201200608 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種硬質塗層及其製備方法及具有該硬質塗 層的被覆件。 【先前彳支術】 [0002] 鍍膜工藝在工業領域有著廣泛的應用，其中，TiN薄膜鍍 覆在刀具或模具表面能大幅提高刀具與模具的使用壽命 。然，隨著金屬切削加工朝高切削速度、高進給速度、 高可靠性、長壽命、高精度與良好的切削控制性方面發 Ο 展，對表面塗層的性能提出了更高的要求。TiN塗層於硬 度、耐磨損、抗氧化燒蝕性等方面已經漸漸不能滿足進 ' 一步的需求。 【發明内容】 [0003] 有鑒於此，有必要提供一種耐磨損、耐高溫的硬質塗層 〇 [0004] 另外，有必要提供一種上述硬質塗層的製備方法。 〇 [0005] 還有必要提供一種具有上述硬質塗層的被覆件。 [0006] 一種硬質塗層，形成於硬質基體表面上，該硬質塗層主 要由鈦-矽-氮三組元構成，該硬質塗層中鈦原子的含量 由靠近該基體至遠離該基體的方向呈梯度減少，矽原子 的含量由靠近基體至遠離基體的方向呈梯度增加。 [0007] 一種被覆件，包括一硬質基體及形成於該基體上的硬質 塗層，該硬質塗層主要由鈦-矽-氮三組元構成，該硬質 塗層中鈦原子的含量由靠近該基體至遠離該基體的方向 099121603 表單編號 A0101 第 3 頁/共 11 頁 0992038028-0 201200608 呈梯度減少，矽原子的含量由靠近基體至遠離基體的方 向呈梯度增加。 [0008] 一種硬質塗層的製備方法，包括以下步驟： [0009] 將承鍍基體放入一電弧離子鍍膜機中，將純鈦靶材與純 矽靶材間隔地置於電弧離子鍍膜機的弧源位置上；201200608 VI. Description of the Invention: [Technical Field] [0001] The present invention relates to a hard coat layer, a method for producing the same, and a coated member having the hard coat layer. [Previous 彳 术 】 [0002] The coating process has a wide range of applications in the industrial field. Among them, the coating of TiN film on the surface of the tool or mold can greatly improve the service life of the tool and the mold. However, as metal cutting progresses toward high cutting speeds, high feed rates, high reliability, long life, high precision, and good cutting control, higher demands are placed on the performance of surface coatings. TiN coatings have gradually failed to meet the needs of the next step in terms of hardness, wear resistance, and oxidation ablation. SUMMARY OF THE INVENTION [0003] In view of the above, it is necessary to provide a hard coating resistant to abrasion and high temperature. [0004] In addition, it is necessary to provide a method for preparing the above hard coating. 〇 [0005] It is also necessary to provide a covering having the above hard coat layer. [0006] A hard coating layer formed on a surface of a hard substrate mainly composed of a titanium-niobium-nitrogen three-component, the content of titanium atoms in the hard coating layer being from the substrate to a direction away from the substrate The gradient is reduced and the content of germanium atoms increases in a gradient from the substrate to the direction away from the substrate. [0007] A covering member comprising a hard substrate and a hard coating layer formed on the substrate, the hard coating layer mainly composed of a titanium-niobium-nitrogen three-component, the content of titanium atoms in the hard coating layer being close to the The substrate is in a direction away from the substrate 099121603 Form No. A0101 Page 3 of 11 0992038028-0 201200608 The gradient is reduced, and the content of germanium atoms increases in a gradient from the substrate to the direction away from the substrate. [0008] A method for preparing a hard coat layer, comprising the following steps: [0009] placing a substrate to be plated in an arc ion coater, and placing the pure titanium target and the pure tantalum target at an interval in the arc ion coater Arc source position;
