TWI490361B - Preparation of niobium target - Google Patents
Preparation of niobium target Download PDFInfo
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- TWI490361B TWI490361B TW102141249A TW102141249A TWI490361B TW I490361 B TWI490361 B TW I490361B TW 102141249 A TW102141249 A TW 102141249A TW 102141249 A TW102141249 A TW 102141249A TW I490361 B TWI490361 B TW I490361B
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- bismuth
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- Extrusion Of Metal (AREA)
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Description
本發明涉及靶材技術領域，尤其涉及一種鈮靶材及其製備方法。The invention relates to the technical field of targets, in particular to a bismuth target and a preparation method thereof.
靶材是在濺射沉積技術中用作陰極的材料，該材料能夠在帶正電荷的陽離子撞擊下以分子、原子或離子的形式脫離陰極而在陽極表面重新沉積。靶材作為一種具有高附加值的特種電子材料，其被廣泛用於濺射尖端技術的薄膜材料。根據應用，靶材主要包括半導體領域用靶材、記錄介質用靶材、顯示薄膜用靶材、先進觸控屏及顯示器、光學靶材和超導靶材等。The target is a material used as a cathode in sputter deposition techniques that can be redeposited on the anode surface in the form of molecules, atoms or ions in the form of molecules, atoms or ions under the impact of positively charged cations. As a special electronic material with high added value, the target is widely used as a thin film material for sputtering tip technology. According to the application, the target mainly includes a target for a semiconductor field, a target for a recording medium, a target for a display film, an advanced touch screen and a display, an optical target, and a superconducting target.
磁控濺射是製備薄膜材料的主要技術之一，它利用離子源產生離子，產生的離子在真空環境中經過加速聚集，從而形成高速度能的離子束流，轟擊固體表面，離子和固體表面原子發生動能的交換，使固體表面的原子離開固體表面並沉積在基體表面。被轟擊的固體是用濺射法沉積薄膜的原材料，稱為濺射靶材。Magnetron sputtering is one of the main techniques for preparing thin film materials. It uses ions to generate ions. The generated ions are accelerated and aggregated in a vacuum environment to form a high-speed energy ion beam, bombarding solid surfaces, ions and solid surfaces. The exchange of kinetic energy of atoms causes atoms on the solid surface to leave the solid surface and deposit on the surface of the substrate. The bombarded solid is a raw material for depositing a thin film by sputtering, which is called a sputtering target.
濺射靶材的形狀有長方體、正方體、圓柱體和不規則形狀。長方體、正方體和圓柱體形狀靶材為實心，濺射過程中，圓環形永磁體在靶材表面建立環形磁場，在軸間等距離的環形表面上形成刻蝕區，其缺點是薄膜沉積厚度均勻性不易控制，靶材的利用率較低，僅為20%~30%。目前國內外都在推廣應用旋轉空心圓管磁控濺射靶，其優點是該空心圓管靶材可繞固定的條狀磁鐵組件旋轉，因而360°靶面可被均勻刻蝕，利用率高達80%。一般來說，濺射靶材的晶粒尺寸必須控制在100微米以下，甚至其結晶結構的趨向性也必須受到嚴格的控制。The shape of the sputtering target has a rectangular parallelepiped, a cube, a cylinder, and an irregular shape. The cuboid, cube and cylinder shape targets are solid. During the sputtering process, the circular permanent magnet establishes a toroidal magnetic field on the surface of the target, forming an etched area on the annular surface equidistant between the axes, and the disadvantage is the thickness of the thin film deposition. Uniformity is not easy to control, and the utilization rate of the target is low, only 20% to 30%. At present, the rotary hollow tube magnetron sputtering target is popularized at home and abroad. The advantage is that the hollow tube target can be rotated around the fixed strip magnet assembly, so that the 360° target surface can be uniformly etched, and the utilization rate is high. 80%. In general, the grain size of the sputtering target must be controlled below 100 microns, and even the directionality of its crystalline structure must be strictly controlled.
鈮濺射靶材作為製備鈮及其合金薄膜材料的重要原料，在液晶平板顯示器、光學鏡頭、電子成像、信息儲存、太陽能電池和玻璃鍍膜等光電領域及船舶、化工等腐蝕環境中具有廣泛的應用。鈮濺射靶材對產品的內部晶粒尺寸以及表面粗糙度的要求較高，其中軸向方向晶粒大小要求均勻一致，晶粒尺寸50~100μm，表面粗糙度要求Ra1.6um，因此研究者對鈮靶材的生產方法進行了深入的研究。例如：公開號為CN102489951A的中國專利公開了一種濺射用鈮管狀靶材的製備方法，該方法包括以下步驟：製備鈮管坯；採用鋼包套將鈮管坯內、外壁及兩頭緊密包覆，焊接密封，然後進行熱擠壓，得到鈮管靶；將鈮管靶進行酸洗和熱處理，即得到鈮管狀靶材。上述方法只是採用熱擠壓的方法對鈮管坯進行加工，從而無法保證鈮濺射靶材內部晶粒組織均勻性和表面粗糙度。As a key raw material for the preparation of tantalum and its alloy thin film materials, tantalum sputtering targets are widely used in the photovoltaic field such as liquid crystal flat panel display, optical lens, electronic imaging, information storage, solar cell and glass coating, and corrosive environments such as ships and chemicals. application. The sputtering target has high requirements on the internal grain size and surface roughness of the product. The grain size in the axial direction is uniform, the grain size is 50~100μm, and the surface roughness is Ra. 1.6um, so the researchers conducted in-depth research on the production methods of bismuth targets. For example, Chinese Patent Publication No. CN102489951A discloses a method for preparing a tubular target for sputtering, which comprises the steps of: preparing a tube blank; and tightly coating the inner and outer walls of the tube blank and the two ends with a steel sheath. The welded seal is then subjected to hot extrusion to obtain a fistula target; the fistula target is subjected to pickling and heat treatment to obtain a tantalum tubular target. The above method only uses the hot extrusion method to process the tube blank, thereby failing to ensure the uniformity of the grain structure and the surface roughness of the sputtering target.
本發明解决的技術問題在於提供一種鈮靶材及其製備方法，通過本發明製備的鈮靶材內部晶粒組織均勻且具有較低的表面粗糙度值。The technical problem to be solved by the present invention is to provide a bismuth target and a preparation method thereof, and the ruthenium target prepared by the invention has uniform grain structure inside and has a low surface roughness value.
有鑒於此，本發明提供了一種鈮靶材的製備方法，包括以下步驟：a)將鈮管坯進行預熱，在預熱後的鈮管坯表面塗抹玻璃粉；b)將步驟a)得到的鈮管坯進行熱擠壓，將熱擠壓後的鈮管坯進行酸洗，將酸洗後的鈮管坯進行熱處理；c)採用第一刀具對步驟b)得到的鈮管坯的內孔進行鏜銑，得到鈮靶材；所述第一刀具的刀頭為雙刀頭或單刀頭，所述第一刀具的刀杆的長度大於5000mm，所述雙刀頭在所述刀杆工作端沿軸線方向依次設置，所述刀頭的刃傾角為負值。In view of the above, the present invention provides a method for preparing a bismuth target, comprising the steps of: a) preheating a bismuth tube blank, applying a glass frit on the surface of the preheated bismuth tube blank; b) obtaining step a) The tube blank is hot-extruded, the hot-pressed tube blank is pickled, and the pickled tube body is heat-treated; c) the first tool is used to the inside of the tube blank obtained in step b) The hole is boring and milling to obtain a boring target; the cutter head of the first cutter is a double cutter head or a single cutter head, and the length of the cutter cutter of the first cutter is greater than 5000 mm, and the double cutter head works at the cutter cutter The ends are sequentially disposed in the axial direction, and the blade inclination angle of the cutter head is a negative value.
優選的，所述鈮管坯的製備過程具體為：a1)將鈮鑄錠進行預熱，在預熱後的鈮鑄錠表面塗抹玻璃粉； a2)將步驟a1)得到的鈮鑄錠進行第一次熱鍛造，將第一次熱鍛造後的鈮鑄錠進行酸洗，將酸洗後的鈮鑄錠進行熱處理；a3)將步驟a2)得到的鈮鑄錠進行鑽孔及車削外表面，得到鈮管坯。Preferably, the preparation process of the tube blank is specifically: a1) preheating the tantalum ingot, and applying the glass powder on the surface of the precasted tantalum ingot; A2) performing the first hot forging of the niobium ingot obtained in the step a1), pickling the niobium ingot after the first hot forging, and subjecting the pickled ingot to heat treatment; a3) step a2) The obtained crucible ingot is drilled and the outer surface is turned to obtain a crucible.
優選的，步驟a2)中所述熱處理之後還包括：將熱處理後的鈮鑄錠進行第二次熱鍛造，將第二次鍛造後的鈮鑄錠再次熱處理。Preferably, after the heat treatment in the step a2), the heat-treated bismuth ingot is subjected to a second hot forging, and the second forged bismuth ingot is heat-treated again.
優選的，步驟a)中在預熱後的鈮管坯表面塗抹玻璃粉之後還包括：將塗抹玻璃粉的鈮管坯進行預熱，在預熱後的鈮管坯的表面再次塗抹玻璃粉。Preferably, after the glass powder is applied to the surface of the preheated tantalum tube in step a), the method further comprises: preheating the glass tube coated with the glass powder, and applying the glass powder to the surface of the preheated tantalum tube blank again.
優選的，所述鈮管坯進行鏜銑之後還包括：c1)將鏜銑後的鈮管坯的外圓進行車削，所述車削的第二刀具的前角為30°~40°，後角為4°~6°；主偏角為50°~60°，副偏角為10°~15°；刃傾角為10°~15°；刀尖圓弧半徑為0.3~0.4mm。Preferably, after the boring and milling of the boring tube blank, the method further comprises: c1) turning the outer circle of the boring and milling boring blank, the front angle of the second tool being turned is 30°~40°, the rear angle It is 4°~6°; the main declination is 50°~60°, the declination angle is 10°~15°; the rake angle is 10°~15°; the radius of the tool nose arc is 0.3~0.4mm.
優選的，所述第一次熱鍛造具體為：將步驟a1)得到的鈮鑄錠加熱至365℃~472℃，保溫2h~4.5h，將保溫後的鈮鑄錠進行鐓粗和拔長。Preferably, the first hot forging is specifically: heating the bismuth ingot obtained in the step a1) to 365 ° C to 472 ° C, and maintaining the enthalpy of the ingot after the heat preservation for 2 h to 4.5 h.
