TWI534279B - 鍍膜件及其製備方法 - Google Patents

鍍膜件及其製備方法 Download PDF

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TWI534279B
TWI534279B TW101110524A TW101110524A TWI534279B TW I534279 B TWI534279 B TW I534279B TW 101110524 A TW101110524 A TW 101110524A TW 101110524 A TW101110524 A TW 101110524A TW I534279 B TWI534279 B TW I534279B
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layer
metal substrate
carburizing
carbon
chromium
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曹達華
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富智康（香港）有限公司
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Description

鍍膜件及其製備方法
本發明涉及一種鍍膜件及其製備方法，尤其涉及一種具有較高硬度的裝飾膜的鍍膜件及其製備方法。
物理氣相沉積(PVD)由於比較環保，而且製備的膜層具有金屬質感以及較好的附著性，故被廣泛用於在電腦、通信和消費類電子產品的金屬外殼上製備裝飾性膜層。然，消費者除了對這些產品的外殼的裝飾性有較高的要求外，對外殼的表面硬度及耐磨性要求也越來越高。一般裝飾性PVD膜層的厚度為2-4微米，經PVD鍍膜處理的外殼表面，其複合硬度通常只有HV600，若要進一步提高硬度，通常需要增加膜層厚度。然，隨著膜層沉積厚度的增加，不僅增加成本，且膜層過厚容易導致膜層表面發朦，光亮度降低，顏色異常。故，單獨的PVD工藝難以滿足這種需求。
有鑒於此，本發明提供一種具有較高硬度的裝飾膜的鍍膜件。
另外，本發明還提供一種上述鍍膜件的製備方法。
一種鍍膜件，包括金屬基體，該鍍膜件還包括形成於該金屬基體表層的滲碳-矽層、形成於該滲碳-矽層上的結合層以及形成於該結合層上的顏色層，該滲碳-矽層係藉由對金屬基體進行真空離子滲碳-矽處理而於金屬基體表層滲入碳、矽元素而形成，該結 合層由金屬形成，該顏色層由金屬元素與非金屬元素組成。
一種鍍膜件的製備方法，包括對金屬基體進行真空離子滲碳-矽處理，以於該金屬基體的表層滲入碳、矽元素而形成一滲碳-矽層，以及採用磁控濺射方法在該滲碳-矽層上依次沉積一結合層及一顏色層，其中，沉積該結合層係在濺射條件下，以鉻、鈦及鋯中的一種為靶材，在靶材上施加電源使靶材物質濺射並沉積到滲碳-矽層表面；沉積該顏色層係在濺射條件下，以鉻或鈦為靶材，以乙炔、氧氣及氮氣中的一種或多種為反應氣體，在靶材上施加電源使靶材物質濺射並沉積到結合層表面。
上述鍍膜件的製備方法先採用碳和矽共滲於金屬基體表層獲得該滲碳-矽層，由於碳和矽同屬IVA族，具有很多相似的性質，易形成SiC、Si及C的共滲，而且SiC的硬度接近金剛石的硬度，因此，該滲碳-矽層可為後續膜層(結合層及顏色層)提供更硬的基底，從而可使鍍膜件獲得更高的表面複合硬度。
