TWI476167B - 用於高效能玻璃纖維之組成物及以其形成之纖維 - Google Patents
用於高效能玻璃纖維之組成物及以其形成之纖維 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
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Description
本發明一般而言係有關於用以製造連續高強度玻璃纖維之組成物及自該組成物形成之纖維。
用於製造連續高強度玻璃纖維絲束之一般玻璃組成物為“S-玻璃”。該名詞S-玻璃可定義主要由鎂、鋁、及矽等之氧化物所組成的玻璃種類,且其化學組成可製造機械強度高於E-玻璃纖維之玻璃纖維。該S-玻璃種類之化學組成可製造高強度玻璃纖維並可以使這些玻璃用於高強度應用,諸如防彈盔甲。ASTM International將S-玻璃定義為主要由鎂、鋁、及矽等之氧化物所組成之玻璃種類,且其證明合格的化學組成符合可應用的材料規格並可產生高機械強度(D578-05)。The Deutsches Institut fr Normung(DIN)將S-玻璃定義為未添加CaO且具有部份MgO之鋁矽酸鹽玻璃,其中MgO之含量為約10重量%(鋁矽酸鹽玻璃之定義為主要由三氧化鋁及二氧化矽與其它氧化物所組成之玻璃)(DIN 1259-1)。
R-玻璃為典型上可形成適用於航太複合材料應用之纖維的另一高強度、高模數玻璃種類。該R-玻璃種類主要由氧化矽、氧化鋁、氧化鎂、及氧化鈣所組成,其化學組成可製造機械強度高於S-玻璃纖維之玻璃纖維。與在纖維形成期間需要較高熔化及加工溫度之S-玻璃比較,R-玻璃通常含有較少氧化矽及較多氧化鈣(CaO)。
表IA-IE揭示用於許多習知高強度玻璃組成物之組成。
通常係藉在鉑襯裏之熔化容器內熔化該等組成物之成份而製成典型的R-玻璃及S-玻璃。由於在此等熔化器內製造纖維的成本,所以形成R-玻璃及S-玻璃纖維之成本明顯高於E-玻璃纖維。因此,本項技藝需要能形成可用以自直接熔化方法形成高效能玻璃纖維的玻璃組成物之方法。
本發明為用於形成適用於高強度應用之連續玻璃纖維的玻璃組成物。由於該組成物之相當低纖維化溫度,所以在耐火材料襯裏之爐內進行低成本直接熔化可以花費不多地使該組成物形成玻璃纖維。一旦形成纖維,該玻璃組成物可提供S-玻璃之強度特性。本發明之一組成物包括64-75重量% SiO2
、16-24重量% Al2
O3
、8-11重量% MgO及0.25至3.0重量% R2
O,其中R2
O之含量為Li2
O及Na2
O之總和。本發明該組成物包括64-75重量% SiO2
、16-24重量% Al2
O3
、8-11重量% MgO及0.25至3.0重量% Li2
O。在一較佳實施例中,該玻璃組成物係由64-70重量% SiO2
、17-22重量% Al2
O3
、9-11重量% MgO及1.75-3.0重量% R2
O所組成,其中R2
O之含量為Li2
O及Na2
O之總和。在另一較佳實施例中,該玻璃組成物係由64-70重量% SiO2
、17-22重量% Al2
O3
、9-11重量% MgO及1.75-3.0重量% Li2
O所組成。該組成物較佳不含超過約5.0重量%之選自由CaO、P2
O5
、ZnO、ZrO2
、SrO、BaO、SO3
、F2
、B2
O3
、TiO2
及Fe2
O3
所組成之群組的氧化物或化合物。
藉本發明而製成之高效能複合纖維的所欲性質包括小於約2650℉(1454℃)、較佳小於約2625℉(1441℃)、更佳小於約2600℉(1427℃)且最佳小於約2575℉(1413℃)之纖維化溫度、及較佳比該纖維化溫度低至少80℉(44.44℃)、更佳低至少約120℉(66.67℃)、且最佳低至少約150℉(83.33℃)之液相溫度。本發明亦包括自此種組成物形成之纖維。