優選的，步驟a)中所述預熱的溫度為700℃~950℃。Preferably, the preheating temperature in the step a) is from 700 ° C to 950 ° C.
優選的，步驟b)中所述熱擠壓的溫度為1000℃~1300℃，所述熱處理的溫度為930℃~1300℃。Preferably, the temperature of the hot extrusion in the step b) is from 1000 ° C to 1300 ° C, and the temperature of the heat treatment is from 930 ° C to 1300 ° C.
優選的，步驟c)中所述刀杆的長度為5500mm~6500mm。Preferably, the length of the shank in step c) is 5500 mm~6500 mm.
優選的，步驟c)中所述雙刀頭平行於一條直線。Preferably, the double cutter head in step c) is parallel to a straight line.
優選的，步驟c)中所述雙刀頭之間的距離控制在30mm~50mm。例如，對於粗加工而言，雙刀頭之間合適的距離為50mm；對於精加工而言，雙刀頭之間合適的距離為30mm。Preferably, the distance between the double cutter heads in step c) is controlled to be 30 mm to 50 mm. For example, for roughing, the proper distance between the double cutter heads is 50 mm; for finishing, the suitable distance between the double cutter heads is 30 mm.
本發明還提供了一種上述方案製備的鈮靶材，所述鈮靶材的晶粒度為5~6.5級。The present invention also provides a ruthenium target prepared by the above scheme, wherein the ruthenium target has a grain size of 5 to 6.5.
本發明提供了一種鈮靶材及其製備方法，在鈮靶材製備過程中，首先將鈮管坯進行熱擠壓，然後將熱擠壓後的鈮管坯進行內孔的加工，從而得到鈮靶材。與現有技術相比，本發明在製備鈮靶材的過程中，首先在鈮管坯表面塗抹了玻璃粉，由於鈮管坯表面噴塗有玻璃粉，使其在擠壓過程中具有較好的潤滑效果，從而使鈮管坯的表面質量較好；隨後的熱擠壓加工與熱處理有助於鈮管坯晶粒的細化與均勻化；最後將擠壓後的鈮管坯進行機加工，通過選用特殊刀具對鈮管坯的內孔進行鏜銑，使斷屑能夠連續自內孔排出，避免了斷屑積聚於內孔而影響內孔表面加工的問題，從而得到了內部晶粒均勻和表面粗糙度值較低的鈮靶材。The invention provides a bismuth target and a preparation method thereof. In the preparation process of the bismuth target, the burr blank is first subjected to hot extrusion, and then the hot extruded slab tube is processed into the inner hole to obtain 铌. Target. Compared with the prior art, in the process of preparing the bismuth target, the invention firstly applies the glass powder on the surface of the stern tube blank, and the surface of the slab tube is sprayed with the glass powder, so that it has better lubrication during the extrusion process. The effect is that the surface quality of the tube blank is better; the subsequent hot extrusion processing and heat treatment contribute to the refinement and homogenization of the billet blank; finally, the extruded tantalum billet is machined through The special hole is used to boring and milling the inner hole of the tube blank, so that the chip breaking can be continuously discharged from the inner hole, avoiding the problem that the chip breaking accumulates in the inner hole and affecting the surface processing of the inner hole, thereby obtaining internal grain uniformity and surface. A ruthenium target with a low roughness value.
圖1為本發明實施例1製備的鈮靶材的金相照片；圖2為本發明實施例2製備的鈮靶材的金相照片；圖3為本發明對比例1生產的鈮濺射靶材的金相照片；以及圖4為本發明對比例1生產的鈮濺射靶材的金相照片。1 is a metallographic photograph of a ruthenium target prepared in Example 1 of the present invention; FIG. 2 is a metallographic photograph of a ruthenium target prepared in Example 2 of the present invention; and FIG. 3 is a tantalum sputtering target produced in Comparative Example 1 of the present invention. A metallographic photograph of the material; and Figure 4 is a metallographic photograph of the tantalum sputtering target produced in Comparative Example 1 of the present invention.
為了進一步理解本發明，下面結合實施例對本發明優選實施方案進行描述，但是應當理解，這些描述只是為進一步說明本發明的特徵和優點，而不是對本發明申請專利範圍的限制。In order to further understand the present invention, the preferred embodiments of the present invention are described in the accompanying drawings, but the description of the present invention is not intended to limit the scope of the invention.
本發明實施例公開了一種鈮靶材的製備方法，包括以下步驟：a)將鈮管坯進行預熱，在預熱後的鈮管坯表面塗抹玻璃粉；b)將步驟a)得到的鈮管坯進行熱擠壓，將熱擠壓後的鈮管坯進行酸洗，將酸洗後的鈮管坯進行熱處理；c)採用第一刀具對步驟b)得到的鈮管坯的內孔進行鏜銑，得到鈮靶材；所述第一刀具的刀頭為雙刀頭或單刀頭，所述第一刀具的刀杆的長度大於5000mm，所述雙刀頭在所述刀杆工作端沿軸線方向依次設置，所述刀頭的刃傾角為負值。The embodiment of the invention discloses a method for preparing a bismuth target, comprising the steps of: a) preheating the bismuth tube blank, applying glass powder on the surface of the preheated bismuth tube blank; b) 铌 obtained in step a) The tube blank is hot-extruded, the hot-pressed tube body is pickled, and the pickled tube body is heat-treated; c) the first hole is used to perform the inner hole of the tube blank obtained in step b) Boring and milling, obtaining a target; the cutter head of the first cutter is a double cutter head or a single cutter head, and the length of the cutter cutter of the first cutter is greater than 5000 mm, and the double cutter head is along the working end of the cutter cutter The axial direction is sequentially set, and the blade inclination angle of the cutter head is a negative value.
按照本發明，首先需要準備原材料鈮鑄錠。本發明對於所述 鈮鑄錠的製備方法並沒有特別的限制，但是為了使鈮靶材具有更加均勻的晶粒組織和保證鈮靶材中鈮的純度，所述鈮鑄錠的製備方法優選按照下述方法製備：首先將鈮礦石與氫氟酸、硫酸混合，萃取其中的鈮液，所述鈮液經氨氣沉澱後得到氫氧化鈮；將所述氫氧化鈮燒結後得到氧化鈮；將鋁粉與所述氧化鈮混合，並在真空中還原，得到金屬粗鈮；將所述粗鈮在水平結晶器中進行熔煉，得到熔煉鈮板；將所述鈮板在電子束爐中進行熔煉，從而得到鈮鑄錠。According to the present invention, it is first necessary to prepare a raw material bismuth ingot. The present invention is for the The preparation method of the ruthenium ingot is not particularly limited, but in order to have a more uniform grain structure of the ruthenium target and to ensure the purity of ruthenium in the ruthenium target, the preparation method of the ruthenium ingot is preferably prepared as follows: Firstly, the cerium ore is mixed with hydrofluoric acid and sulfuric acid to extract the cerium liquid, and the cerium is precipitated by ammonia gas to obtain cerium hydroxide; the cerium hydroxide is sintered to obtain cerium oxide; The cerium oxide is mixed and reduced in a vacuum to obtain a crude metal ruthenium; the crude ruthenium is smelted in a horizontal crystallizer to obtain a smelting ruthenium plate; the ruthenium plate is smelted in an electron beam furnace to obtain a bismuth casting ingot.
上述粗鈮在水平結晶器中進行熔煉的過程中，由於水平結晶器真空度較高，則熔體的過熱度較高，鈮金屬液態維持時間較長，能夠將金屬鈮中的間隙雜質、低熔點金屬雜質和蒸汽壓較高的金屬雜質除去，從而能夠得到純度較高的熔煉鈮板。而所述鈮板在電子束爐熔煉過程中，所述電子束爐的功率較大，高速運動的電子打在熔煉鈮板和熔池內，動能轉化為熱能，將熔煉鈮板熔化滴入熔融態的熔池裏，對金屬鈮進行精煉，由於電子束爐的真空度較高，則熔體的過熱度很高，金屬鈮在以液體滴入熔池過程和鈮金屬在熔池液態維持時間較長，同樣也能夠將金屬鈮中的間隙雜質、低熔點金屬雜質和蒸汽壓較高的金屬雜質除去，從而達到精煉的效果，得到純度較高的金屬鈮錠，純度99.95%。In the process of smelting the above-mentioned rough crucible in the horizontal crystallizer, since the degree of vacuum of the horizontal crystallizer is high, the superheat degree of the melt is high, and the liquid metal of the base metal is maintained for a long time, and the gap impurities in the metal crucible can be low. Melting metal impurities and metal impurities having a high vapor pressure are removed, so that a smelting crucible having a high purity can be obtained. When the raft is in the electron beam furnace smelting process, the electron beam furnace has a large power, and the high-speed moving electrons are driven in the smelting raft and the molten pool, and the kinetic energy is converted into heat energy, and the smelting slab is melted and melted into the molten state. In the molten pool of the state, the metal crucible is refined. Due to the high vacuum of the electron beam furnace, the superheat of the melt is high, the metal crucible is dripped into the molten pool by the liquid, and the liquid metal is maintained in the molten pool. Longer, it is also possible to remove interstitial impurities, low melting point metal impurities and metal impurities with high vapor pressure in the metal crucible to achieve the refining effect, and obtain a metal crucible having a higher purity, purity. 99.95%.
按照上述方法將鈮鑄錠製備完成後，則開始鈮靶材的製備過程。在對鈮管坯進行熱擠壓的步驟b)之前，作為優選方案所述鈮管坯的製備方法，包括：a1)將鈮鑄錠進行預熱，在預熱後的鈮鑄錠表面塗抹玻璃粉；a2)將步驟a1)得到的鈮鑄錠進行第一次熱鍛造，將第一次熱鍛造後的鈮鑄錠進行酸洗，將酸洗後的鈮鑄錠進行熱處理；a3)將步驟a2)得到的鈮鑄錠進行鑽孔及車削外表面，得到鈮管坯。After the preparation of the tantalum ingot is completed as described above, the preparation process of the tantalum target is started. Before the step b) of hot pressing the tube blank, the method for preparing the tube blank according to the preferred embodiment comprises: a1) preheating the tantalum ingot, and applying the glass on the surface of the preheated tantalum ingot. Powder; a2) The first ingot is forged in the first hot forging of the crucible ingot obtained in the step a1), the pickled ingot after the first hot forging is pickled, and the pickled ingot is subjected to heat treatment; a3) the step A2) The obtained tantalum ingot is drilled and turned to the outer surface to obtain a tantalum tube blank.