本發明藉由C及Si離子共滲處理配合PVD鍍膜工藝，在不增加PVD膜層厚度、膜層表面不發朦的基礎上，使鍍膜件的耐磨性及耐刮傷性能獲得較大提高。
10‧‧‧鍍膜件
11‧‧‧金屬基體
13‧‧‧滲碳-矽層
14‧‧‧結合層
15‧‧‧顏色層
20‧‧‧真空離子滲碳-矽設備
21‧‧‧真空爐
22‧‧‧加熱器
23‧‧‧離子源
25‧‧‧真空泵
圖1係本發明一較佳實施例鍍膜件的剖視圖。
圖2係圖1所示鍍膜件的製備過程中所用真空離子滲碳-矽設備滲碳-矽設備的結構示意圖。
請參閱圖1，本發明較佳實施例的鍍膜件10包括金屬基體11、形成於金屬基體11上的滲碳-矽層13、形成於滲碳-矽層13上的結合層14及形成於結合層14的顏色層15。
金屬基體11可為不銹鋼，還可為鈦合金、鋁合金等金屬。
該滲碳-矽層13藉由對金屬基體11的表層進行真空離子滲碳-矽處理形成。該滲碳-矽層13中碳元素的品質百分含量比金屬基體11中碳元素的品質百分含量高0.12%-0.42%，滲碳-矽層13中矽元素的品質百分含量比金屬基體11中矽元素的品質百分含量高0.05%-0.3%。滲碳-矽層13的厚度為0.1mm-0.3mm。
該結合層14為鉻、鈦或鋯等結合力較強、與金屬基體11熱膨脹係數相近的金屬形成。結合層14主要用於提高顏色層15的附著力。當金屬基體11為不銹鋼時，結合層14優選為鉻。結合層14的厚度可為0.1μm-0.3μm。
該顏色層15由金屬元素與非金屬元素組成，其主要為鍍膜件10提供裝飾性的外觀。為了使顏色層15具有較高的耐磨性，顏色層15還應當具有較高的硬度。比如，該顏色層15可為碳化鉻、氮化鉻、氮氧化鉻、碳化鈦、氮化鈦及氮碳化鈦中的一種。
在本發明一實施例中，該顏色層15由碳元素與鉻元素組成。顏色層15中碳元素與鉻元素的原子個數比大約為1：(0.3-1)，且顏色層15中碳元素的品質百分含量由靠近結合層14至遠離結合層14的方向呈梯度增加。顏色層15的厚度可為2.0μm-2.5μm。
所述結合層14與顏色層15可分別藉由磁控濺射方法形成。
上述鍍膜件10的製備方法，主要包括對金屬基體11的表層進行真 空離子滲碳-矽處理形成該滲碳-矽層13，以及採用磁控濺射方法在該滲碳-矽層13上依次沉積該結合層14及該顏色層15。
所述真空離子滲碳-矽處理係在一真空離子滲碳-矽設備20(如圖2所示)中進行。該真空離子滲碳-矽設備20包括一真空爐21、用於使金屬基體11升溫的加熱器22、設置於真空爐21內的一離子源23以及用以對真空爐21抽真空的真空泵25。所述離子源23用於將滲碳-矽氣體電離，向真空爐21提供含碳離子及矽離子的離化氣體。
真空離子滲碳-矽處理時，將金屬基體11放置於真空爐21中，開啟真空泵25，將真空爐21排氣至壓強為0.1Pa-1.0Pa，然後開啟加熱器22使金屬基體11升溫至450℃-600℃，向離子源23充入滲碳氣體甲烷(CH4)、滲矽氣體矽烷(SiH4)及惰性氣體氬氣。甲烷、矽烷及氬氣之間的流量比為(1-2)：(1-2)：(2-3)。甲烷及矽烷被離子源23電離成為離化氣體進入真空爐21，使真空爐21內氣壓為0.5Pa-2.5Pa。離化氣體中的碳離子與矽離子衝擊金屬基體11而進入金屬基體11表層，由此於金屬基體11表層形成該滲碳-矽層13。真空離子滲碳-矽處理的時間為180min-300min。然後向真空爐21充入冷卻氣體(如氬氣)對金屬基體11進行冷卻。充入冷卻氣體後真空爐21內壓力為1.0atm-2.0atm。經大約20min-40min後，取出金屬基體11。