[0010] 對電弧離子鍍膜機的真空室抽真空後通入氬氣與反應氣 體氮氣，調節偏壓至-1 50 — 500V，開啟鈦靶，並調節鈦 靶電流為70~ 1 0 0A，同時開啟矽靶，並在預定時間内，將 矽靶電流從40〜50A逐步增加至70~100A後維持不變，在 預定時間内，逐步將鈦靶電流從70〜100A降低至30〜50A ，由此於承鍍基體上沉積出一主要由鈦-矽-氮三組元構 成的硬質塗層，該硬質塗層中鈦原子的含量隨著該塗層 厚度的增加而逐漸減少，矽原子的含量隨著該塗層厚度 的增加而增加。 [0011] 相較於習知技術，上述硬質塗層與基體結合處鈦原子含 量較高，塗層主要表現為TiN相，而TiN具有與高速鋼、 硬質合金、金屬陶瓷等高硬度的基體材料匹配良好的熱 膨脹係數，因此介面處内應力小，介面結合優良；該硬 質塗層表層矽原子含量較高，塗層主要表現為SiN相，[0010] After vacuuming the vacuum chamber of the arc ion coating machine, argon gas and reaction gas nitrogen are introduced, the bias voltage is adjusted to -150 to 500V, the titanium target is turned on, and the titanium target current is adjusted to 70 to 100A, Turn on the target, and gradually increase the target current from 40~50A to 70~100A within a predetermined time, and then gradually reduce the titanium target current from 70~100A to 30~50A within the predetermined time. A hard coating mainly composed of titanium-niobium-nitrogen three components is deposited on the substrate, and the content of titanium atoms in the hard coating is gradually decreased as the thickness of the coating increases, and the content of germanium atoms is decreased. It increases as the thickness of the coating increases. [0011] Compared with the prior art, the titanium alloy has a higher content of titanium atoms in the junction of the hard coating layer and the substrate, and the coating mainly exhibits a TiN phase, and the TiN has a high hardness matrix material such as a high speed steel, a hard alloy, or a cermet. A good thermal expansion coefficient is matched, so the internal stress at the interface is small, and the interface is excellent; the surface of the hard coating has a high content of germanium atoms, and the coating mainly exhibits a SiN phase.
SiN硬度較高，導熱率低。 [0012] 上述硬質塗層的製備方法藉由調節Ti靶的電流於沉積過 程中遞減，調節Si靶的電流於沉積過程中遞增，使塗層 成分亦隨著塗層沉積厚度變化而呈梯度變化，即使得硬 質塗層與基體結合處TiN含量較高，與基體結合良好；硬 099121603 表單編號A0101 第4頁/共11頁 0992038028-0 201200608 質塗層表面SiN含量高，因此塗層硬度高’耐磨損。 【實施方式] [0013] Ο [0014] Ο [0015] 本發明較佳實施例的硬質塗層主要由鈦-矽-氮三組元構 成’該硬質塗層形成在各類切削刀具、精密量具及模具 等硬質基體的表面。於該硬質塗層中，鈦原子的個數含 里隨者该塗層厚度的増加而逐漸減少，即鉢原子於該硬 質塗層中的個數含量由靠近基體至遠離基體的方向呈梯 度減少；矽原子的個數含量隨著該塗層厚度的增加而增 加’即矽原子在該硬質塗層中的個數令量由靠近基體至 遠離基體的方向呈獲度增加；而氮原長蜱含量基本不變 。若將該硬質塗層的組成用表示，以鈇原子與 石夕原子個數的總量為1 〇〇%，x表示鈦原子個數佔鈦原子與 矽原子個數總量的百分數，則其中X的值隨該硬質塗層的 厚度的增加而逐漸減少，且20%SxS8_，較佳地，30% SxS60%。 I %ν...· ·; %：,：：： s \ - f 該硬質塗層的厚度為1〜8//m，優選3〜5 ;zm。該硬質塗層 的顯微硬度為40GPa以上。 上述硬質塗層的塗層組分成梯度變化，與基體結合處鈦 原子含量較高，塗層主要表現為TiN相，而TiN具有與高 速鋼、硬質合金、金屬陶瓷等高硬度的基體材料匹配良 好的熱膨脹係數’因此介面處内應力小，介面結合優良 :該硬質塗層表層矽原子含量較高，塗層主要表現為SiN 相’ SiN硬度較高’導熱率低，當該硬質塗層用於切削刀 具時，在切削過程中向刀具基體傳熱少，加的SiN本身具 有較好的高溫潤滑性，因此可使刀具具有優良的綜合切 099121603 表單編號A0101 第5頁/共11頁 0992038028-0 201200608 削性能。 [0016] 具有上述硬質塗層的被覆件包括該硬質基體及形成在該 硬質基體上的一硬質塗層。該被覆件可為各類切削刀具 、精密量具及模具等。該硬質基體可為高速鋼、硬質合 金、金屬陶瓷、陶瓷、燒結金剛石等具有較高硬度的材 料。該硬質塗層具有如上所述特徵。 [0017] 下面以電弧離子鍍合成上述硬質塗層的方法為例，對該 硬質塗層的製備方法進行說明。該硬質塗層的製備方法 主要包括如下步驟： [0018] ( 1 )對承鍍基體進行表面化學超聲波清洗，即將承鍍基 體放入盛裝有乙醇及/或丙酮溶液的超聲波清洗器中進行 震動清洗，以除去承鍍基體表面的雜質與油污等，清洗 完畢後烘乾備用。所述基體材質可為高速鋼、硬質合金 、金屬陶竟等。 [0019] (2)將經上述清洗的承鍍基體放入一電弧離子鍍膜機中 ，將純鈦靶材與純矽靶材相間隔地置於電弧離子鍍膜機 的孤源位置上。 [0020] (3)對電弧離子鍍膜機的真空室抽真空至10_3Pa級（本 實施例為3. 0x1 0_3Pa)，通入流量為300seem (標準狀 態毫升/分鐘）高純氬氣，並通入流量為200〜280sccm的 反應氣體氮氣，使真空室内壓力達0.卜2Pa。所述氮氣流 量優選為240sccm。調節偏壓至-150〜-250V。開啟鈦靶 ，並調節鈦靶電流為70〜100A，同時開啟矽靶，並在 30〜40分鐘内，將矽靶電流從40〜50A均勻增加至 099121603 表單編號A0101 第6頁/共11頁 0992038028-0 201200608 70〜100A。維持矽靶電流在70〜100A，在20〜30分鐘内， 逐步將鈦靶電流從70~ 100A均勻降低至30〜50A，由此在 承鍍基體上沉積出一硬質塗層。該硬質塗層具有如上所 述特徵。沉積過程中，氮氣的流量保持不變，使塗層中 氮原子的含量基本不變。 [0021] ( 4 )關閉負偏壓及鈦靶與矽靶電流，停止通入氬氣與氮 氣，待所述硬質塗層冷卻後，向真空室内通入空氣，打 開真空室門，取出鍍覆好的基體。 Q [0022] 上述硬質塗層的製備方法藉由調節鈦靶的電流在沉積過 程中遞減，調節矽靶的電流在沉積過程中遞增，使塗層 成分亦隨著塗層沉積厚度變化而呈梯度變化，即使得硬 質塗層與基體結合處（即塗層初始沉積處）ΠΝ含量較高 ，與基體結合良好；該硬質塗層表面SiN含量高，故塗層 硬度高，耐磨損。 [0023] 可以理解，上述硬質塗層的製備方法還可包括沉積塗層 前，在電弧離子鍍膜機内對承鍍基體進行離子清洗。 