上述製備鈮管坯的過程中，首先將鈮鑄錠進行預熱，並在預 熱後的鈮鑄錠表面塗抹玻璃粉。所述預熱有利於鈮鑄錠表面的玻璃粉與鈮鑄錠表面粘結。所述預熱的溫度優選為150℃~250℃，更優選為175℃~225℃，最優選為200℃。為了防止熱鍛過程中鈮鑄錠的吸氫吸氧，將鈮鑄錠預熱後則在鈮鑄錠表面塗覆玻璃粉。所述玻璃粉的厚度優選為1mm~1.5mm，以保證玻璃粉在鈮鑄錠表面能夠塗覆均勻。In the above process for preparing the tantalum tube blank, the tantalum ingot is first preheated and pre-heated. The surface of the hot tanned ingot is coated with glass powder. The preheating facilitates bonding of the glass frit on the surface of the crucible ingot to the surface of the crucible ingot. The preheating temperature is preferably from 150 ° C to 250 ° C, more preferably from 175 ° C to 225 ° C, and most preferably 200 ° C. In order to prevent hydrogen absorption and oxygen absorption of the ingot in the hot forging process, the surface of the crucible ingot is coated with glass frit after the ingot is preheated. The thickness of the glass frit is preferably from 1 mm to 1.5 mm to ensure that the glass frit can be uniformly coated on the surface of the tantalum ingot.
將鈮鑄錠表面塗抹玻璃粉後，則將鈮鑄錠進行第一次熱鍛。 按照本發明，為了提高鈮鑄錠鍛造過程中的塑性，保證鈮鑄錠的鍛透性以及晶粒破碎的充分性，本發明選擇了熱鍛的鍛造方式。 所述第一次熱鍛的具體步驟為：將塗覆抗氧化塗層的鈮鑄錠加熱至365℃~472℃，保溫2h~4.5h後，對鈮鑄錠進行徑向鐓粗和徑向拔長的鍛造。本領域技術人員熟知的，鑄錠是採用電子束爐熔煉的，熔煉的方向是軸向的，即鑄錠長度方向，延軸向熔煉過程中是產生粗晶、枝晶及晶帶的方向，該方向也是塑性較好的方向。 而軸向的鐓粗加工能夠在軸向上破碎鑄造態的粗晶、枝晶等組織，使晶粒細化，同時軸向鐓粗和軸向拔長鈮鑄錠容易變形，不易開裂。After the surface of the cast ingot is coated with glass frit, the ingot is subjected to the first hot forging. According to the present invention, in order to improve the plasticity during the forging process of the bismuth ingot, and to ensure the forgeability of the bismuth ingot and the sufficiency of the grain breakage, the present invention selects the forging method of hot forging. The specific step of the first hot forging is: heating the bismuth ingot coated with the anti-oxidation coating to 365 ° C ~ 472 ° C, after holding for 2 h ~ 4.5 h, the radial indentation and radial direction of the ingot casting Long forging. As is well known to those skilled in the art, the ingot is smelted by an electron beam furnace, and the direction of the smelting is axial, that is, the length direction of the ingot, and the directions of the coarse crystal, the dendrites, and the crystal ribbon are generated during the axial smelting process. This direction is also a direction of better plasticity. The axial upsetting process can crush the coarse-grained, dendritic and other structures in the as-cast state in the axial direction, so that the grain is refined, and the axially upset and the axially elongated slab are easily deformed and are not easily cracked.
在第一次熱鍛造完成後，為了避免在後續熱處理過程中抗氧化塗層的汽化對鈮鑄錠表面質量的影響，本發明優選將第一次熱處理後的鈮鑄錠進行酸洗，以將鈮鑄錠表面的玻璃粉除去。所述酸洗的酸液優選為氫氟酸、鹽酸和硫酸的混合溶液。所述氫氟酸為市售的氫氟酸，其質量分數為35.35wt%；所述鹽酸為市售的鹽酸，其濃度為37wt%，所述硫酸為市售的濃硫酸，其濃度為98wt%，所述鹽酸、氫氟酸與硫酸的體積比優選為5：3：2，所述酸液的溫度優選為55℃~75℃，更優選為60~70℃。為了使鈮鑄錠表面的玻璃粉能夠洗滌乾淨，所述酸洗的時間優選為5min~10min。After the first hot forging is completed, in order to avoid the influence of the vaporization of the oxidation resistant coating on the surface quality of the tantalum ingot during the subsequent heat treatment, the present invention preferably picks up the tantalum ingot after the first heat treatment to The glass powder on the surface of the ingot is removed. The acid washed acid solution is preferably a mixed solution of hydrofluoric acid, hydrochloric acid and sulfuric acid. The hydrofluoric acid is a commercially available hydrofluoric acid having a mass fraction of 35.35 wt%; the hydrochloric acid is a commercially available hydrochloric acid having a concentration of 37 wt%, and the sulfuric acid is a commercially available concentrated sulfuric acid having a concentration of 98 wt%. The volume ratio of the hydrochloric acid, hydrofluoric acid and sulfuric acid is preferably 5:3:2, and the temperature of the acid liquid is preferably 55 ° C to 75 ° C, more preferably 60 to 70 ° C. In order to enable the glass frit on the surface of the tantalum ingot to be washed clean, the pickling time is preferably from 5 min to 10 min.
為了消除加工過程中鈮鑄錠內部的殘餘內應力，本發明在第一次熱鍛完成後，將鈮鑄錠進行了熱處理。在鍛造過程中鈮鑄錠 會產生加工硬化，如果不進行熱處理會增加第二次熱鍛的難度，甚至會引起加工開裂，同時為了使第一次鍛造後的鈮鑄錠獲得重新再結晶組織，與後續的第二次熱鍛配合進行再次晶粒破碎，本發明將第一次熱鍛後的鈮鑄錠進行熱處理。所述熱處理的溫度優選為930℃~1300℃，更優選為1100℃~1200℃；所述熱處理的時間優選為60min~100min，更優選為80min~90min。In order to eliminate the residual internal stress inside the bismuth ingot during the processing, the present invention heat-treats the bismuth ingot after the first hot forging is completed. Casting ingots during forging It will produce work hardening. If it is not heat treated, it will increase the difficulty of the second hot forging, and even cause the processing cracking. At the same time, in order to obtain the re-recrystallized structure of the first ingot after the forging, and the subsequent second heat The forging compound performs the grain breakage again, and the present invention heat-treats the first hot-forged tantalum ingot. The temperature of the heat treatment is preferably 930 ° C to 1300 ° C, more preferably 1100 ° C to 1200 ° C; the heat treatment time is preferably 60 min to 100 min, more preferably 80 min to 90 min.
按照本發明，鈮鑄錠進行熱處理後，為了得到內部晶粒均勻細小的鈮靶材，作為優選方案，本發明將熱處理後的鈮鑄錠進行第二次熱鍛。本發明進行第二次熱鍛能夠再次充分的破碎鈮鑄錠內部晶粒組織，達到細化晶粒的效果。所述第二次鍛造的具體步驟為：將步驟a)中熱處理後的鈮鑄錠第二次加熱至365℃~472℃，第二次保溫2h~4.5h，將第二次保溫後的鈮鑄錠進行第二次鐓粗和第二次拔長，所述第一次鍛造與所述第二次鍛造的總加工率為50%~80%。對於鍛造的次數還可以是三次四次甚至更多次，本發明並沒有特別的限制，但是出於成本和效率的考慮，本發明優選進行了兩次鍛造。According to the present invention, in order to obtain a ruthenium target having a uniform inner crystal grain after heat treatment of the ruthenium ingot, the present invention preferably performs the second hot forging of the heat-treated bismuth ingot after heat treatment. The second hot forging of the present invention can fully break the internal grain structure of the ingot casting to achieve the effect of refining the crystal grains. The specific step of the second forging is: heating the bismuth ingot in the step a) to 365 ° C ~ 472 ° C for the second time, the second holding for 2 h ~ 4.5 h, the second heat preservation 铌The ingot is subjected to the second upsetting and the second upsizing, and the total processing rate of the first forging and the second forging is 50% to 80%. The number of forgings may be three or four times or more, and the present invention is not particularly limited, but the present invention preferably performs two forgings for cost and efficiency.
為了防止鈮鑄錠在鍛造過程中吸氫吸氧，作為優選方案，所述第二次熱鍛之前還包括：將步驟a2)熱處理後的鈮鑄錠進行預熱，在預熱後的鈮鑄錠表面塗覆玻璃粉。所述預熱的溫度優選為150℃~250℃，更優選為180℃~230℃，最優選為200℃。In order to prevent the sputum ingot from absorbing hydrogen during the forging process, as a preferred solution, the second hot forging further comprises: preheating the bismuth ingot after the heat treatment in step a2), and casting the slab after preheating. The surface of the ingot is coated with glass frit. The preheating temperature is preferably from 150 ° C to 250 ° C, more preferably from 180 ° C to 230 ° C, and most preferably 200 ° C.
按照本發明，在第二次熱鍛造完成後，為了消除鍛造過程中的殘餘應力，使鈮鑄錠的內部組織均勻細小，則將第二次熱鍛後的鈮鑄錠進行再次熱處理。所述再次熱處理的溫度優選為930℃~1300℃，更優選為1000℃~1200℃；所述再次熱處理的時間優選為60min~100min，更優選為80min~90min。According to the present invention, after the completion of the second hot forging, in order to eliminate the residual stress in the forging process and to make the internal structure of the niobium ingot uniform and fine, the second hot forged niobium ingot is subjected to heat treatment again. The temperature of the reheat treatment is preferably 930 ° C to 1300 ° C, more preferably 1000 ° C to 1200 ° C; and the time of the reheat treatment is preferably 60 min to 100 min, more preferably 80 min to 90 min.
將完成鍛造加工的鈮鑄錠的外表面及兩端頭進行車削，並對車削後的鈮鑄錠進行鑽孔，得到鈮管坯。The outer surface and the both ends of the forged ingot are turned and the turned ingot is drilled to obtain a tantalum billet.