沉積該結合層14係在濺射條件下，以鉻、鈦及鋯中的一種為靶材，在靶材上施加電源使靶材物質濺射並沉積到滲碳-矽層13表面形成結合層14。
沉積該顏色層15係在濺射條件下，以鉻或鈦為靶材，以乙炔( H2)、氧氣(O2)及氮氣(N2)中的一種或多種為反應氣體，在靶材上施加電源使靶材物質濺射並沉積到結合層14表面形成該顏色層15。
所述的磁控濺射條件包括以惰性氣體為濺射氣體，該惰性氣體可為氬氣，其流量可為150sccm(標準狀態毫升/分鐘)-250sccm；鍍膜壓力(即鍍膜時鍍膜室內的絕對壓力)為0.3Pa-0.6Pa；鍍膜溫度為130℃-180℃。
所述電源可為習知的各種用於磁控濺射鍍膜的電源，優選為中頻電源。
下面以結合層14為鉻層、顏色層15由碳元素與鉻元素組成為例，對本發明進行進一步詳細說明。
實施例1
1.超聲清洗
將304不銹鋼材質的金屬基體11放入乙醇溶液中進行超聲波清洗，以除去金屬基體11表面的雜質和油污等，清洗完畢後烘乾備用。
2.真空離子滲碳-矽處理
將金屬基體11放入真空離子滲碳-矽設備20的真空爐21中，開啟真空泵25，將真空爐21排氣至壓強為0.1Pa，然後開啟加熱器22使金屬基體11升溫至450℃，向離子源23充入滲碳氣體甲烷、滲矽氣體矽烷及氬氣。甲烷、矽烷及氬氣之間的流量比為1：1：2，使真空爐21內氣壓為0.5Pa。真空離子滲碳-矽處理的時間為 180min，於金屬基體11表層形成一滲碳-矽層13。然後向真空爐21充入冷卻氣體氬氣，使真空爐21內壓力為1.0atm。經大約20min後，取出金屬基體11。
2.PVD鍍膜
採用磁控濺射設備(深圳南方創新真空技術有限公司生產，型號為SM-1100H)。該磁控濺射設備包括真空室、轉架、磁控靶和偏壓電源。磁控靶為對靶結構，包括兩對鉻靶，每對靶之間形成有一定距離。基體固定在轉架上，轉架旋轉時帶動基體從每對鉻靶之間經過。
洗靶：將真空室中絕對壓力調至6.0×10-3Pa，然後向真空室通入氬氣直至壓力為0.8Pa，開啟鉻靶的電源，調節電源功率為8kW，對鉻靶輝光清洗8分鐘。
離子清洗基體：關閉鉻靶的電源，調節真空室壓力為0.6Pa，對金屬基體11施加-1000V的偏壓，對金屬基體11進行氬氣等離子體清洗15分鐘。
濺射結合層14：向真空室通入氬氣，氬氣流量為150sccm，控制真空室內壓力為0.3Pa，調節真空室內溫度為130℃，開啟鉻靶的電源，調節電源功率為10kW，調節施加於金屬基體11上的偏壓為-100V，對金屬基體11濺射15分鐘，以於金屬基體11表面形成所述由鉻金屬形成的結合層14。結合層14的厚度為0.25μm。
濺射顏色層15：維持上述操作，不同之處在於，調節鉻靶的電源功率為11kW，同時通入反應氣體乙炔，乙炔的初始流量為50sccm，在沉積顏色層15的過程中，每4min將乙炔的流量增大1sccm， 當氮氣的流量到達80sccm時，停止增大乙炔流量，由此在結合層14上沉積該由碳元素與鉻元素組層，且碳元素含量隨厚度遞增的顏色層15。濺射顏色層15的時間為120分鐘。顏色層15的厚度為2.4μm。
關閉鉻靶、偏壓電源並停止通入乙炔，冷卻後取出鍍覆好的金屬基體11，肉眼觀察顏色層15無發朦等顏色異常。