〇 【圖式簡單說明】 [0024] 無 【主要元件符號說明】 [0025] 無 0992038028-0 099121603 表單編號A0101 第7頁/共11頁The SiN has a high hardness and a low thermal conductivity. [0012] The preparation method of the above hard coating layer is carried out by adjusting the current of the Ti target during the deposition process, and the current of the Si target is adjusted to increase during the deposition process, so that the coating composition changes in gradient with the thickness of the deposition layer. That is, the TiN content of the hard coating and the substrate is higher, and the matrix is well bonded; hard 099121603 Form No. A0101 Page 4 / Total 11 Page 0992038028-0 201200608 The surface of the coating has a high SiN content, so the coating hardness is high' durable. [Embodiment] [0013] The hard coating of the preferred embodiment of the present invention is mainly composed of titanium-niobium-nitrogen three components. The hard coating is formed on various cutting tools and precision measuring tools. And the surface of a hard substrate such as a mold. In the hard coating, the number of titanium atoms is gradually decreased as the thickness of the coating increases, that is, the content of germanium atoms in the hard coating is gradually decreased from the substrate to the direction away from the substrate. The number of germanium atoms increases as the thickness of the coating increases. That is, the number of germanium atoms in the hard coat increases from near the substrate to away from the substrate; The content is basically unchanged. When the composition of the hard coat layer is expressed, the total amount of the atom of the ruthenium atom and the shixi atom is 1 〇〇%, and x represents the percentage of the number of titanium atoms in the total number of titanium atoms and ruthenium atoms, wherein The value of X gradually decreases as the thickness of the hard coat layer increases, and 20% SxS8_, preferably 30% SxS 60%. I %ν...··; %:,::: s \ - f The thickness of the hard coat layer is 1 to 8//m, preferably 3 to 5; zm. The hard coat has a microhardness of 40 GPa or more. The coating composition of the above hard coating changes in a gradient, and the titanium atom content at the junction with the matrix is relatively high, and the coating mainly exhibits a TiN phase, and the TiN has a good matching with a high hardness matrix material such as a high speed steel, a hard alloy, or a cermet. The coefficient of thermal expansion is therefore small at the interface and the interface is excellent: the surface of the hard coating has a high content of germanium atoms, and the coating mainly exhibits a high SiN phase 'SiN hardness', and the thermal conductivity is low when the hard coat is used. When cutting the tool, the heat transfer to the tool base during the cutting process is less, and the added SiN itself has better high-temperature lubricity, so that the tool can have an excellent comprehensive cut 099121603 Form No. A0101 Page 5 / Total 11 Page 0992038028-0 201200608 Cutting performance. [0016] The covering member having the hard coat layer includes the hard substrate and a hard coat layer formed on the hard substrate. The coated parts can be various types of cutting tools, precision measuring tools and molds. The hard substrate may be a material having high hardness such as high speed steel, hard