在所述鈮鑄錠加工完成後，則將所述鈮管坯進行熱擠壓加 工，即進行步驟a)的操作。首先將所述鈮管坯進行預熱，並在預熱後的鈮管坯表面塗抹玻璃粉。所述預熱能夠使玻璃粉更好的在鈮管坯表面形成一層緻密的氧化物薄膜，同時使鈮管坯內外溫度均勻，為後續熱擠壓工序作準備。為了使玻璃粉較好地粘連在鈮管坯表面，所述預熱的溫度優選為700℃~950℃，更優選為800℃~900℃。在將鈮管坯預熱後，在預熱後的鈮管坯表面塗抹玻璃粉，使玻璃粉在鈮管坯表面形成一層緻密的薄膜。本領域技術人員熟知的，鈮管坯是心部中空的管狀坯料，因此在塗抹玻璃粉的過程中，所述鈮管坯的表面包括鈮管坯的內表面、外表面以及兩端面。 為了保證玻璃粉噴塗均勻，無孔隙，所述玻璃粉的厚度優選為1mm~2mm。After the processing of the tantalum ingot is completed, the tantalum tube blank is hot extruded Work, that is, the operation of step a). The tube blank is first preheated, and the surface of the preheated tantalum tube is coated with glass frit. The preheating can make the glass powder form a dense oxide film on the surface of the tube blank, and at the same time make the temperature inside and outside the tube blank uniform, and prepare for the subsequent hot extrusion process. In order to better adhere the glass frit to the surface of the tube blank, the preheating temperature is preferably from 700 ° C to 950 ° C, more preferably from 800 ° C to 900 ° C. After preheating the tube blank, the surface of the preheated tube blank is coated with glass frit to form a dense film on the surface of the tube blank. As is well known to those skilled in the art, the tube blank is a hollow tubular blank of the core, so that the surface of the tube blank includes the inner surface, the outer surface, and the both end faces of the tube blank during the application of the glass frit. In order to ensure uniform coating of the glass powder without voids, the thickness of the glass frit is preferably from 1 mm to 2 mm.
在鈮管坯表面噴塗玻璃粉後，作為優選方案，本發明優選將噴塗玻璃粉後的鈮管坯進行預熱，向預熱後的鈮管坯表面再次噴塗玻璃粉。為了保證玻璃粉的充分熔化，使其粘連在鈮錠表面，在鈮錠表面形成一層緻密的抗氧化薄膜，所述預熱的溫度優選為1000℃~1300℃，更優選為1100℃~1200℃；所述預熱的時間優選為1min~15min，更優選為5min~10min。所述噴塗玻璃粉的厚度優選為1mm~2mm。此次噴塗玻璃粉能夠保證鈮錠表面的玻璃粉具有充分的抗氧化和潤滑作用。為了使鈮錠表面的玻璃粉具有充分的抗氧化和潤滑作用，可以在鈮錠表面多次噴塗玻璃粉，本發明並沒有特別的限制，但出於成本以及效率的考慮，本發明優選在鈮管坯表面噴塗兩次玻璃粉。另外，本發明對於玻璃粉的選取沒有特別限制，只要其為用於熱加壓的玻璃粉並且玻璃粉的使用溫度包括鈮管的加工溫度即可。After spraying the glass powder on the surface of the tube blank, as a preferred embodiment, in the present invention, the tube blank after spraying the glass powder is preferably preheated, and the glass powder is sprayed again onto the surface of the preheated tube body. In order to ensure sufficient melting of the glass powder to adhere to the surface of the bismuth ingot, a dense anti-oxidation film is formed on the surface of the bismuth ingot, and the preheating temperature is preferably from 1000 ° C to 1300 ° C, more preferably from 1100 ° C to 1200 ° C. The preheating time is preferably from 1 min to 15 min, more preferably from 5 min to 10 min. The thickness of the sprayed glass frit is preferably from 1 mm to 2 mm. The sprayed glass powder can ensure that the glass powder on the surface of the antimony ingot has sufficient anti-oxidation and lubrication effects. In order to make the glass powder on the surface of the bismuth ingot sufficiently resistant to oxidation and lubrication, the glass powder may be sprayed on the surface of the bismuth ingot multiple times, and the present invention is not particularly limited, but the present invention is preferably used in view of cost and efficiency. Spray the glass powder twice on the surface of the tube blank. Further, the selection of the glass frit in the present invention is not particularly limited as long as it is a glass frit for hot pressurization and the use temperature of the glass frit includes the processing temperature of the crucible.
在將鈮管坯表面噴塗玻璃粉後，即將噴塗玻璃粉後的鈮管坯進行熱擠壓。本領域技術人員熟知的，擠壓的方式按坯料的溫度可分為冷擠壓、熱擠壓和溫擠壓。本發明選用熱擠壓的方式能夠得到均勻的內部組織，同時使坯料易於擠壓成型。所述熱擠壓的 溫度優選為1000℃~1300℃，更優選為1100℃~1200℃，此溫度區間內鈮管坯塑性較好，且容易變形。所述擠壓的擠壓機為本領域技術人員熟知的擠壓機，本發明並沒有特別的限制，所述擠壓機的噸位優選大於等於3000噸，更優選為3500~4500噸，所述擠壓比優選大於等於4.5，更優選為5~7。After spraying the glass powder on the surface of the tube blank, the tube blank after spraying the glass powder is hot extruded. As is well known to those skilled in the art, the manner of extrusion can be divided into cold extrusion, hot extrusion and warm extrusion depending on the temperature of the blank. The invention adopts the method of hot extrusion to obtain uniform internal structure, and at the same time, the blank is easy to be extruded. Hot extruded The temperature is preferably from 1000 ° C to 1300 ° C, more preferably from 1100 ° C to 1200 ° C. In this temperature range, the tube blank is plastic and is easily deformed. The extruded extruder is an extruder known to those skilled in the art, and the invention is not particularly limited, and the tonnage of the extruder is preferably 3,000 tons or more, more preferably 3,500 to 4,500 tons. The extrusion ratio is preferably 4.5 or more, more preferably 5 to 7.
按照本發明，將所述鈮管坯熱擠壓完成後，即將熱擠壓後的鈮管坯進行酸洗，從而將鈮管坯表面的玻璃粉除去，以防止在後續熱處理過程中發生玻璃粉熔化或汽化，影響鈮管坯表面質量。 所述酸洗的酸液優選為氫氟酸和硝酸的混合溶液，所述氫氟酸為市售的氫氟酸，其質量分數為35.35wt%，所述硝酸為市售的鹽酸，其濃度為68%，所述氫氟酸與所述硝酸的體積比優選為3：5，所述酸液的溫度優選為55℃~75℃，更優選為60~70℃。為了消除鈮管坯在擠壓過程中的殘應力，獲得均勻的再結晶組織，本發明將酸洗後的鈮管坯進行熱處理。本發明優選在真空中進行熱處理以防止鈮管坯被氧化，所述熱處理的溫度優選為930℃~1300℃，更優選為1000℃~1200℃，所述熱處理的時間優選為60min~100min，更優選為70min~90min。按照本發明，在熱鍛造完成後達到了鈮鑄錠內部晶粒的初步細化，配合後續的熱擠壓工序，則有利於形成內部均勻的鈮靶材。According to the present invention, after the hot extrusion of the tube blank is completed, the hot-pressed tube blank is pickled to remove the glass powder on the surface of the tube blank to prevent glass powder from occurring during the subsequent heat treatment. Melting or vaporization affects the surface quality of the tube blank. The acid-washed acid solution is preferably a mixed solution of hydrofluoric acid and commercially available hydrofluoric acid having a mass fraction of 35.35 wt%, and the nitric acid is commercially available hydrochloric acid at a concentration thereof. The content ratio of the hydrofluoric acid to the nitric acid is preferably 3:5, and the temperature of the acid liquid is preferably 55 ° C to 75 ° C, more preferably 60 to 70 ° C. In order to eliminate the residual stress of the tube blank during extrusion and obtain a uniform recrystallized structure, the present invention heat-treats the pickled tube billet. The present invention preferably performs heat treatment in a vacuum to prevent the tube blank from being oxidized. The temperature of the heat treatment is preferably 930 ° C to 1300 ° C, more preferably 1000 ° C to 1200 ° C, and the heat treatment time is preferably 60 min to 100 min. It is preferably 70 min to 90 min. According to the present invention, after the hot forging is completed, the preliminary refinement of the inner crystal grains of the niobium ingot is achieved, and the subsequent hot extrusion step is facilitated to form a uniform internal crucible target.
所述鈮管坯完成熱擠壓工序後，將熱擠壓後的鈮管坯再次進行內孔機加工。對於鈮管坯內孔的加工，本發明採用了第一刀具對鈮管坯的內孔進行鏜銑，所述第一刀具的刀頭為雙刀頭或單刀頭，所述第一刀具的刀杆的長度大於5000mm，所述雙刀頭在所述刀杆工作端沿軸線方向依次設置，所述刀頭的刃傾角為負值。優選的，所述雙刀頭平行於一條直線，兩刀頭之間的距離控制在30mm~50mm。優選的，對於粗加工來說，最合適的距離為50mm；而對於精加工來說，最合適的距離為30mm。本領域技術人員熟知的，與鑽鏜床配套的刀具，在對內孔進行機加工過程中，刀具的 一端裝卡在鑽鏜床上，該端稱之為固定端，而另一端用於加工工件，該端則稱之為工作端。After the tube blank is completed in the hot extrusion process, the hot extruded tube billet is again subjected to inner hole machining. For the processing of the inner hole of the tube blank, the first tool is used for boring the inner hole of the tube blank, the cutter head of the first cutter is a double cutter head or a single cutter head, and the cutter of the first cutter The length of the rod is greater than 5000 mm, and the double cutter heads are sequentially disposed in the axial direction at the working end of the cutter bar, and the blade inclination angle of the cutter head is a negative value. Preferably, the double cutter head is parallel to a straight line, and the distance between the two cutter heads is controlled to be 30 mm to 50 mm. Preferably, the most suitable distance for roughing is 50 mm; and for finishing, the most suitable distance is 30 mm. As is well known to those skilled in the art, the tool associated with the drill boring machine, during the machining of the inner hole, the tool One end is mounted on the drill collar, the end is called the fixed end, and the other end is used to machine the workpiece, and the end is called the working end.
