TW574173B - Low oxygen cubic boron nitride and its production - Google Patents

Low oxygen cubic boron nitride and its production Download PDF

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TW574173B
TW574173B TW91124681A TW91124681A TW574173B TW 574173 B TW574173 B TW 574173B TW 91124681 A TW91124681 A TW 91124681A TW 91124681 A TW91124681 A TW 91124681A TW 574173 B TW574173 B TW 574173B
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Michael H Zimmerman
Erik O Einset
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Gen Electric
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Description

(i) (i)574173 致、發明說明 (發明說明應敘明：發明 乃所屬之技術領域、先前技術、内容、實施方式及圖式簡單說明） 相關申請 無 有關聯邦贊助研究之聲明 不適用 發明背景 本發明係關於立方晶系硼氮化物（CBN)材料，更特定言 之’係關於一種具有極高韌性和高熱穩定性的CBN產品。 立方晶系爛氮化物（CBN)是人類已知僅次於鑽石的第二 最硬的材料。CBN係以所屬技術領域已知的高壓/高溫 (HP/HT)方法製造，且可由美國專利第2,947,617號中所說明 的方法代表（一基本單晶體CBN的情況）。美國專利第 4，188，194號說明一種製造燒結的多晶體CBN碟片的方法， 其係使用無任何催化劑的熱分解的六方晶系硼氮化物（PBN) 。對於該等直接轉換方法的一種改良已揭露於美國專利第 4,289,503號，其中氧化硼在轉換方法之前已從HBN粉末的 表面移除。美國專利第5，1〇6,792號從一種不同結構形式的 石墨體硼氮化物（GBN)混合物且無任何催化劑下製作一 CBN複合團塊。 碟片係大量磨料粒子以一自我結合關係結合在一起（參 閱美國專利第3,852,078號和3,876,75 1號）；藉由黏結媒介（美 國專利第 3，136,615號 3,233,988號 3,743,489號 3,767,371號和 3,918,931號）；或藉由其組合。複合碟片係碟片黏結至基材 574173 (2) 發明磉:¾ ，諸如接合的金屬碳化物。美國專利第3,9 18,219號教導與 碳化物團塊接觸將六方晶系硼氮化物（HBN)催化轉換至 CBN，以形成複合CBN碟片。碟片或複合碟片可使用在切 割工具、鑽頭、塗料工具和磨耗零件的坏料（參閱美國專 利第 3，136,615 號和 3,233,988號）。 多晶體CBN碟片時常使用於機製硬鐵合金工件，此係由 於其與含鐵工件相當無反應性。因此，CBN材料時常被製 成切割、銳切和旋轉工具。C B N晶體的軔性，由標準脆弱 性試驗測量，可為研磨性能的因數。脆弱性試驗包括在控 制情況下球磨一數量產品並篩滤殘留物以測量該產品的解 離。韌性指數（TI)係於室溫測量，熱韌性指數（TTI)係產品 於高溫燒火之後測量。在許多情況，晶體韌性愈大，輪磨 或機製工具裡的晶體壽命愈長，因此，工具的壽命愈長。 這導致較少的工具磨耗，且最後，較低整體工具成本。 化學物理期刊第63冊第9號第3812頁（ 1975年11月1日）， Corrigan等人丨'Direct Transition Among Allotropic Forms of Boron Nitride at High Pressure and Temperatures”討論在 HBN的 HP/HT 轉換時，雜質（舉例來說，氧）對CBN的效應（參閱第3814頁） 。