實施例1的樣品記做S1。
實施例2
1.超聲清洗
將304不銹鋼材質的金屬基體11放入乙醇溶液中進行超聲波清洗，以除去金屬基體11表面的雜質和油污等，清洗完畢後烘乾備用。
2.真空離子滲碳-矽處理
將金屬基體11放入真空離子滲碳-矽設備20的真空爐21中，開啟真空泵25，將真空爐21排氣至壓強為1.0Pa，然後開啟加熱器22使金屬基體11升溫至600℃，向離子源23充入滲碳氣體甲烷、滲矽氣體矽烷及氬氣。甲烷、矽烷及氬氣之間的流量比為2：2：3，使真空爐21內氣壓為2.0Pa。真空離子滲碳-矽處理的時間為300min，於金屬基體11表層形成一滲碳-矽層13。然後向真空爐21充入冷卻氣體氬氣，使真空爐21內壓力為2.0atm。經大約40min後，取出金屬基體11。
2.PVD鍍膜
採用磁控濺射設備(深圳南方創新真空技術有限公司生產，型號為SM-1100H)。該磁控濺射設備包括真空室、轉架、磁控靶和偏壓電源。磁控靶為對靶結構，包括兩對鉻靶，每對靶之間形成有一定距離。基體固定在轉架上，轉架旋轉時帶動基體從每對鉻靶之間經過。
洗靶：將真空室中絕對壓力調至5.0×10-3Pa，然後向真空室通入氬氣直至壓力為1.0Pa，開啟鉻靶的電源，調節電源功率為12kW，對鉻靶輝光清洗2分鐘。
離子清洗基體：關閉鉻靶的電源，調節真空室壓力為0.6Pa，對金屬基體11施加-1100V的偏壓，對金屬基體11進行氬氣等離子體清洗20分鐘。
濺射結合層14：向真空室通入氬氣，氬氣流量為200sccm，控制真空室內壓力為0.7Pa，調節真空室內溫度為180℃，開啟鉻靶的電源，調節電源功率為18kW，調節施加於金屬基體11上的偏壓為-150V，對金屬基體11濺射5分鐘，以於金屬基體11表面形成所述由鉻金屬形成的結合層14。結合層14的厚度為0.2μm。
濺射顏色層15：維持上述操作，不同之處在於，調節鉻靶的電源功率為19kW，同時通入反應氣體乙炔，乙炔的初始流量為60sccm，在沉積顏色層15的過程中，每2min將乙炔的流量增大1sccm，當氮氣的流量到達90sccm時，停止增大乙炔流量，由此在結合層14上沉積該由碳元素與鉻元素組層，且碳元素含量隨厚度遞增的顏色層15。濺射顏色層15的時間為60分鐘。顏色層15的厚度為2.2μm。
關閉鉻靶、偏壓電源並停止通入乙炔，冷卻後取出鍍覆好的金屬基體11，肉眼觀察顏色層15無發朦等顏色異常。
實施例2的樣品記做S2。
對比例1
該對比例中，除了未對金屬基體進行真空離子滲碳-矽處理之外，其他均與實施例1相同。對比例的樣品記做D1。
對比例2
該對比例中，除了未對金屬基體進行真空離子滲碳-矽處理之外，其他均與實施例2相同。對比例的樣品記做D2。
測試
使用下面的方法對實施例1-2及對比例1-2的樣品的維氏硬度、鉛筆硬度及耐彈簧力(Rod Scrach Test)進行了測試。所述三種測試的標準已經為業界熟知，故不再列出。測試結果如下表所示：
由測試結果可知，在對金屬基體11進行PVD鍍膜前，對金屬基體 11進行真空離子滲碳-矽處理可使鍍膜件10的表面複合硬度及耐刮傷性獲得明顯提高。
本發的鍍膜件10可為筆記型電腦、個人數位助理等電子裝置的殼體，或為其他裝飾類產品的殼體。