在對內孔加工的過程中，通過選用特殊的刀具，使鈮管坯內孔加工過程中，保持小吃刀深度小的走刀量，從而使斷屑逐漸成球團狀，有利於鈮斷屑的排出，以防止斷屑積聚於內孔中對內孔表面質量的影響。在內孔鏜銑的過程中，為了使鈮管坯的斷屑連續由內孔自動排出，在鏜銑的過程中，同時連接高壓硫化油對內孔進行鏜銑。所述硫化油具有潤滑冷却的作用，而高壓硫化油則促進了斷屑的排出。所述鏜銑過程中鑽鏜床的轉速優選為80轉/min~125轉/min；所述鏜銑的切削深度優選為0.5mm~1.2mm。In the process of machining the inner hole, by using a special cutter, the depth of the snack knife is kept small during the processing of the inner hole of the tube blank, so that the chip breaking gradually becomes a pellet shape, which is favorable for the chip breaking. Discharge to prevent the accumulation of chip breaking in the inner hole to affect the surface quality of the inner hole. In the process of boring and milling of the inner hole, in order to continuously discharge the chip breaking of the boring tube blank from the inner hole, the inner hole is boring and milling at the same time in the process of boring and milling. The vulcanized oil has the function of lubricating and cooling, and the high-pressure vulcanized oil promotes the discharge of chip breaking. The rotation speed of the drilling and boring machine in the boring and milling process is preferably 80 rpm/125 rpm/min; the cutting depth of the boring and milling is preferably 0.5 mm to 1.2 mm.
鈮管坯的內孔加工完成後，為了保證鈮管坯尺寸精准和表面粗糙度，本發明對鈮管坯的外圓進行車削。按照本發明，外圓車削的方法優選為：將得到的鈮坯裝卡在臥式車床上，以內孔為基準，對所述鈮管狀靶材的外圓進行車削，所述車削的第二刀具的前角(γ)為30°~40°，後角(α)為4°~6°；主偏角(φ)為50°~60°，副偏角為10°~15°；刃傾角(λ)為10°~15°；刀尖圓弧半徑為0.3~0.4mm。作為優選方案，所述車削的進給量：粗車(F)優選為0.25~0.3mm/轉，精車(f)優選為0.15~0.2mm/轉；切削深度：粗車(T)優選為2~5mm，精車(t)為0.8~1.2mm；切削速度：粗車(ν)優選為40m/min，精車優選為60m/min。為了提高車削過程中的精度，所述第二刀具優選為硬質合金刀具，更優選為鎢鈷類硬質合金刀具。所述鎢鈷類硬質合金刀具分為YG3、YG6、YG8等多種牌號，牌號後的數字表示含鈷量的百分數，其餘是碳化鎢；牌號後的數據越大，其韌性越好，適用於產品的粗加工。因此車削過程中粗車優選為YG8刀具，精加工優選為YG6刀具。After the inner hole of the tube blank is processed, in order to ensure the dimensional accuracy and surface roughness of the tube blank, the present invention turns the outer circle of the tube blank. According to the present invention, the method of external turning is preferably: loading the obtained blank into a horizontal lathe, turning the outer circle of the tubular target with the inner hole as a reference, and the second tool for turning The rake angle (γ) is 30°~40°, the back angle (α) is 4°~6°; the main declination (φ) is 50°~60°, and the auxiliary declination is 10°~15°; (λ) is 10°~15°; the radius of the tool nose arc is 0.3~0.4mm. Preferably, the feeding amount of the turning: the roughing vehicle (F) is preferably 0.25 to 0.3 mm/rev, the finishing vehicle (f) is preferably 0.15 to 0.2 mm/rev; and the cutting depth: the roughing vehicle (T) is preferably 2~5mm, fine car (t) is 0.8~1.2mm; cutting speed: rough car (ν) is preferably 40m/min, and fine car is preferably 60m/min. In order to improve the accuracy in the turning process, the second tool is preferably a cemented carbide tool, more preferably a tungsten-cobalt-type cemented carbide tool. The tungsten-cobalt type hard alloy cutter is divided into YG3, YG6, YG8 and other grades. The number after the grade indicates the percentage of cobalt content, and the rest is tungsten carbide; the larger the data after the grade, the better the toughness is suitable for the product. Roughing. Therefore, the roughing is preferably a YG8 tool during the turning process, and the finishing is preferably a YG6 tool.
本發明提供了一種鈮靶材及其製備方法，在鈮靶材製備過程中，首先將鈮管坯進行熱擠壓，然後將熱擠壓後的鈮管坯進行內孔的加工，從而得到鈮靶材。與現有技術相比，本發明在製備鈮 靶材的過程中，首先在鈮管坯表面塗抹了玻璃粉，由於鈮管坯表面噴塗有玻璃粉，使其在擠壓過程中具有較好的潤滑效果，從而使鈮管坯的表面質量較好；隨後的熱擠壓加工與熱處理有助於鈮管坯晶粒的細化與均勻化；最後將擠壓後的鈮管坯進行機加工，通過選用特殊的刀具對鈮管坯的內孔進行鏜銑，使斷屑能夠連續自內孔排出，避免了斷屑積聚於內孔而影響內孔表面加工的問題，從而得到了內部晶粒均勻和表面粗糙度較低的鈮靶材。其次，本發明在鈮管坯製備過程中採用了熱鍛造的方法，熱鍛造與熱擠壓相結合的方法，更有利於得到內部組織均勻的鈮靶材；另一方面，通過採用第二刀具對鈮靶材的外圓進行機加工，使得到的鈮靶材的尺寸更加精准，同時使鈮靶材的表面粗糙度較低。實驗結果表明，鈮靶材外表面粗糙度Ra1.6μm，內孔表面粗糙度Ra6.3μm。The invention provides a bismuth target and a preparation method thereof. In the preparation process of the bismuth target, the burr blank is first subjected to hot extrusion, and then the hot extruded slab tube is processed into the inner hole to obtain 铌. Target. Compared with the prior art, in the process of preparing the bismuth target, the invention firstly applies the glass powder on the surface of the stern tube blank, and the surface of the slab tube is sprayed with the glass powder, so that it has better lubrication during the extrusion process. The effect is that the surface quality of the tube blank is better; the subsequent hot extrusion processing and heat treatment contribute to the refinement and homogenization of the billet blank; finally, the extruded tantalum billet is machined through The special tool is used to boring the inner hole of the tube blank, so that the chip breaking can be continuously discharged from the inner hole, which avoids the problem that the chip breaking accumulates in the inner hole and affects the surface processing of the inner hole, thereby obtaining uniform internal crystal grains. A ruthenium target with a low surface roughness. Secondly, the present invention adopts a hot forging method in the preparation process of the tantalum tube blank, and the combination of hot forging and hot extrusion is more advantageous for obtaining a uniform target of the internal structure; on the other hand, by using the second cutter The outer circumference of the target is machined to make the size of the target target more precise, while at the same time making the surface roughness of the target. The experimental results show that the outer surface roughness Ra of the target 1.6μm, inner hole surface roughness Ra 6.3 μm.
本發明還提供了一種鈮靶材，所述鈮靶材按上述方法製備。 本領域技術人員熟知的，晶粒度是表徵晶粒大小的尺度，按照標準GB/T 6394-2002，晶粒度共分8級，1~4級為粗晶粒(對應於約89.8~254μm)，5~8級為細晶粒(對應於約22.5~63.5μm)。本發明製備的鈮靶材的晶粒度為5~6.5級(對應於約37.8~63.5μm)。The present invention also provides a ruthenium target which is prepared as described above. As is well known to those skilled in the art, the grain size is a scale for characterizing the grain size. According to the standard GB/T 6394-2002, the grain size is divided into 8 grades, and the grades 1 to 4 are coarse grains (corresponding to about 89.8 to 254 μm). ), grades 5-8 are fine grains (corresponding to about 22.5 to 63.5 μm). The ruthenium target prepared by the present invention has a grain size of 5 to 6.5 (corresponding to about 37.8 to 63.5 μm).
為了進一步理解本發明，下面結合實施例對本發明提供的鈮靶材及其製備方法進行詳細說明，本發明的保護範圍不受以下實施例的限制。In order to further understand the present invention, the ruthenium target provided by the present invention and the preparation method thereof will be described in detail below with reference to the examples, and the scope of protection of the present invention is not limited by the following examples.