J. Phys.Chem·, 66，第 1 556 頁（1962)，Dreger等人 n Sublimation and Decomposition Studies on Boron Nitride and Aluminum Nitride” ，建議加熱BN至1200°-2000°C以釋放氮氣且留下硼塗層。 等向性HBN經真空燒火以移除氧化硼以預備金屬化已於美 國專利第3,926,571號第3欄提及。初步乾燥HBN已揭露於美 國專利第4，150,098號第3欄。最後，美國專利第4,289,503號 574173 (3) 發明說明續:¾ 於HBN熱分解範圍中的溫度藉由在惰性大氣之下真空燒火 或加熱預處理HBN以除去氧化硼並留下硼表面塗層。然後 ，該經預處理的HBN被轉換成CBN。 發明概要 不管用以製造CBN產品的技術如何，CBN產品的韌性指 數（T1)可藉由在含有除氧劑下進行高溫/高壓（HP/HT)方法
加以改良。除氧劑包含Al、Si和Ti。該HP/HT方法依習用方 式進行，包括有或無催化材料參與的情況下。視需要，HP/HT 方法的HBN原料可經預處理以除去來自該處的氧化物。 本發明的另一方面係一種具有氧含量小於約300 ppm，有 利地較少於約200 ppm，和較佳地較少於約100 ppm的CBN產 品。 本發明的優點包含改良任何CBN產品（不管它如何製作） 的韌性指數的能力。另一優點係改良CBN產品韌性指數而 不會有害地不利影響CBN產品的其他必要性質的能力。進 一步的優點係製造極低含氧量產品的能力。這些和其他優 點對於基於本揭示的熟習此項技藝者係明顯易見的。 圖式簡單說明 為能較完整瞭解本發明的本質和目的，應該參考下列詳 細說明並配合附圖進行，下列詳細說明係配合附圖： 圖1繪出已製造的多種CBN晶體的晶體韌性和氧含量關係 圖2繪出已接受熱處理的多種CBN晶體的晶體韌性與氧含 量關係； 574173 (4) 發明說明 圖3繪出使用一催化劑系統製造之CBN晶體的晶體韌性與 氧含量關係；和 圖4繪出使用一催化劑系統且接受熱處理製作的CBN晶體 的晶體韌性與氧含量關係。 附圖會在下述更詳細說明。 本發明詳細說明 本發明有關測量氧含量低於舉例來說約300 ppm的CBN晶 體。該等晶體可藉由任何已知化學於除氧狀況下，諸如， 舉例來說，藉由在成長化學中包含除氧劑材料（π除氧劑’’） 。適當的除氧劑包含，舉例來說，Al、Si或Ti，其形成非 常穩定的氧化物，可作用以降低合成化學裡的氧以產生具 有氧含量低於該目標（約300 ppm)的晶體。 加入至原料的除氧劑數量足以降低CBN產品的氧含量至 所需要的含量，例如，達到一必要目標TI。過量除氧劑可 使用於CBN產品，但會有影響其他必要性質的危險。然後 ，寬廣地，除氧劑數量可從為加至反應槽之原料之約0.005 至0.5 wt-%範圍。 除氧劑，舉例來說，Al、Si或Ti以下列形式之一或多項 出現在反應槽：（a)元素金屬，和（b)任何自由形成能比金 屬氧化物、碳化物、氮化物等更高的化合物。在CBN方法 期間，除氧劑被轉換成氧化物。該等除氧劑氧化物通常未 併入至CBN晶體内，使其藉由後續的處理來排除暨實際且 成本不昂貴。 任何製造CBN晶體的技術可用於本發明。因此，經燒結 574173 (5) 發明競明身矿 的CBN晶體、碟片和重新燒結的CBN材料可藉由減少存在 的氧量來改良其韌性。在CBN的催化形成方面，可使用催 化和黏結材料，諸如在美國專利第3,233,988號和3,918,219號 詳細說明的催化形成的CBN碟片，以及美國專利第3,743,489 號和3,767,371號的黏結媒介。單晶體CBN亦可在有來自HBN 之催化劑金屬或合金的存在情況下製造。 美國專利第4,188,194號教導一較佳直接轉換的方法，其 中一燒結的多晶體CBN碟片藉由較佳放置定向的熱分解六 方晶系测氮化物（PBN)在一反應槽而製成，其中棚氮化物 實質上沒有催化活性材料。反應槽條件包含約5〇和1〇〇 Kbars 壓力之間和至少約1800°C之溫度，（在BN相圖的CBN穩定區 域裡）。當HBN被研磨至小粒度時，一改良方法被揭露在美 國專利第4,289,503號，其中氧化硼係在轉換方法之前從HBN 粉末的表面移除。美國專利第5,106,792號從不同結構形式 的GBN混合物製造CBN/CBN複合團塊。美國專利第4,673,414 號藉著一無催化劑的HP/HT方法重新燒結多晶體CBN。這些 方法的各種變化在所屬技術領域中係習知的。這些引證案 的揭示以引用的方式明白地併入本文。