10分鐘而作燒成。 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.

在可將氧化物玻璃良好地溶掉除去之情況下係評估為「◎」，在可溶掉之情況係評估為「○」，在不怎麼溶掉之情況係評估為「△」，在無法溶掉之情況係評估為「×」。在氧化物No.1~38的實施例方面，係在水溶性方面優異，可容易從試驗片作除去。 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.

〔實施例2〕 [Example 2]

使用在實施例1所製作之氧化物玻璃膏而實施附陶瓷熱障塗層的Ni基合金之孔加工。氧化物玻璃組 成係採取：V2O5為70mol%，P2O5為30mol%(實施例的No.4)。將氧化物玻璃膏塗佈於陶瓷熱障塗層，在加熱至150℃之熱板上予以乾燥10分鐘。乾燥後，以雷射實施孔加工。所使用之雷射係光纖雷射。孔徑係採取 0.8mm與 1.4mm，孔角度係採取90°與45°。在氣體方面係採用Ar氣體，氣壓係採取0.5MPa。於圖2繪示雷射孔加工之程序圖。1係表示Ni基合金，2係表示底基層，3係表示熱障塗層(陶瓷層)，4係表示氧化物玻璃層，5係表示雷射，6係表示加工殘渣(焊渣)，7係表示孔加工部。 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.

在加工後的表面係附著了推測為Ni基合金金屬成分之焊渣。將加工後的試驗片浸漬於水，而與氧化物玻璃一起，將焊渣作除去。在水洗淨後的試驗片中氧化物玻璃係無法以肉眼作確認，幾乎被除去。與無氧化物玻璃層之情況作比較時，外觀上，無焊渣和浮渣的附著，獲得在表面清淨方面優異之孔加工構件。 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.

使用高頻感應耦合電漿原子發射光譜分析裝置，而對於雷射加工部附近進行分析之結果，檢測出V。V成分係不含於陶瓷層、Ni基合金中，故應認為是氧化物玻璃的殘渣。陶瓷層係藉熱噴塗，而附於Ni基合金，故應認為是：在表面有細微的凹凸，氧化物玻璃侵入於該凹凸。另外確認了即使在陶瓷熱障塗層的表面些微殘留V成分在隔熱性能方面仍不會變化。 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.

在本實施例中係在雷射方面採用光纖雷射但只要可進行孔加工則不限定於此。氣體種類、氣壓方面亦 可作適當變更，在以下的實施例中亦為如此。 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.

在比較例中亦實施與上述同樣的試驗。氧化物玻璃組成係採取：V2O5為40mol%，TeO2為40mol%，Ag2O為20mol%(比較例的No.4)。在加工後的表面係附著了焊渣或浮渣。雖將此試驗片浸漬於水2h，但氧化物玻璃係未水溶，焊渣、浮渣、氧化物玻璃係仍附著於熱障塗層。 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.

〔實施例3〕 [Example 3]

在實施例2中係使用氧化物玻璃膏而形成氧化物玻璃層，但在本實施例中係將氧化物玻璃粉末藉冷噴塗，而吹至熱障塗層上而形成氧化物玻璃層這點為不同。採用之粉末的粒徑係10~30μm。其他實驗條件係如同實施例2。 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.

在加工後的表面係附著了推測為Ni基合金金屬成分之焊渣。將加工後的試驗片浸漬於水，而與氧化物玻璃一起，將焊渣作除去。在水洗淨後的試驗片中氧化物玻璃係無法以肉眼作確認，幾乎被除去。與無氧化物玻璃層之情況作比較時，外觀上，無焊渣和浮渣的附著，獲得在表面清淨方面優異之孔加工構件。 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.

使用高頻感應耦合電漿原子發射光譜分析裝置，而對於雷射加工部附近進行分析之結果，檢測出V。V成分係不含於陶瓷層、Ni基合金中，故應認為是氧化物玻璃的殘渣。 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.

如本實施例採用冷噴塗法時，在如發電廠之大型裝置方面亦可效率佳地形成氧化物玻璃層，故可縮短加工時間。 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.

〔實施例4〕 [Example 4]

對於在實施例1所製作之氧化物玻璃膏加入Ni合金粉末而實施附陶瓷熱障塗層的Ni基合金之孔加工。Ni基合金粉末的粒徑係採取30~60μm，膏體中的含有率採取30體積%。其他實驗條件係如同實施例2。 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.

在加工後的表面係附著了推測為Ni基合金金屬成分之焊渣。將加工後的試驗片浸漬於水，而與氧化物玻璃一起，將焊渣作除去。在水洗淨後的試驗片中氧化物玻璃係無法以肉眼作確認，幾乎被除去。與無氧化物玻璃層之情況作比較時，外觀上，無焊渣和浮渣的附著，獲得在表面清淨方面優異之孔加工構件。 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.