實施例1Example 1
該實施例中所用的玻璃粉為用於熱擠壓及穿孔工藝的玻璃粉，具有100目的平均粒度，得自北京天力創玻璃科技開發有限公司(型號：855-7噴塗粉)。進行以下工藝：步驟一、五氧化二鈮通過鋁熱還原得到氧化鈮，將氧化鈮分別在水平爐熔煉和電子束爐熔煉，得到直徑為Φ 190mm、長度為390mm，化學成分為Nb99.95%的鈮錠； 步驟二、將步驟一得到的鈮錠預熱200℃，塗抹玻璃粉，錠材加熱至400℃，保溫3h，對鈮錠軸向鐓粗至210mm，拔長至200×200×280mm；步驟三、將步驟二得到的鈮錠進行酸洗：HCl：HF：H2SO4=5：3：2(體積比)，酸洗時間10分鐘，去除表面雜質及玻璃粉，肉眼觀察鈮金屬光澤無雜斑即可；步驟四、將步驟三得到的鈮錠進行熱處理：熱處理溫度為1000℃，保溫時間為60min；步驟五、將步驟四得到的鈮錠鐓粗至220mm，鍛造打方190×190×Lmm，最後鍛造打圓到Φ 200mm；步驟六、將步驟五得到的鈮錠進行酸洗：HCl：HF：H2SO4=5：3：2(體積比)，酸洗時間10分鐘，去除表面雜質及玻璃粉，肉眼觀察鈮金屬光澤無雜斑後進行熱處理，熱處理的溫度為1000℃，保溫時間為60min；步驟七、通過車床對步驟六得到的鈮錠進行車削外表面及兩端頭，去除缺陷後進行鑽孔，得到尺寸為：外徑Φ 195mm，內徑100mm，長度為350mm，一端頭倒外角30mm×45°的鈮管坯；步驟八、將步驟七得到的鈮管坯採用低溫中頻爐對鈮管坯進行預熱，預熱溫度為900℃，預熱後在鈮管坯料內外表面及兩端頭塗抹玻璃粉；步驟九、將步驟八得到的鈮管坯轉至二次中頻感應爐中進行二次加熱，加熱溫度為1050℃，保溫10分鐘；步驟十、將步驟九得到的鈮管坯進行二次塗抹玻璃粉，玻璃粉厚度控制在1~2mm之間，保證塗抹均勻無孔隙；步驟十一、將在步驟十得到的鈮管坯傳送至擠壓筒內進行擠壓，此擠壓機噸位應大於3000噸。擠壓後得到外徑為Φ 160mm，內徑為90mm，長度為560mm的鈮靶管；步驟十二、將步驟十一得到的鈮靶管進行酸洗，酸洗：HF： HNO3=3：5(體積比)，酸液加熱75℃，最終去除表面玻璃粉，肉眼觀察鈮金屬光澤無雜斑即可；步驟十三、將步驟十二得到的鈮靶管進行真空熱處理，溫度1050℃保溫60分鐘；熱處理後進行校直，直線度1.0mm後，矯直設備為兩輥矯直機；步驟十四、將步驟十三得到的鈮管靶材裝卡到深孔鑽鏜床上，通過採用雙刀頭與加長刀杆的刀具相配合，再連接高壓硫化油進行鏜銑內孔，刀杆的長度為5600mm，在鏜銑過程中車床轉速80~125轉/min，吃刀深度為0.5~1.2mm。內孔鏜銑完成後車削兩端頭，保證兩端頭切面垂直軸線完成後尺寸為：Φ內為100±0.15mm，長度為482±1mm；步驟十五、將步驟十四得到的鈮旋轉靶材裝卡在臥式車床上，以內孔為基準進行找正然後車削外圓，外圓車削過程中選用刀具材料YG8；前角γ為30°，後角α為4°；主偏角φ為60°，副偏角為10°；刃傾角採用λ為10°，刀尖圓弧半徑為粗車R為0.4mm。進給量：粗車F為0.25mm/轉，精車f為0.15mm/轉；切削深度：粗車T為2mm，精車t為0.8mm；切削速度：粗車ν為40m/min；精車60m/min。最後車削完成後尺寸：Φ外為155±0.1mm，Φ內為100±0.15mm，長度為482±1mm；步驟十六、將步驟十五得到的旋轉鍍膜鈮靶材在300~400轉/min過程中使用砂紙、研磨布、研磨膏對外表面進行拋光精處理，使其表面粗糙度達到Ra1.6μm；步驟十七、將步驟十六得到的旋轉鍍膜鈮靶材裝卡到藥室拋光機上與砂紙、研磨布、研磨膏相配合進行內孔處理，轉數為280~350轉/min，最終使其內孔表面粗糙度達到Ra6.3μm。The glass frit used in this example is a glass frit for hot extrusion and perforation process, having an average particle size of 100 mesh, obtained from Beijing Tianli Chuang Glass Technology Development Co., Ltd. (model: 855-7 spray powder). The following processes are carried out: Step 1, bismuth pentoxide is obtained by thermal reduction of aluminum, and cerium oxide is smelted in a horizontal furnace and an electron beam furnace to obtain a diameter of Φ 190 mm, a length of 390 mm, and a chemical composition of Nb. 99.95% antimony ingot; Step 2: Preheat the crucible ingot obtained in step 1 at 200 ° C, apply glass powder, heat the ingot to 400 ° C, keep it for 3 h, and straighten the crucible ingot to 210 mm, and lengthen to 200 × 200×280mm; Step 3: The bismuth ingot obtained in the second step is pickled: HCl: HF: H2SO4=5:3:2 (volume ratio), pickling time is 10 minutes, surface impurities and glass powder are removed, and the naked eye is observed. The metal luster can be free of speckles; step 4: heat treatment of the niobium ingot obtained in the third step: heat treatment temperature is 1000 ° C, holding time is 60 min; step 5, the crucible ingot obtained in step 4 is up to 220 mm, forging and square 190 × 190 × Lmm, the final forging rounded to Φ 200mm; Step six, the picking ingot obtained in step 5 is pickled: HCl: HF: H2SO4 = 5: 3: 2 (volume ratio), pickling time 10 minutes, The surface impurities and the glass powder are removed, and the heat treatment is performed at a temperature of 1000 ° C and a heat retention time of 60 min after the naked eye is observed without speckle. Step 7: Turning the outer surface and both ends of the bismuth ingot obtained in step 6 by a lathe The head, after removing the defect, drilling, the size is: The outer diameter is 195 mm, the inner diameter is 100 mm, the length is 350 mm, and the end of the tube is 30 mm×45°. The step is to use the low temperature intermediate frequency furnace to preheat the tube blank. The preheating temperature is 900 ° C. After preheating, the glass powder is applied to the inner and outer surfaces of the briquette billet and the ends thereof. Step 9. The crucible tube obtained in step 8 is transferred to a secondary medium frequency induction furnace for secondary heating and heating. The temperature is 1050 ° C, and the temperature is kept for 10 minutes; Step 10, the tube blank obtained in the step 9 is applied twice to the glass powder, and the thickness of the glass powder is controlled between 1 and 2 mm to ensure uniform application without voids; The tube blank obtained in step 10 is sent to the extrusion barrel for extrusion, and the tonnage of the extruder should be greater than 3,000 tons. After extrusion, a target tube having an outer diameter of 160 mm, an inner diameter of 90 mm and a length of 560 mm is obtained; step 12, picking the target tube obtained in step 11 by pickling, pickling: HF: HNO3=3:5 (volume ratio), the acid liquid is heated at 75 ° C, and finally the surface glass powder is removed, and the ruthenium metal luster is free from speckles by the naked eye; Step 13. The ruthenium target tube obtained in the step 12 is subjected to vacuum heat treatment, and the temperature is kept at 1050 ° C for 60 times. Minute; straightening after heat treatment, straightness After 1.0mm, the straightening device is a two-roll straightening machine; in step 14, the fistula target obtained in step 13 is loaded onto the deep-hole drilling boring machine, and the double-cutter head is matched with the tool of the elongated arbor Then, the high-pressure vulcanized oil is connected to the boring and milling inner hole. The length of the arbor is 5600mm. During the boring and milling process, the lathe speed is 80~125 rev/min, and the depth of the knife is 0.5~1.2mm. After the inner hole is boring and milling, the ends of the two ends are turned, and the vertical axis of the head cut surface is ensured to be: 100±0.15mm in Φ and 482±1mm in length; Step 15. Install the rotating target obtained in step 14. It is stuck on the horizontal lathe, and the inner hole is used as the reference for the alignment and then the outer circle is turned. In the outer turning process, the tool material YG8 is selected; the rake angle γ is 30°, the back angle α is 4°, and the main declination angle φ is 60°. The secondary declination is 10°; the rake angle is 10°, and the radius of the tool nose is 0.4 mm for the rough R. Feeding amount: rough car F is 0.25mm/rev, finishing car f is 0.15mm/rev; cutting depth: rough car T is 2mm, fine car t is 0.8mm; cutting speed: rough car ν is 40m/min; fine Car 60m/min. After the final turning, the dimensions are: 155±0.1mm outside the Φ, 100±0.15mm in the Φ, and 482±1mm in the length; Step 16. The rotating coating target obtained in the step 15 is in the process of 300~400 rpm. Sandpaper, abrasive cloth, and abrasive paste are used to polish the outer surface to achieve a surface roughness of Ra. 1.6μm; Step 17. The rotating coating target obtained in step 16 is loaded onto the chamber polishing machine and matched with sandpaper, abrasive cloth and abrasive paste for internal hole treatment, and the number of revolutions is 280~350 rev/min. , eventually, the inner surface roughness of the inner hole reaches Ra 6.3 μm.
本實例製備的鈮靶材晶粒組織均勻，晶粒度為5.0~6.5級(本實施例中未提到的公差均為±1mm)。圖1為本實施例生產的鈮靶材的金相照片，由圖1可知，鈮靶材的內部晶粒組織細小均勻。The ruthenium target prepared in this example has uniform grain structure and a grain size of 5.0 to 6.5 (the tolerances not mentioned in this embodiment are all ± 1 mm). Fig. 1 is a metallographic photograph of a ruthenium target produced in the present embodiment. As can be seen from Fig. 1, the internal grain structure of the ruthenium target is fine and uniform.