因此，可在此處所 引用的參考文獻中找到用以形成CBN產品和形成CNB產品 的原料的HP/ΗΤ方法。 在本發明的一特點，HP/HT方法係在一或多種無或有催 化劑存在下進行。在一具體實施例中，該方法係以一全無 氧含量的催化劑存在下進行。 ”全無氧含量的催化劑”意即氧並非任一催化劑化合物的 -10 - 574173 (7) 讎關 圖1表示多種CBN產品的晶體韌性（由標準韌性試驗測量） 和氧含量（由LECO氧和氮分析器測量（型號TC-436，Leco公 司提供，3000 Lakeview Avenue，St. Joseph，MI))的關係。這 些CBN產品係利用催化劑系統製成，主要含有鹼和鹼土金
屬氮化物、醯胺、氫氧化物和氫化物。類似地，圖2表示 在800°C熱處理30分鐘之後之晶體韌性與氧含量的關係。 CBN產品熱處理的目的係想要模擬CBN晶體在滾壓製造期 間所承受的熱輪廓。圖1和2的數據係陳述於表1如下。 表1 平均氧濃度 (ppm) 標準偏差 線性迴歸分配 的重量 韌性指數〇1) 熱韌性指數 (TTI) 1091 71 0.000198 53.1 54.6 1072 72 0.000193 65.4 64.9 996 37 0.00073 65.6 64.9 856 25 0.0016 51.1 49.3 1803 119 7.06 E-05 54.7 40.8 1674 137 5.33 E-05 54.5 45.6 1471 29 0.001189 53.1 64.8 I 393 32 0.000977 67.4 64.8 335 17 0.00346 72.8 68.1 611 50 0.004 66.5 68 1321 18 0.003086 56.5 54.4 1261 80 0.000156 60.1 55.6 1225 21 0.002268 62.2 67.2 1189 65 0.000237 62.7 66 CBN晶體的平均韌性隨著多樣試驗材料的氧含量增加而
降低是清楚的。對於熱處理之後的材料，氧含量的效應強 -12- 574173 (8) 發明說明績頁丨 度約較高50%(圖1與圖2線斜度）。 實例2 圖1和2的材料試驗代表廣泛多樣的合成化學，如上所述 。如果試驗限制使用單一化學系統，氧含量對韌性的影響 更為顯著。因此，執行使用氮化三經、氫化經、氫氧化魏 催化劑系統製造的CBN晶體的TI試驗。這些試驗的結果顯 示於圖3和4以及表2，如下。
表2 平均氧濃度 (ppm) 標準偏差 線性迴歸分配 的重量 韌性指數(TI) 熱韌性指數| (TTI) 1803 119 7.06 E-05 54.7 40.8 1674 137 5.33 E-05 54.5 45.6 1471 29 0.001189 53.1 52.9 | 611 50 0.004 66.5 68 1321 18 0.003086 56.5 54.4 1261 80 0.00156 60.1 55.6 1225 21 0.002268 62.2 67.2 1189 65 0.000237 62.7 66
如圖3和4所示。在熱處理之後，氧含量對韌性的影響特 別高，可從曲線的斜度看出。當使用相同的催化劑系統至 各種氧含量的合成晶體時，因為未受控制的變數較少，所 以改良的闕聯性上升。 ---------------- 這些試驗結果導致較低氧含量改良CBN晶體的韌性的結 論，不管用以合成CBN晶體的化學為何。該等較大韌性的 晶體被預期在輪磨或機製展現較長壽命，因此，工具的壽 命愈長。這導致較少的工具磨耗，且最後，導致較低整體 -13- 574173 (9) 發明說明;續莱 工具成本。 實例3 在這個實例中，變體I代表以Li3N、LiOH、LiH催化劑系 統製造的CBN晶體。變體II代表以Li3N、LiH催化劑系統製 造的CBN晶體，其中Li的總量與變體I過程相同。 進行每一催化劑系統的三項過程。資料記錄陳述於表3 如下。 表3 材料 氧（ppm) 平均氧 (ppm) 標準 差氧 TI TTI TI-TTI 過程1 過程2 過程3 變體I 1879 1863 1666 1803 119 54.7 40.8 13.9 |變體II 1305 1316 1341 1321 18 56.5 54.4 2.1 這些結果顯示使用含氧催化劑（LiH-Li3N-LiOH)提供氧至 產品CBN晶體，與僅使用LiH和Li3i^t為催化劑系統的合成 產品比較，其降低該等晶體TI和TTI。 實例4 在這些一系列過程中，變體I代表實例2的變體I。變體III 代表相同的催化劑系統，但添加Si元素0.12 wt-%。變體IV 代表相同的催化劑系統，但添加0.2 wt-% Si3N4(與變體III相 同的Si含量）。資料記錄陳述於表4如下。 574173
