TWI472496B - 耐火性玻璃陶瓷 - Google Patents

耐火性玻璃陶瓷 Download PDF

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TWI472496B
TWI472496B TW102128859A TW102128859A TWI472496B TW I472496 B TWI472496 B TW I472496B TW 102128859 A TW102128859 A TW 102128859A TW 102128859 A TW102128859 A TW 102128859A TW I472496 B TWI472496 B TW I472496B
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glass
glass ceramic
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Halsey Beall George
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Corning Inc
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Description

耐火性玻璃陶瓷
本發明是有關內部晶核形成玻璃陶瓷製品的形成，該內部晶核形成玻璃陶瓷製品可在1350-1450℃範圍內加熱相當長時間，而不會有形狀上明顯的變形或改變。這些玻璃陶瓷的主要晶相是鋇長石(BaAl2 Si2 O8 )或其鍶等價物(SrAl2 Si2 O8 )，或這些組成份的固態溶體或混合物，其全部屬於長石礦物群。
藉由控制玻璃製品的結晶來生產玻璃陶瓷製品。一般而言，通常加入晶核形成劑到形成玻璃的批料，熔融後將此熔融物冷卻以形成均勻的玻璃物體。
然後，對玻璃物體執行通常包含兩個階段的加熱處理時程。首先，將玻璃加熱到玻璃的轉變溫度範圍之上，導致其內部晶核形成的發展。之後，加熱晶核形成玻璃到較高的溫度，一般是在玻璃的軟化點以上以導致核上晶體的成長。因為在晶核形成步驟期間，在無數的晶核上出現結晶，所以晶體呈均勻的微粒狀，並且均質地擴散在玻璃基質中。
晶體通常包含製品的優勢，因此賦予製品比原始玻 璃更類似於晶相的性質。然而，因為物體從玻璃原地結晶，因此完全沒有空隙，是無孔隙的。
假使粒狀較大，矽半導體在顯示或光伏打裝置上會更有效率。矽在1417℃下熔融，並且當保持在其熔融點以下時，接著結晶成大粒狀。這是因為晶核形成在這樣的高溫下是沒有效率的，但可以最大化粒子的增長。由於這些結晶薄膜的增長一開始需要施加熔態矽的薄膜到基板表面，因此很重要的事是基板材料本身是惰性，可抵抗高溫，有大致匹配矽的熱膨脹係數(CTE)。如果矽在惰性基板上熔融，接下來在接近其熔融點時再結晶，假使基板大致匹配矽的CTE，則在冷卻至室溫之後將保持為連貫的大粒狀薄膜。本發明的玻璃陶瓷可調整到匹配或者非常接近矽的CTE。更者，某些也可顯示光伏打行為的低氧化半導體，譬如還原鈦酸鹽和某些鉭酸鹽類需要較高的溫度(1300℃以上)以有效燒結。因此，這些材料的薄膜需要可抵抗1400℃以上燒結溫度的基板。更者，也需要可在某些引擎元件中替代超合金的陶瓷材料，譬如使用在飛機引擎和柴油渦輪增壓器的元件。氮化矽是一種選擇，但其很難製造也因而相當昂貴。
於是，我們需要可在薄膜晶體矽生產上使用作為惰性基板的高溫玻璃陶瓷材料，該高溫玻璃陶瓷材料可調整到非常匹配矽的CTE，可承受高到1450℃的溫度，可抗氧化，可藉由壓模技術或只是鑄型到石墨或其他模子，在流體玻璃狀態精確成形。
本發明提供高破裂韌性和低熱膨脹係數的玻璃陶瓷，此玻璃陶瓷的形成包括下列重量百分比之組成份：