實施例2Example 2
採用與實施例1中相同的玻璃粉，進行如下工藝：步驟一、五氧化二鈮通過鋁熱還原得到氧化鈮，將氧化鈮分別在水平爐熔煉和電子束爐熔煉，得到直徑為Φ290mm、長度為620mm，化學成分為Nb99.95%的鈮錠；步驟二、將步驟一得到的鈮錠預熱200℃，塗抹玻璃粉，錠材加熱至400℃，保溫3h，對鈮錠軸向鐓粗至340mm，拔長至280×280×520mm；步驟三、將步驟二得到的鈮錠進行酸洗：HCl：HF：H2SO4=5：3：2(體積比)，酸洗時間10分鐘，去除表面雜質及玻璃粉，肉眼觀察可見鈮金屬光澤無雜斑即可；步驟四、將步驟三得到的鈮錠進行熱處理：熱處理溫度為1000℃，保溫時間為60min；步驟五、將步驟四得到的鈮錠進行鐓粗至290mm，鍛造打方255×255×Lmm，最後鍛造打圓到Φ275mm；步驟六、將步驟五得到的鈮錠進行酸洗：HCl：HF：H2SO4=5：3：2(體積比)，酸洗時間10分鐘，去除表面雜質及玻璃粉，肉眼觀察可見鈮金屬光澤無雜斑後進行熱處理，熱處理的溫度為1000℃，保溫時間為60min；步驟七、通過車床對步驟六得到的鈮錠進行車削外表面及兩端頭，去除缺陷後進行鑽孔；最後得到尺寸為：外徑Φ 264mm，內徑125mm，長度為650mm，一端頭倒外角30mm×45°的鈮管坯；步驟八、將步驟七得到的鈮管坯採用低溫中頻爐對鈮管坯進行預熱，預熱溫度為900℃，預熱後對鈮管坯料進行內外表面及兩端頭塗抹玻璃粉；步驟九、將步驟八得到的鈮管坯轉至二次中頻感應爐中進行二次加熱，加熱溫度為1050℃，保溫10分鐘；步驟十、將步驟九得到的鈮管坯進行二次塗抹玻璃粉，玻璃 粉厚度控制在1~2mm之間，保證塗抹均勻無孔隙；步驟十一、將在步驟十得到的鈮管坯傳送至擠壓筒內進行擠壓，此擠壓機噸位應大於3000噸。擠壓後得到外徑為Φ 165mm，內徑120mm，長度為2700mm的鈮靶管；步驟十二、將步驟十一中得到的鈮靶管進行酸洗，酸液：HF：HNO3=3：5(體積比)，酸液加熱60℃，最終去除表面玻璃粉，肉眼觀察鈮金屬光澤無雜斑即可；步驟十三、將步驟十二得到的鈮靶管進行真空熱處理，溫度1050℃保溫60分鐘；熱處理後進行校直，直線度1.0mm後，矯直設備為兩輥矯直機；步驟十四、將步驟十三得到的鈮管靶材裝卡到深孔鑽鏜床上，通過採用具有雙刀頭與加長刀杆的刀具，再連接高壓硫化油進行鏜銑內孔，刀杆的長度為6000mm，在鏜銑過程中車床轉速80~125轉/min，吃刀深度為0.5~1.2mm。內孔鏜銑完成後車削兩端頭，保證兩端頭切面垂直軸線完成後尺寸為：Φ內為125±0.15mm，長度為2413±1mm；步驟十五、將步驟十四中得到的鈮旋轉靶材裝卡在臥式車床上，以內孔為基準進行找正然後車削外圓，外圓車削過程中選用刀具材料YG8；前角γ為40°，後角α為6°；主偏角φ為60°，副偏角為15°；刃傾角採用λ為15°，刀尖圓弧半徑為0.4mm。進給量：粗車F為0.3mm/轉，精車f為0.2mm/轉；切削深度：粗車T為5mm，精車t為1.2mm；切削速度：粗車ν為40m/min；精車60m/min；最後車削完成後尺寸：Φ外為155±0.1mm，Φ內為125±0.15mm，長度為2413±1mm；步驟十六、將步驟十五得到的旋轉鍍膜鈮靶材在300~400轉/min過程中使用砂紙、研磨布、研磨膏對外表面進行拋光精處理，使其表面粗糙度達到Ra1.6μm；步驟十七、將步驟十六得到的旋轉鍍膜鈮靶材裝卡到藥室拋 光機上與砂紙、研磨布、研磨膏相配合進行內孔處理，轉數為280~350轉/min，最終使其內孔表面粗糙度達到Ra6.3μm。Using the same glass powder as in Example 1, the following process is carried out: Step 1, bismuth pentoxide is obtained by thermal reduction of aluminum to obtain cerium oxide, and cerium oxide is separately smelted in a horizontal furnace and an electron beam furnace to obtain a diameter of Φ290 mm and a length. 620mm, chemical composition Nb 99.95% antimony ingot; Step 2: Preheat the crucible ingot obtained in step 1 to 200 ° C, apply glass powder, heat the ingot to 400 ° C, keep warm for 3 h, upset to 340 mm in the axial direction of the crucible, and lengthen to 280× 280×520mm; Step 3: Acid-washing the bismuth ingot obtained in the second step: HCl: HF: H2SO4=5:3:2 (volume ratio), pickling time 10 minutes, removing surface impurities and glass powder, visible to the naked eye The metal luster has no speckle; step 4: heat treatment of the niobium ingot obtained in step 3: heat treatment temperature is 1000 ° C, holding time is 60 min; step 5, the crucible ingot obtained in step 4 is upset to 290 mm, forging The square is 255×255×Lmm, and the forging is rounded to Φ275mm; Step 6. The bismuth ingot obtained in the fifth step is pickled: HCl: HF: H2SO4=5:3:2 (volume ratio), pickling time: 10 minutes , removing surface impurities and glass powder, and visually observing the metallic luster without speckle, heat treatment, the heat treatment temperature is 1000 ° C, and the holding time is 60 min; Step 7. Turning the outer surface of the crucible ingot obtained in step 6 by lathe and Both ends of the head, after the defect is removed, drilling is performed; After obtaining the dimensions: outer diameter Φ 264mm, inner diameter 125mm, length 650mm, one end head inverted outer angle 30mm × 45 ° 铌 tube blank; step VIII, the step VII obtained 铌 tube blank using low temperature intermediate frequency furnace 铌 tube The billet is preheated, and the preheating temperature is 900 ° C. After preheating, the inner and outer surfaces and the both ends of the fistula billet are coated with glass frit; step IX, the tube billet obtained in step 8 is transferred to the secondary medium frequency induction furnace. The second heating is performed, the heating temperature is 1050 ° C, and the temperature is kept for 10 minutes; in step 10, the glass tube powder obtained in the step 9 is secondly coated with the glass powder, and the thickness of the glass powder is controlled between 1 and 2 mm to ensure uniform application without voids; Step 11. Transfer the tube blank obtained in step 10 to the extrusion barrel for extrusion. The tonnage of the extruder should be greater than 3,000 tons. After extrusion, a target tube having an outer diameter of Φ 165 mm, an inner diameter of 120 mm and a length of 2700 mm is obtained; in step 12, the target tube obtained in the step 11 is pickled, and the acid solution: HF: HNO3 = 3:5 (volume ratio), the acid liquid is heated at 60 ° C, and finally the surface glass powder is removed, and the ruthenium metal luster is observed without speckle by the naked eye; Step 13. The ruthenium target tube obtained in the step 12 is subjected to vacuum heat treatment, and the temperature is kept at 1050 ° C for 60. Minute; straightening after heat treatment, straightness After 1.0 mm, the straightening device is a two-roll straightening machine; in step 14, the fistula target obtained in step 13 is loaded onto the deep-hole drilling boring machine by using a cutter having a double-cutter head and an elongated arbor. Then connect the high-pressure vulcanized oil to the boring and milling inner hole. The length of the arbor is 6000mm. During the boring and milling process, the lathe speed is 80~125 rev/min, and the depth of the knife is 0.5~1.2mm. After the inner hole is boring and milling, the ends of the two ends are turned to ensure that the vertical axis of the head cut surface is completed: the inner diameter of Φ is 125±0.15mm, and the length is 2413±1mm; step fifteen, the 铌 rotating target obtained in step fourteen The card is mounted on a horizontal lathe, and the inner hole is used as a reference to perform the alignment and then the outer circle is turned. The tool material YG8 is selected during the outer turning process; the rake angle γ is 40°, the back angle α is 6°, and the main declination angle φ is 60. °, the secondary declination is 15°; the rake angle is 15°, and the radius of the tool nose is 0.4 mm. Feeding amount: rough car F is 0.3mm/rev, finishing car f is 0.2mm/rev; cutting depth: rough car T is 5mm, finishing car t is 1.2mm; cutting speed: rough car ν is 40m/min; fine The car is 60m/min; after the final turning, the size is 155±0.1mm outside the Φ, 125±0.15mm in the Φ, and the length is 2413±1mm; Step 16. The rotating coating target obtained in the step 15 is 300~ In the process of 400 rpm, sandpaper, abrasive cloth and abrasive paste are used to polish the outer surface to achieve a surface roughness of Ra. 1.6μm; Step 17. The rotating coating target obtained in step 16 is loaded onto the chamber polishing machine and matched with sandpaper, abrasive cloth and abrasive paste for internal hole treatment, and the number of revolutions is 280~350 rev/min. , eventually, the inner surface roughness of the inner hole reaches Ra 6.3 μm.
本實例製備的鈮靶材晶粒組織均勻，晶粒度為5.0~6.5級(本實施例中未提到的公差均為±1mm)。圖2為本實施例製備的鈮靶材的金相照片，由圖2可知，鈮靶材的內部晶粒組織細小均勻。The ruthenium target prepared in this example has uniform grain structure and a grain size of 5.0 to 6.5 (the tolerances not mentioned in this embodiment are all ± 1 mm). 2 is a metallographic photograph of the ruthenium target prepared in the present embodiment. As can be seen from FIG. 2, the internal grain structure of the ruthenium target is fine and uniform.