上述鍍膜件10的製備方法先採用碳和矽共滲於金屬基體11表層獲得一滲碳-矽層13，由於碳和矽同屬IVA族，具有很多相似的性質，易形成SiC、Si及C的共滲，而且SiC的硬度接近金剛石的硬度，因此，該滲碳-矽層13可為後續膜層(結合層14及顏色層15)提供更硬的基底，從而可使鍍膜件10獲得更高的表面複合硬度。
本發明藉由C及Si離子共滲處理配合PVD鍍膜工藝，在不增加PVD膜層厚度、膜層表面不發朦的基礎上，使鍍膜件10的耐磨性及耐刮傷性能獲得較大提高。
10‧‧‧鍍膜件
11‧‧‧金屬基體
13‧‧‧滲碳-矽層
14‧‧‧結合層
15‧‧‧顏色層

Claims (9)

  1. 一種鍍膜件，包括金屬基體，其改良在於：該鍍膜件還包括形成於該金屬基體表層的滲碳-矽層、形成於該滲碳-矽層上的結合層以及形成於該結合層上的顏色層，該滲碳-矽層係藉由對金屬基體進行真空離子滲碳-矽處理而於金屬基體表層滲入碳、矽元素而形成，其中所述滲碳-矽層中碳元素的品質百分含量比金屬基體中碳元素的品質百分含量高0.12%-0.42%，矽元素的品質百分含量比金屬基體中矽元素的品質百分含量高0.05%-0.3%，該結合層由金屬形成，該顏色層由金屬元素與非金屬元素組成。
  2. 如申請專利範圍第1項所述之鍍膜件，其中所述滲碳-矽層的厚度為0.1mm-0.3mm。
  3. 如申請專利範圍第1項所述之鍍膜件，其中所述金屬基體為不銹鋼，該結合層為鉻。
  4. 如申請專利範圍第1項所述之鍍膜件，其中所述顏色層由碳元素與鉻元素組成，顏色層中碳元素與鉻元素的原子個數比為1：(0.3-1)，且顏色層中碳元素的品質百分含量由靠近結合層至遠離結合層的方向呈梯度增加。
  5. 如申請專利範圍第1項所述之鍍膜件，其中所述顏色層為氮化鉻、氮氧化鉻、碳化鈦、氮化鈦及氮碳化鈦中的一種。
  6. 如申請專利範圍第1項所述之鍍膜件，其中所述顏色層藉由磁控濺射方法形成。
  7. 一種鍍膜件的製備方法，包括對金屬基體進行真空離子滲碳-矽處理，以於該金屬基體的表層滲入碳、矽元素而形成一滲碳-矽層，其中所述滲碳 -矽層中碳元素的品質百分含量比金屬基體中碳元素的品質百分含量高0.12%-0.42%，矽元素的品質百分含量比金屬基體中矽元素的品質百分含量高0.05%-0.3%，以及採用磁控濺射方法在該滲碳-矽層上依次沉積一結合層及一顏色層，其中，沉積該結合層係在濺射條件下，以鉻、鈦及鋯中的一種為靶材，在靶材上施加電源使靶材物質濺射並沉積到滲碳-矽層表面；沉積該顏色層係在濺射條件下，以鉻或鈦為靶材，以乙炔、氧氣及氮氣中的一種或多種為反應氣體，在靶材上施加電源使靶材物質濺射並沉積到結合層表面。
  8. 如申請專利範圍第7項所述之鍍膜件的製備方法，其中所述真空離子滲碳-矽處理包括：將金屬基體放置於一真空爐中，將真空爐抽真空至壓強為0.1Pa-1.0Pa，並將金屬基體升溫至450℃-600℃，向真空爐充入含碳離子及矽離子的離化氣體，使真空爐內氣壓為0.5Pa-2.5Pa，所述碳離子與矽離子衝擊金屬基體而進入金屬基體表層，由此於金屬基體表層形成該滲碳-矽層，該真空離子滲碳-矽處理的時間為180min-300min。
  9. 如申請專利範圍第7項所述之鍍膜件的製備方法，其中所述磁控濺射條件包括以惰性氣體為濺射氣體，濺射氣體的流量為150sccm-250sccm；鍍膜壓力為0.3Pa-0.6Pa；鍍膜溫度為130℃-180℃。
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