玻璃陶瓷包括長石做為主要的晶相。主相是鋇長石(BaAl2 Si2 O8 )或其鍶等價物(SrAl2 Si2 O8 )，或鋇長石(BaAl2 Si2 O8 )及其鍶等價物(SrAl2 Si2 O8 )的固態溶體或混合物。次晶相則包括鈦酸鋁，富鋁紅柱石，銳鈦礦和金紅石。在大多數應用上，玻璃陶瓷是小於剩餘玻璃量的25%。
在某些應用上，玻璃陶瓷最好是無鹼金屬的，而且真正沒有其他的助熔劑。在其他實施範例中，可以加入助熔劑或其他成分，但通常不超過5%的重量。
在某實施範例，玻璃陶瓷在25-1000℃的溫度範圍下，CTE是從30-55×10-7 /℃，軟化點溫度是超過1450℃，破裂韌性超過1.2 K1c MPa‧m1/2 ，破裂模數(M.O.R.)超過90 MPa，使用的溫度超過1250℃，最好高達1450℃或更高。
本發明已指出數種玻璃陶瓷的應用，包括耐高溫的應用，譬如在光伏打裝置，冶金鑄模，天線罩和引擎元件所需用到的基板。
進一步要說明的是生產加熱到1250℃-1450℃的溫 度範圍，而不會有形狀上變形或改變的玻璃陶瓷製品的方法。特定實施範例包括的步驟為熔融包括至少一種晶核形成劑的原始批料到1550℃-1750℃的溫度一段期間，足以達到熔態均質熔融物；從熔融物形成所需形狀的玻璃製品；在700℃到850℃的溫度範圍退火玻璃製品；在800℃到900℃的溫度加熱處理玻璃製品一段期間，足以達到晶核形成劑均質的擴散和核的成長；在950℃到1450℃的溫度範圍結晶該玻璃一段期間，足以達到最大的結晶度，因而將玻璃製品轉變成玻璃陶瓷製品；以及冷卻玻璃陶瓷製品。
本發明揭示一種內部晶核形成玻璃陶瓷，該內部晶核形成玻璃陶瓷可在1250-1450℃範圍內加熱相當長時間，而不會有形狀上明顯的變形或改變。這些玻璃陶瓷的主要晶相是鋇長石(BaAl2 Si2 O8 )或其鍶等價物(SrAl2 Si2 O8 )，或這些組成份的固態溶體或混合物。玻璃陶瓷包括當實質玻璃材料在提升的溫度下加熱而產生實質結晶材料時所形成的任何材料。加熱處理引發一或多個晶核形成。晶核形成的加速可藉著加入諸如氧化鈦(TiO2 )的成份到玻璃來達成，該成分在加熱玻璃後均勻地沈積。當達到所要的結晶水準時即完成加熱處理。對大多數的玻璃陶瓷而言，這是出現在當結晶達到百分之五十，更常是超過百分之八十的重量百分比時。
這些玻璃陶瓷材料具有絕佳的耐火性質，由在1600 ℃-1675℃範圍溫度下可熔融至良好品質之玻璃製成，這是其他業界的玻璃或玻璃陶瓷母玻璃所建立有效熔融的範圍。
本發明的玻璃陶瓷包括多個晶相，但絕大多數是由長石主晶相所構成。在很多應用上，剩餘的玻璃應該夠堅硬，導致從材料形成的複合製品在超過1250℃，超過1300℃，超過1350℃，和超過1400℃的溫度下不會有形狀上的變形或改變。換言之，本發明玻璃陶瓷製品的實施範例使用的溫度是大於1250℃且可高達1450℃。「使用溫度」一詞是指從玻璃陶瓷形成的製品，當放在負載或本身重量下不會變形。為了達到此目的，結晶應該至少約70%的重量，最好超過80%的結晶。剩餘的玻璃一般是少於25%的量。
鋇長石是單斜結構，晶體空間群I2/c，其鍶等價物是有相同晶體空間群的類似單斜結構。這些端成分之間的固態溶體被認為是寬廣但不完全。這些鋇長石型態的晶體作為玻璃陶瓷主要相的價值至少有兩重：i)高的熔融點，就純的鋇端成分而言約是1750℃，而鍶端成分約是1710℃，和鈦酸鹽晶核形成劑的效果以及玻璃陶瓷內呈現的剩餘玻璃結合起來可允許到約1450℃的熱穩定性，和ii)，其相對低的CTE從25-1000℃是40-55×10-7 /℃的範圍。和大量的矽土剩餘玻璃結合起來，真正的玻璃陶瓷CTE值可降低至30-45×10-7 /℃(25-1000℃)的範圍，絕佳的矽匹配基板，和夠低的CTE值以提供好的抗熱震阻力，可用在引擎元件，天線罩，和冶金鑄模。據此，所揭示的玻璃陶瓷，CTE範圍大約30-55×10-7 /℃(25-1000℃)。列在表格1的特定範例證實了CTE範圍在 36.9-43.7×10-7 /℃(25-1000℃)。藉著改變組成份內矽土玻璃的百分比，我們可以在更大的揭示範圍內改變CTE。然而在需要堅硬度的某些應用上，矽土玻璃的改變應該維持在需要的限制範圍以避免加熱處理到約1400℃之溫度點後，製品明顯的變形。