實施例3Example 3
採用與實施例1中相同的玻璃粉，進行如下工藝：步驟一、氧化二鈮通過鋁熱還原得到氧化鈮，將氧化鈮分別在水平爐熔煉和電子束爐熔煉，得到直徑為Φ 460mm、長度為350mm，化學成分為Nb99.95%的鈮錠；步驟二、將步驟一得到的鈮錠預熱200℃，塗抹玻璃粉，錠材加熱400℃，保溫3h；對鈮錠進行軸向鐓粗至200mm拔長至290×290×690mm；步驟三、將步驟二得到的鈮錠進行酸洗：HCl：HF：H2SO4=5：3：2(體積比)，酸洗時間10分鐘，去除表面雜質及玻璃粉，肉眼觀察可見鈮金屬光澤無雜斑即可；步驟四、將步驟三所得到的鈮錠進行熱處理：熱處理溫度為1000℃，保溫時間為60min；步驟五、將步驟四得到的鈮錠鐓粗至320mm，鍛造打方300×300×Lmm，最後鍛造打圓到Φ 310mm；步驟六、將步驟五得到的鈮錠進行酸洗HCl：HF：H2SO4=5：3：2(體積比)，酸洗時間10分鐘，去除表面雜質及玻璃粉，肉眼觀察可見鈮金屬光澤無雜斑後進行熱處理，溫度為1000℃，保溫時間為60min；步驟七、通過車床對步驟六得到的鈮錠進行車削外表面及兩端頭，去除缺陷後進行鑽孔。最後得到尺寸為：外徑Φ 290mm，內徑125mm，長度為750mm，一端頭倒外角30mm×45°的鈮管待擠壓坯； 步驟八、將步驟七得到的鈮管坯採用低溫中頻爐對鈮管坯進行預熱，預熱溫度為900℃，預熱後對鈮管坯料進行內外表面及兩端頭塗抹玻璃粉；步驟九、將步驟八得到的鈮管坯轉至二次中頻感應爐中進行二次加熱，加熱溫度為1050℃，保溫10分鐘；步驟十、將步驟九中得到的鈮管坯進行二次塗抹玻璃粉，玻璃粉厚度控制在1~2mm之間，保證塗抹均勻無孔隙；步驟十一、將在步驟十完成的鈮管坯傳送至擠壓筒內進行擠壓，此擠壓機噸位應大於3000噸。擠壓後得到外徑為Φ 165mm，內徑為120mm，長度為4000mm的鈮靶管；步驟十二、將步驟十一得到的鈮靶管進行酸洗，酸液：HF：HNO3=3：5(體積比)，酸液加熱65℃，最終去除表面玻璃粉，肉眼觀察可見鈮金屬光澤無雜斑即可；步驟十三、將步驟十二得到的鈮靶管進行真空熱處理，溫度1050℃保溫60分鐘；熱處理後進行校直，直線度1.0mm後，矯直設備為兩輥矯直機；步驟十四、將步驟十三所得的鈮靶材裝卡到深孔鑽鏜床上，通過採用具有雙刀頭與加長刀杆的刀具，再連接高壓硫化油進行鏜銑內孔，刀杆的長度為6500mm，在鏜銑過程中車床轉速80~125轉/min，吃刀深度為0.5~1.2mm。內孔鏜銑完成後車削兩端頭，保證兩端頭切面垂直軸線完成後尺寸為：Φ內為125±0.15mm，長度為3749±1mm；步驟十五、將步驟十四得到的鈮旋轉靶材裝卡在臥式車床上，以內孔為基準進行找正然後車削外圓，外圓車削過程中選用刀具材料YG8；前角γ為35°，後角α為5°；主偏角φ為60°，副偏角為12°；刃傾角採用λ為13°，刀尖圓弧半徑為粗車R為0.4mm；進給量：粗車F為0.28mm/轉，精車f為0.18mm/轉；切削深度：粗車T為4mm，精車t為1.0mm；切削速度：粗車ν為 40m/min；精車60m/min。最後車削完成後尺寸：Φ外為155±0.1mm，Φ內為125±0.15mm，長度3749±1mm；步驟十六、將步驟十五得到的旋轉鍍膜鈮靶材在300~400轉/min過程中使用砂紙、研磨布、研磨膏對外表面進行拋光精處理，使其表面粗糙度達到Ra1.6μm；步驟十七、將步驟十六得到的旋轉鍍膜鈮靶材裝卡到藥室拋光機上與砂紙、研磨布、研磨膏相配合進行內孔處理，轉數為280~350轉/min，最終使其內孔表面粗糙度達到Ra6.3μm。Using the same glass powder as in Example 1, the following process is carried out: Step one, bismuth oxide is obtained by thermal reduction of aluminum to obtain cerium oxide, and cerium oxide is separately smelted in a horizontal furnace and an electron beam furnace to obtain a diameter of Φ 460 mm and a length. 350mm, chemical composition Nb 99.95% antimony ingot; Step 2, preheat the crucible ingot obtained in step one to 200 ° C, apply glass powder, ingot heating 400 ° C, heat preservation for 3 h; axial indentation of crucible ingot to 200 mm to length to 290 × 290 × 690mm; Step 3, pickling the bismuth ingot obtained in the second step: HCl: HF: H2SO4 = 5: 3: 2 (volume ratio), pickling time 10 minutes, remove surface impurities and glass powder, visible to the naked eye The metal luster can be free of speckles; step 4: heat treatment of the niobium ingot obtained in step 3: heat treatment temperature is 1000 ° C, holding time is 60 min; step 5, the crucible ingot obtained in step 4 is up to 320 mm, forged Square 300 × 300 × Lmm, the final forging rounded to Φ 310mm; Step six, the bismuth ingot obtained in step 5 is pickled HCl: HF: H2SO4 = 5: 3: 2 (volume ratio), pickling time 10 minutes, The surface impurities and the glass powder are removed, and the surface of the tantalum ingot obtained by the step 6 is turned by the heat treatment at a temperature of 1000 ° C and a holding time of 60 min. Drill holes after removing defects. Finally, the dimensions are: outer diameter Φ 290mm, inner diameter 125mm, length 750mm, one end head inverted angle 30mm × 45° tube to be extruded; step eight, the step tube seven obtained tube blank is used in low temperature intermediate frequency furnace Preheating the tube blank, preheating temperature is 900 ° C, after preheating, the inner and outer surfaces and the ends of the tube blank are coated with glass powder; step IX, the tube blank obtained in step 8 is transferred to the secondary intermediate frequency The secondary heating is carried out in the induction furnace, the heating temperature is 1050 ° C, and the temperature is kept for 10 minutes; in step 10, the tube blank obtained in the step 9 is twice coated with the glass powder, and the thickness of the glass powder is controlled between 1 and 2 mm to ensure the application. Uniform and non-porous; Step 11. Transfer the tube blank completed in step 10 to the extrusion cylinder for extrusion. The tonnage of the extruder should be greater than 3,000 tons. After extrusion, a target tube having an outer diameter of 165 mm, an inner diameter of 120 mm and a length of 4000 mm is obtained; in step 12, the target tube obtained in step 11 is pickled, and the acid solution: HF: HNO3 = 3:5 (volume ratio), the acid liquid is heated at 65 ° C, and finally the surface glass powder is removed, and the ruthenium metal gloss can be seen without visible spots by the naked eye; Step 13. The ruthenium target tube obtained in the step 12 is subjected to vacuum heat treatment, and the temperature is kept at 1050 ° C. 60 minutes; straightening after heat treatment, straightness After 1.0mm, the straightening device is a two-roll straightening machine; in step 14, the sputum target obtained in step 13 is loaded onto the deep hole drilling boring machine by using a cutter with a double cutter head and an elongated cutter shank, and then The high-pressure vulcanized oil is connected to the boring and milling inner hole. The length of the arbor is 6500mm. During the boring and milling process, the lathe speed is 80~125 rev/min, and the depth of the knife is 0.5~1.2mm. After the inner hole is boring and milling, the ends of the two ends are turned to ensure that the vertical axes of the head cut surfaces at both ends are: 125±0.15mm in the Φ and 3749±1mm in the length; Step 15 and the 铌Rotating target obtained in the step 14 It is stuck on the horizontal lathe, and the inner hole is used as the reference to correct and then the outer circle is turned. In the outer turning process, the tool material YG8 is selected; the rake angle γ is 35°, the back angle α is 5°; the main declination angle φ is 60°. The secondary declination is 12°; the rake angle is 13°, the radius of the tool nose is 0.4mm for the rough R; the feed amount is 0.28mm/rev for the rough car F and 0.18mm/rev for the refined car f. Cutting depth: rough car T is 4mm, finishing car t is 1.0mm; cutting speed: rough car ν is 40m/min; finishing car 60m/min. After the final turning, the dimensions are: 155±0.1mm outside the Φ, 125±0.15mm in the Φ, and 3749±1mm in the length; Step 16. The rotating coating target obtained in the step 15 is in the process of 300~400 rpm. Use sandpaper, abrasive cloth, and abrasive paste to polish the outer surface to achieve a surface roughness of Ra 1.6μm; Step 17. The rotating coating target obtained in step 16 is loaded onto the chamber polishing machine and matched with sandpaper, abrasive cloth and abrasive paste for internal hole treatment, and the number of revolutions is 280~350 rev/min. , eventually, the inner surface roughness of the inner hole reaches Ra 6.3 μm.
對比例1Comparative example 1
1)將兩次電子束熔煉製備的質量純度不小於99.95%，直徑為240mm，長度為400mm的扒皮鈮錠，採用深孔鑽打孔後結合線切割沿軸線方向從內掏出直徑為115mm的同軸芯部，得到外徑為240mm，內徑為115mm，長度為400mm的鈮管坯；2)採用不銹鋼包套材料將步驟1)中所述鈮管坯包覆密封，然後將包覆後的鈮管坯在電爐中加熱至1050℃，並保溫2h，將保溫後的包覆有不銹鋼包套材料的鈮管錠在臥式擠壓機上擠壓，控制擠壓比為8，得到外徑為140mm，內徑為113mm，長度為3080mm的鈮管靶(含包套材料)；3)將步驟2)中所述鈮管靶校直後進行酸洗，然後對酸洗後的鈮管靶進行真空熱處理；所述真空熱處理的制度為；熱處理溫度為980℃，保溫時間為1h；所述酸洗的酸液為氫氟酸、硝酸和水按照1：2：4的體積比混合而成，其中硝酸和氫氟酸均為化學純試劑；4)將步驟3)得到的鈮管靶機械加工，去除包套材料，機加工平頭，然後對鈮管靶內、外表面進行拋光處理，得到壁厚為7mm，外徑為134mm的濺射用成品鈮管狀靶材。圖3與圖4為本實施例製備的鈮管狀靶材的金相照片，由圖可知，本實施例製備的鈮管狀靶材的晶粒粗大且不均勻。1) Two-hole electron beam smelting prepared with a purity of not less than 99.95%, a diameter of 240 mm, and a length of 400 mm, which are drilled with a deep hole and combined with a wire cut to draw a diameter of 115 mm from the inside along the axial direction. For the coaxial core, a crucible tube having an outer diameter of 240 mm, an inner diameter of 115 mm and a length of 400 mm is obtained; 2) the crucible tube blank in the step 1) is covered and sealed with a stainless steel sheath material, and then the coated The tube billet is heated to 1050 ° C in an electric furnace and kept for 2 h. The indented tube ingot coated with stainless steel wrap material is pressed on a horizontal extruder to control the extrusion ratio to 8 and the outer diameter is obtained. It is a 140mm, an inner diameter of 113mm, a length of 3080mm of a fistula target (including a sheath material); 3) the tube target in step 2) is straightened and then pickled, and then the pickled tube target is subjected to pickling Vacuum heat treatment; the vacuum heat treatment system is; heat treatment temperature is 980 ° C, holding time is 1 h; the pickled acid liquid is hydrofluoric acid, nitric acid and water are mixed according to a volume ratio of 1:2:4, Wherein nitric acid and hydrofluoric acid are chemically pure reagents; 4) machining the fistula target obtained in step 3) Removing the sheath material, machined flat head, and then the inside of niobium tube target, the outer surface is polished to give a wall thickness of 7mm, with an outer diameter of 134mm sputtering niobium finished tubular target. 3 and FIG. 4 are metallographic photographs of the tantalum tubular target prepared in the present embodiment, and it can be seen from the figure that the crystal grains of the tantalum tubular target prepared in the present embodiment are coarse and uneven.
以上實施例的說明只是用於幫助理解本發明的方法及其核心思想。應當指出，對於本技術領域的普通技術人員來說，在不脫離本發明原理的前提下，還可以對本發明進行若干改進和修飾，這些改進和修飾也落入本發明申請專利範圍的保護範圍內。The above description of the embodiments is merely to assist in understanding the method of the present invention and its core idea. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principles of the present invention. These modifications and modifications are also within the scope of the scope of the present invention. .
對所公開的實施例的上述說明，使本領域專業技術人員能夠實現或使用本發明。對這些實施例的多種修改對本領域的專業技術人員來說將是顯而易見的，本文中所定義的一般原理可以在不脫離本發明的精神或範圍的情况下，在其它實施例中實現。因此，本發明將不會被限制於本文所示的這些實施例，而是要符合與本文所公開的原理和新穎特點相一致的最寬的範圍。The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments are obvious to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments shown herein, but the scope of the invention is to be accorded
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