使用高頻感應耦合電漿原子發射光譜分析裝置，而對於雷射加工部附近進行分析之結果，檢測出V。V成分係不含於陶瓷層、Ni基合金中，故應認為是氧化物玻璃的殘渣。 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.

〔實施例5〕 [Example 5]

使用在實施例1所製作之氧化物玻璃膏，而對於如圖3所示在印刷電路板用的含玻璃環氧樹脂貼上銅箔之板，進行孔加工。8係表示玻璃環氧樹脂，9係表示 銅箔。 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.

銅箔的厚度係18μm。氧化物玻璃組成係採取：V2O5為70mol%，P2O5為30mol%。將氧化物玻璃膏藉網印而塗佈於覆銅板，在加熱至150℃之熱板上予以乾燥10分鐘。乾燥後，以雷射實施孔加工。所使用之雷射係CO2雷射。從氧化物玻璃層之上照射CO2雷射而實施孔加工。孔徑係採取 0.1mm，孔角度係採取90°。氧化物玻璃層係良好地吸收CO2雷射，故對於銅箔亦可進行孔加工。在加工後的表面係附著了推測為Cu之加工殘渣。將加工後的試驗片浸漬於水，而與氧化物玻璃一起，將加工殘渣作除去。在水洗淨後的試驗片，氧化物玻璃係無法以肉眼作確認，幾乎被除去。使用高頻感應耦合電漿原子發射光譜分析裝置，而對於雷射加工部附近進行分析之結果，未檢測出V。應認為是：銅箔的表面係非常平滑，故氧化物玻璃係藉水洗而被完全除去。 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.

與無氧化物玻璃層之情況作比較時，外觀上，無焊渣和浮渣的附著，獲得在表面清淨方面優異之孔加工構件。 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.

在本實施例中，係將氧化物玻璃藉網印，而作塗佈，但藉點膠機方式，而僅塗佈於孔加工部仍可獲得同樣的效果。 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.

在比較例中亦實施與上述同樣的試驗。氧化物玻璃組成係採取：V2O5為40mol%，TeO2為40mol%，Ag2O為20mol%(比較例的No.4)。在加工後的表面係 附著了焊渣或浮渣。雖將此試驗片浸漬於水2h，但氧化物玻璃係未水溶，焊渣、浮渣、氧化物玻璃係仍附著於銅箔，並無效果。 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.

〔實施例6〕 [Example 6]

使用在實施例1所製作之氧化物玻璃膏而對於316不銹鋼，如圖4所示進行切斷。10係表示316不銹鋼，11係表示切斷構件。 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.

氧化物玻璃組成係採取：V2O5為70mol%，P2O5為30mol%。將氧化物玻璃膏塗佈於316不銹鋼，在加熱至150℃之熱板上予以乾燥10分鐘。乾燥後，以雷射切斷316不銹鋼。所使用之雷射係光纖雷射。板厚係6mm，在切斷用氣體方面係採用Ar氣體。氣體係採取0.5MPa。在加工後的表面係附著了焊渣。將加工後的試驗片浸漬於水，而與氧化物玻璃一起，將焊渣作除去。在水洗淨後的試驗片中氧化物玻璃係無法以肉眼作確認，被除去。與無氧化物玻璃層之情況作比較時，外觀上，無焊渣和浮渣的附著，獲得在表面清淨方面優異之切斷加工構件。 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.

〔實施例7〕 [Example 7]

使用在實施例1所製作之氧化物玻璃膏而對於316不銹鋼，如圖5所示進行焊接。氧化物玻璃組成係採取：V2O5為70mol%，P2O5為30mol%。將氧化物玻璃 膏塗佈於316不銹鋼，在加熱至150℃之熱板上予以乾燥10分鐘。乾燥後，使316不銹鋼對上而實施雷射焊接。所使用之雷射係光纖雷射。板厚係6mm，在遮護氣體方面係採用Ar氣體。氣體流量係採取30L/min。在加工後的表面係附著了焊渣。將加工後的試驗片浸漬於水，而與氧化物玻璃一起，將焊渣作除去。在水洗淨後的試驗片中氧化物玻璃係無法以肉眼作確認，被除去。與無氧化物玻璃層之情況作比較時，外觀上，無焊渣和浮渣的附著，獲得在表面清淨方面優異之焊接加工構件。 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.