雖然使用TiO2 作為晶核形成劑已被證實為有效，但其他可能作為晶核形成劑的選擇包括：ZrO2 ；譬如鉑，銠，銥，鉛或金的金屬；或譬如ZnS的硫化物。其他的選擇還有V2 O5 、MoO3 、SrF2 、BaF2 、WO3 及NiO。
本發明實施例之玻璃陶瓷組成份份範圍在SiO2 -Al2 O3 -SrO-BaO-TiO2 系統中以及以重量百分比包含下列範圍：SiO2 25-45、Al2 O3 23-37、SrO 0-30、BaO 0-35、和TiO2 5-15。SrO+BaO總和在15及35重量百分比之間以及(SrO+BaO)/Al2 O3 之莫耳比值較佳地小於1.2，更佳地小於1.1以及仍然更佳地小於1.0。高達5%重量比的其他成份(例如ZrO2 、K2 O、ZnO、CaO等)可加入以改善最終複合物之特定物理特性(CTE，穩定性等)。然而，應該要注意的是，加入額外的成分通常會降低最終組成份的熔融點，因而影響這些材料在防火應用上的優勢。對於有關在超過1000℃溫度下和矽接觸的電子應用，其成分基本上最好是不含鹼金屬或其他可經由和矽反應而還原至元素狀態的氧化物(例如PbO、ZnO、CuO、P2 O5 等)。
在更多限制的SiO2 -Al2 O3 -BaO-TiO2 系統中也可以發現小範圍的可熔融玻璃成分，可加熱處理成顯示本發明所 有特性的玻璃陶瓷。這可以下列的重量百分比界定出：SiO2 31-41、Al2 O3 27-33、BaO 24-32、和TiO2 6-12。
在另一更限制的SiO2 -Al2 O3 -BaO-TiO2 系統中也同樣可以發現的較大範圍的可熔融玻璃成分，可加熱處理成顯示本發明所有特性的玻璃陶瓷。這可以下列的重量百分比來定義：SiO2 30-45、Al2 O3 25-37、SrO 18-28、和TiO2 6-12。其中沒有鋇且以鍶為主的玻璃陶瓷在需要較低密度材料的應用或者出現毒性問題的應用上可能更有用。
從以上所列成份形成玻璃製品的方法包括壓模，滾動，鑄造，離心旋轉，和其他可用在現行玻璃科技的技術。這些玻璃流體的本質使其更可適應精準的鑄造，可展示具有窄的凸緣且超過一英吋的厚鑄造。然後將形成的玻璃製品退火，通常溫度在700℃和850℃之間。
在玻璃製品形成和退火之後，加熱處理製品將其轉變成玻璃陶瓷。一般而言，將玻璃製品放至瓦斯爐或電爐，在800℃和900℃之範圍的溫度加熱處理，晶核形成期間可以短至10分鐘，長至數小時，隨著均質擴散和鈦酸鹽晶核成長而定。接著，於結晶期間提升溫度到較高的溫度，該較高的溫度通常在950-1450℃的範圍內。結晶期間應該維持4-6小時，或者視選擇的成分需要達到最大化的結晶而定。保留一些矽土的剩餘玻璃以幫忙降低玻璃陶瓷的CTE。
主要的晶相是單斜結構鋇長石型態的長石，不是鋇或鍶端成分，就是這些端成分之間的固態溶體或固態溶體混合物。除了主要鋇長石型態的相，在這些玻璃陶瓷中還呈現 重要的副相。這些副相包括至少一種鈦酸鹽相，通常是鋁鈦酸鹽(Al2 TiO5 )或金紅石(TiO2 )，和矽土玻璃相。也可以呈現富鋁紅柱石(Al6 Si2 O13 )作為副相，一般是小於約10%的量，變化則視精準的組成份而定。
晶體是細粒的，通常在0.5和20微米之間，其微結構是均勻的。當加熱處理到1400℃或以上，玻璃陶瓷的表面通常是呈灰色到白色，而內部通常還是灰色。較白的表面推測是由於玻璃陶瓷內呈現的還原鈦(Ti3+ )小量的氧化。