(ίο) 表4 材料 _ 氧（ppm) 平均氧 標準 TI TTI TI-TTI 過程1 過程2 過程3 (ppm) 差氧 變體I 1879 1863 1666 1803 119 54.7 40.8 13.9 變體III 1195 1250 1121 1189 65 62.7 66.0 -3.3 變體IV 1236 1201 1239 1225 21 62.2 67.2 -5.0 這些結果顯示元素Si和氮化碎兩者都是有效的除氧劑。 給人深刻印象的是熱韌性指數與室溫韌性指數比較係增加 實例5 在這些一系列過程中，進行評估不同濃度除氧劑的影響 。變體V使用LiNH2、添加0.75 wt-% Si3N4的LiH催化劑系統 。變體VI使用相同的催化劑系統，但添加1.8 wt-% Si3N4。 記錄的結果陳述於表5如下。 表5 I 材料 氧(ppm) 平均氧( 標準差 TI TTI TI-TTI 過程1 過程2 過程3 ppm) 氧 變體I 1879 1863 1666 1803 119 54.7 40.8 13.9 |變體V 392 362 426 393 32 67.4 64.8 2.6 丨變體VI 343 315 346 335 17 72.8 68.1 4.7 這些結果再次顯示藉由除氧劑的添加可改良勃性。對於 試驗的化學物，這些結果也顯示為了要降低氧含量至需要 的3 00 ppm含量附近，需要較高的除氧劑含量。在此處所報 告的數據尚未達成氧目標300 ppm含量，其僅展示任一給定 的CBN化學物，其韌性可藉由降低其含有的氧含量而改良 。它亦展示可達到目標300 ppm含量。 -15-

Claims (1)

  1. 574173
    .利申請案 修正 替換本（92年”） ¢21日補㊆ 拾、申請專利範圍 1· 一種改良由高溫/高壓（HP/ΗΤ)方法製成之CBN產品之韌 性的方法，其包含下列階段： (a) 由除氧劑和形成CBN產品的原料形成換合物； (b) 將該摻合物承受CBN高溫/高壓（HP/ΗΤ)方法以形 成CBN產品； 該摻合物中的除氧劑數量須足以改良該CBN產品的韌 性。 2.如申請專利範圍第1項之方法，其中該除氧劑為一或多種 Al、Si或 Ti。 3·如申請專利範圍第1項之方法，其中除氧劑數量在〇·〇〇5 和0·5 wt-%之間。 4·如申請專利範圍第2項之方法，其中除氧劑數量在0·005 和0.5 wt-%之間。 5·如申請專利範圍第2項之方法，其中該除氧劑為一或多種 形式之元素金屬、金屬碳化物或金屬氮化物。 6·如申請專利範圍第4項之方法，其中該除氧劑為一或多種 形式之元素金屬、金屬碳化物或金屬氮化物。 7. 如申請專利範圍第1項之方法，其中除氧劑數量足以降低 該CBN產品的氧含量至小於300 ppm。 8. 如申請專利範圍第1項之方法，其中該HP/HT方法係於一 或多種有或無催化劑存在下進行。 9. 如申請專利範圍第8項之方法，其中該HP/HT方法係於無 574173 申請專利範圍績頁 氧含量的催化劑存在下進行。 10. 如申請專利範圍第7項之方法，其中該HP/HT方法係於全 無氧含量的催化劑存在下進行。 11. 如申請專利範圍第1項之方法，其中該除氧劑係從該CBN 產品移除。 12. 如申請專利範圍第7項之方法，其中該除氧劑係從該CBN 產品移除。 13. 如申請專利範圍第9項之方法，其中該除氧劑係從，該CBN 產品移除。 14. 如申請專利範圍第10項之方法，其中該除氧劑係從該CBN 產品移除。 15. —種具有改良韌性之CBN產品，其係由根據申請專利範 圍第7項之方法製得。 16. —種具有改良韌性之CBN產品，其係由根據申請專利範 圍第10項之方法製得。 17. —種具有改良韌性之CBN產品，其係由根據申請專利範 圍第1 2項之方法製得。 18. —種具有改良韌性之CBN產品，其係由根據申請專利範 圍第14項之方法製得。
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