alloy, cermet, ceramic, sintered diamond or the like. The hard coat has the features described above. [0017] Next, a method of synthesizing the hard coat layer by arc ion plating will be described as an example, and a method of preparing the hard coat layer will be described. The preparation method of the hard coating mainly comprises the following steps: [1] (1) performing surface chemical ultrasonic cleaning on the substrate to be plated, that is, the substrate is placed in an ultrasonic cleaner containing an ethanol and/or acetone solution for vibration cleaning. In order to remove impurities and oil stains on the surface of the substrate, after drying, it is dried for use. The base material may be high speed steel, hard alloy, metal ceramic or the like. [0019] (2) The plated substrate subjected to the above cleaning is placed in an arc ion plating machine, and the pure titanium target is placed at a source position of the arc ion coating machine at a distance from the pure ruthenium target. [0020] (3) The vacuum chamber of the arc ion coating machine is evacuated to a level of 10_3 Pa (in this embodiment, 3. 0x1 0_3Pa), and a flow rate of 300 seem (standard state ml/min) of high-purity argon gas is introduced and passed. The flow rate is 200~280sccm of the reaction gas nitrogen, so that the pressure in the vacuum chamber reaches 0. 2Pa. The nitrogen flow rate is preferably 240 sccm. Adjust the bias voltage to -150~-250V. Turn on the titanium target, adjust the titanium target current to 70~100A, open the target at the same time, and increase the target current from 40~50A to 099121603 in 30~40 minutes. Form No. A0101 Page 6 / Total 11 Page 0992038028 -0 201200608 70~100A. Maintaining the target current at 70~100A, the titanium target current is gradually reduced from 70~100A to 30~50A in 20~30 minutes, thereby depositing a hard coating on the substrate. The hard coat layer has the features as described above. During the deposition process, the flow rate of nitrogen is kept constant, so that the content of nitrogen atoms in the coating is substantially constant. [0021] (4) turning off the negative bias voltage and the titanium target and the target current, stopping the introduction of argon gas and nitrogen gas. After the hard coating layer is cooled, air is introduced into the vacuum chamber, the vacuum chamber door is opened, and the plating is taken out. Good substrate. Q [0022] The method for preparing the hard coating described above is to reduce the current of the titanium target during the deposition process, and the current of the ruthenium target is increased during the deposition process, so that the coating composition also has a gradient with the thickness of the coating deposition. The change, that is, the junction of the hard coating and the substrate (ie, the initial deposition of the coating) has a high content of bismuth and good bonding with the substrate; the surface of the hard coating has a high SiN content, so the coating has high hardness and wear resistance. It will be understood that the method of preparing the hard coat layer may further include ion-cleaning the substrate to be plated in the arc ion coater before depositing the coating. 〇 [Simple diagram description] [0024] None [Main component symbol description] [0025] None 0992038028-0 099121603 Form number A0101 Page 7 of 11