本發明的玻璃陶瓷可形成任何數目的製品。特別適用於製品的玻璃陶瓷需要較低的CTE，優良的破裂韌性，優良的強度，抗氧化，和高溫需求。例如，破裂韌性通常是大於1.2 K1c MPa‧m1/2 。破裂韌性可以超過2，或甚至2.5 K1c MPa‧m1/2 。測得的破裂模數是超過89±5 M.O.R.(MPa)。玻璃陶瓷的固有抗氧化性質使得玻璃陶瓷可以使用在氮化矽會氧化的應用。
可能的使用包括半導體結晶的基板。熔融所需的使用溫度需要高到1450℃，接著再結晶矽成最大的粒狀，其中光伏打或其他半導體應用的效能可達到單晶的效能。更者，矽的CTE匹配和鋇長石型態長石玻璃陶瓷可允許連續薄膜的形成和接下來的冷卻。這在譬如氧化鋁的其他耐火陶瓷基板是無法達成的，因為其CTE太高會造成矽薄膜在冷卻後的張力裂痕。
另一種本發明鋇長石(BaAl2 Si2 O8 )和鍶長石(SrAl2 Si2 O8 )玻璃陶瓷材料可能的使用包括高溫引擎元件。進 階引擎元件可耐1450℃高溫的能力是很重要的。鋇長石型態玻璃陶瓷稍低的CTE，加上優良的抗變強度，韌性，和流體精準鑄造的能力可使這些玻璃陶瓷在這些方面具有和昂貴的氮化矽競爭的條件。試驗也證實了這些所揭示的玻璃陶瓷可耐超過1400℃和1450℃高溫，而不會產生形狀上的變形和改變。這些材料的軟化溫度是超過1450℃。
耐火、細粒和無孔隙性鋇長石型態玻璃陶瓷更進一步的可能應用是用在高溫金屬和合金鑄造時的精準鑄模。
還有另一種本發明鋇長石(BaAl2 Si2 O8 )和鍶長石(SrAl2 Si2 O8 )玻璃陶瓷材料更進一步的使用，包括需要高溫使用，抗熱震和無鹼金屬以作為優質微波透明引導的天線罩，或飛彈鼻錐體。鋇長石玻璃陶瓷比目前使用的基於菫青石之天線罩還耐火150℃以上。
鋇長石(BaAl2 Si2 O8 )和鍶長石(SrAl2 Si2 O8 )在結晶文獻中的描述是單斜結構，屬於I2/c晶體空間群。本發明玻璃陶瓷的主相長石同樣地也被認為是單斜的。
範例
以下的表格1提供依據本發明代表性組成份的範例。除非特別指明，組成份的資料是重量百分比而且是整批的。
使用下列原料適當的量，整批的成分可產生1公斤的玻璃：BERKELEY Sand(SILICOSIL 75)、低鹼鋁土、碳化鋇、碳化鍶、和二氧化鈦。這些批料在TURBULA攪拌器中攪拌15分鐘，然後放在650 mm的白金坩堝中。將這個坩堝 放在GLOBAR電爐中，以1650℃加熱16小時，批料會融化成品質優良的熔態玻璃。然後將熔融物注入鋼模中，以產生約4×8×3/4英吋大小的玻璃塊。在冷卻後，玻璃塊被移到退火爐以775℃放置數小時，然後冷卻。產生的玻璃切片後依據表格1的時程加熱處理。靜置之前和期間的加熱速率大約是300℃/hr。在加熱處理期間產生的晶相以X射線繞射來測定。以標準ASTM技術測得這些特性。
顯然地，本發明許多改變及變化為可能的。因而，應了解在下列申請專利範圍之範疇內，本發明能夠以異於特定所說明方式實施。雖然本發明已對特定較佳實施例加以說明，本發明不同的變化，改變，以及添加情況為業界熟知此技術者明瞭的。所有該等改變，變化，以及添加情況屬於本 發明之範疇，以及僅受到本發明所附申請專利範圍限制。

Claims (17)

  1. 一種製造玻璃陶瓷物件的方法，該方法包括下列步驟：熔融包括至少一種晶核形成劑且不含PbO、ZnO、CuO、及P2 O5 的原始批料到1550℃-1750℃的溫度一段時間，該段時間足以達到熔態均質熔融物；從該熔融物形成所需形狀之一玻璃物件；在700℃到850℃的溫度範圍對該玻璃物件進行退火；在800℃到900℃的溫度加熱處理該玻璃物件一段時間，該段時間足以達到晶核形成劑均質的分散和晶核的成長；在950℃到1450℃的溫度範圍使玻璃結晶一段時間，該段時間足以達到最大的結晶度，因而將該玻璃物件轉變成一玻璃陶瓷物件；以及冷卻該玻璃陶瓷物件；並且藉此使該玻璃陶瓷物件在1250-1450℃範圍內加熱時不會變形或形狀產生變化。