根據以上，在陶瓷或金屬上，以如表1所示之在洗淨性方面優異的玻璃而形成保護層，使得即使在雷射加工時產生焊渣等的殘渣，仍可連同玻璃作洗淨。藉此，與利用遮蔽劑等之現有技術相較下雷射加工為簡單，獲得清淨之表面的構材。雷射加工係不限於上述的孔加工，切斷、焊接，亦可為不貫通基材之加工。 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基合金 1‧‧‧Ni base alloy

2‧‧‧底基層 2‧‧‧ basement

3‧‧‧熱障塗層 3‧‧‧ Thermal barrier coating

4‧‧‧氧化物玻璃層 4‧‧‧Oxide glass layer

5‧‧‧雷射 5‧‧‧Laser

6‧‧‧加工殘渣 6‧‧‧Processing residue

7‧‧‧孔加工部 7‧‧‧ Hole Processing Department

Claims (15)

一種雷射加工構件之製造方法，具備在構件的表面形成保護層之保護程序、及對於前述保護層照射雷射而對於前述構件進行加工之加工程序，特徵在於：前述保護層為含P之氧化物玻璃，具備在前述加工程序後將前述保護層以液體溶掉之除去程序。 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 has a removal process in which the protective layer is dissolved in a liquid after the processing procedure described above. 如申請專利範圍第1項之雷射加工構件之製造方法，其中，前述氧化物玻璃係進一步包含V。 The method of producing a laser processing member according to the first aspect of the invention, wherein the oxide glass system further comprises V. 如申請專利範圍第1項之雷射加工構件之製造方法，其中，前述氧化物玻璃係進一步包含V，在氧化物換算下P2O5為5~50mol%，V2O5為50~95mol%，P2O5+V2O5≧68mol%。 The method for producing a laser processing member according to the first aspect of the invention, wherein the oxide glass system further comprises V, wherein 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%. 如申請專利範圍第1項之雷射加工構件之製造方法，其中，前述氧化物玻璃係進一步包含Na，在氧化物換算下P2O5為40~70mol%，Na2O為25~50mol%。 The method for producing a laser processing member according to the first aspect of the invention, wherein 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%. . 如申請專利範圍第1項之雷射加工構件之製造方法，其中，前述氧化物玻璃係進一步包含Fe、Li、Na、K、Ba、Ca、B中之任一者。 The method for producing a laser processing member according to the first aspect of the invention, wherein the oxide glass system further comprises any one of Fe, Li, Na, K, Ba, Ca, and B. 如申請專利範圍第1項之雷射加工構件之製造方法，其中，前述保護程序係將前述氧化物玻璃的粉末吹至前述構件上而形成前述保護層。 The method of manufacturing a laser processing member according to the first 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. 如申請專利範圍第1項之雷射加工構件之製造方法，其中，前述保護程序係將包含前述氧化物玻璃之膏體塗佈於前述構件，予以乾燥，而形成前述保護層。 The method for producing a laser processing member according to the first aspect of the invention, 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. 如申請專利範圍第1項之雷射加工構件之製造方法，其中，前述液體係水。 The method for producing a laser processing member according to the first aspect of the invention, wherein the liquid system is water. 一種雷射加工方法，具備在構件的表面形成保護層之保護程序、及對於前述保護層照射雷射而對於前述構件進行加工之加工程序，特徵在於：前述保護層為含P之氧化物玻璃，具備在前述加工程序後將前述保護層以液體溶掉之除去程序。 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 described above. 如申請專利範圍第9項之雷射加工方法，其中，前述氧化物玻璃係進一步包含V。 The laser processing method of claim 9, wherein the oxide glass system further comprises V. 如申請專利範圍第9項之雷射加工方法，其中，前述氧化物玻璃係進一步包含V，在氧化物換算下P2O5為5~50mol%，V2O5為50~95mol%，P2O5+V2O5≧68mol%。 The laser processing method according to claim 9, wherein the oxide glass system further comprises V, and in the oxide conversion, P 2 O 5 is 5 to 50 mol%, and V 2 O 5 is 50 to 95 mol%, P. 2 O 5 +V 2 O 5 ≧68 mol%. 如申請專利範圍第9項之雷射加工方法，其中，前述氧化物玻璃係進一步包含Na，在氧化物換算下P2O5為40~70mol%，Na2O為25~50mol%。 The laser processing method according to claim 9, wherein 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%. 如申請專利範圍第9項之雷射加工方法，其中，前述保護程序係將前述氧化物玻璃的粉末吹至前述構件上而形成前述保護層。 The laser processing method according to claim 9, wherein the protective step is performed by blowing a powder of the oxide glass onto the member to form the protective layer. 如申請專利範圍第9項之雷射加工方法，其中，前述保護程序係將包含前述氧化物玻璃之膏體塗佈於前述構件，予以乾燥，而形成前述保護層。 The laser processing method according to claim 9, wherein the protective step is performed by applying a paste containing the oxide glass to the member and drying the layer to form the protective layer. 如申請專利範圍第9項之雷射加工方法，其中，前述液體係水。 The laser processing method of claim 9, wherein the liquid system is water.
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