  2. 如請求項1所述之製造玻璃陶瓷物件的方法，其中該玻璃陶瓷物件在25-1000℃溫度範圍內之熱膨脹係數在30-55×10-7 /℃範圍內。
  3. 一種玻璃陶瓷，其自一種組成物形成，該組成物包含如下以重量%表示之組成份：SiO2 25-40%， 其中該玻璃陶瓷包含鍶長石作為主要晶相，且其中該組成物不含鹼金屬且不含能夠經由與矽反應而還原至元素狀態之氧化物。
  4. 如請求項3所述之玻璃陶瓷，其中該玻璃陶瓷進一步包含鋇長石(BaAl2 Si2 O8 )。
  5. 如請求項3所述之玻璃陶瓷，其中該玻璃陶瓷在25-1000℃溫度範圍內之熱膨脹係數在30-55×10-7 /℃範圍內。
  6. 如請求項3所述之玻璃陶瓷，其中該玻璃陶瓷之軟化點溫度超過1450℃，且該玻璃陶瓷之使用溫度超過1250℃。
  7. 如請求項3所述之玻璃陶瓷，其中該組成物進一步包含總共小於5重量%之額外成份。
  8. 如請求項3所述之玻璃陶瓷，其中該玻璃陶瓷之破裂韌性超過1.2 K1c MPa‧m1/2 。
  9. 如請求項3所述之玻璃陶瓷，其中該玻璃陶瓷之破裂模數超過89±5 M.O.R.(MPa)。
  10. 如請求項3所述之玻璃陶瓷，其中該組成物包含在20-30重量%之間的SrO+BaO含量。
  11. 如請求項3所述之玻璃陶瓷，其中該玻璃陶瓷進一步包含次晶相，該次晶相係選自鈦酸鋁、多鋁紅柱石、及金紅石。
  12. 一種使用溫度超過約1250℃之玻璃陶瓷物件，該玻璃陶瓷物件包含主要為一種單斜長石之均勻細粒晶體，該晶體係由一玻璃物體經由原位結晶作用而形成，該玻璃物體包含如下以重量%表示之組成份：SiO2 25-40%、Al2 O3 23-37%、BaO 0-35%、SrO 18-30%，且SrO+BaO/Al2 O3 莫耳比值<1.2；以及至少一種相對於主要玻璃組成物為過量之晶核形成劑，該晶核形成劑係選自由TiO2 、ZnS、ZrO2 、V2 O5 、MoO3 、CaF2 、WO3 、NiO、Au、Pt、Rh、及Ir所組成之群組；且其中該玻璃陶瓷物件不含鹼金屬且不含能夠經由與矽反應而還原至元素狀態之氧化物。
  13. 如請求項12所述之玻璃陶瓷物件，該玻璃陶瓷物件進一步顯現超過1300℃之使用溫度。
  14. 如請求項12所述之玻璃陶瓷物件，該玻璃陶瓷物件進一 步顯現超過1350℃之使用溫度。
  15. 一種玻璃陶瓷物件，該玻璃陶瓷物件在25-1000℃溫度範圍內之熱膨脹係數在30-55×10-7 /℃範圍內，且在1300-1450℃之範圍內加熱時不會變形或形狀產生變化，其中該玻璃陶瓷物件不含鹼金屬且不含能夠經由與矽反應而還原至元素狀態之氧化物。
  16. 一種玻璃陶瓷，其自一種組成物形成，該組成物包含如下以重量%表示之組成份：
  17. 如請求項16所述之玻璃陶瓷，其中SrO/Al2 O3 之莫耳比值小於1.2。
TW102128859A 2007-08-28 2008-08-26 耐火性玻璃陶瓷 TWI472496B (zh)

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US20110072853A1 (en) 2011-03-31
TWI408114B (zh) 2013-09-11
KR20100071051A (ko) 2010-06-28
EP2205533A1 (en) 2010-07-14
WO2009029263A1 (en) 2009-03-05
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