本發明之玻璃分批組成物的纖維化性質包括纖維化溫度、液相線、及δ-T(ΔT)。該纖維化溫度之定義為相當於100泊(Poise)之黏度的溫度,如下文更詳細論述,降低的纖維化溫度可減少該等纖維之製造成本,可得到更長的襯套壽命、增加通過料量、可以使該玻璃在耐火材料襯裏的熔化器內熔化、並可減少能源消耗。例如於較低的纖維化溫度下,襯套係於較冷的溫度下操作且不會儘快“鬆垂(sag)”。鬆垂為發生在長時間維持於高溫下之襯套的現象。經由降低纖維化溫度,可降低該襯套之鬆垂速率並可延長襯套壽命。此外,由於在特定時間內於特定能量輸入下可熔化更多玻璃,所以較低的纖維化溫度可得到較高的通過料量。因此,可降低製造成本。此外,較低的纖維化溫度亦可以使使用本發明組成物所形成之玻璃熔化在耐火材料襯裏的熔化器內,因為其熔化及纖維化溫度低於許多市售耐火材料之較高使用溫度。
玻璃之液相線的定義為液態玻璃及其初級結晶相之間存在平衡的最高溫度。於高於該液相線之所有溫度下,該玻璃無呈其初級相之晶體。於低於該液相線的溫度下,可形成晶體。熔體內之晶體會導致該襯套內之阻塞及該等纖維之脆弱。
另一纖維化性質為δ-T(ΔT),其之定義為該纖維化溫度與液相線之差異。在該等玻璃纖維形成期間,較大ΔT可提供較大程度之可撓性且有助於抑制在熔化與纖維化期間該玻璃之去玻化(亦即在熔體內形成結晶)。增加該ΔT亦可藉獲得更長襯套壽命及提供用於形成纖維之較寬製程容忍度而降低該等玻璃纖維之製造成本。
本發明該等玻璃適於熔化在廣泛用以製造玻璃強化纖維之傳統市售耐火材料襯裏之玻璃熔化器內。起始的分批組份典型上包括SiO2
(磨碎的氧化矽沙)、及Al2
O3
(煅燒氧化鋁)或葉蠟石(pyrophyllite)、以及得自來源材料之鏈改質劑,諸如滑石、菱鎂礦(magnesite)或白雲石(dolomite)。材料,諸如菱鎂礦,內所含之碳係以碳之氧化物(諸如CO2
)形式經。
根據本發明所形成之纖維較佳可包括64-75重量%SiO2
、16-24重量% Al2
O3
、8-11重量% MgO及0.25至3.0重量% R2
O,其中R2
O之含量為Li2
O及Na2
O之總和。該組成物更佳可包括0.25至3.0重量%非Li2
O及Na2
O之組合的Li2
O。在另一較佳實施例中,該玻璃組成物係由64-70重量% SiO2
、17-22重量% Al2
O3
、9-11重量% MgO及1.75至3.0重量% R2
O所組成,其中R2
O之含量為Li2
O及Na2
O之總和。該組成物更佳可包括1.75至3.0重量% LiO2
。根據本發明所形成之纖維典型上可包括少量CaO、P2
O5
、ZnO、ZrO2
、SrO、BaO、SO3
、F2
、B2
O3
、TiO2
及Fe2
O3
,其等之總含量較佳小於5重量%、且更佳小於約4重量%。此外,根據本發明之方法及組成物所形成之纖維可具有小於2650℉(1454℃)、較佳小於約2625℉(1441℃)、更佳小於約2600℉(1427℃)且最佳小於約2575℉(1413℃)之纖維化溫度及較佳比該纖維化溫度低至少80℉、更佳低至少約120℉(66.67℃)、且最佳低至少約150℉(83.33℃)之液相線溫度。而且,本發明該玻璃可具有超過680KPSI之原始纖維強度、更佳超過700KPSI之強度、且較佳超過約730KPSI之強度。此外,該等玻璃纖維較佳可具有大於12.0MPSI、更佳大於約12.18MPSI、且最佳大於約12.6MPSI之模數。
較佳使用自合適耐火材料,諸如氧化鋁、氧化鉻、氧化矽、氧化鋁-氧化矽、氧化鋯、氧化造-氧化鋁-氧化矽、或以類似氧化物為主之耐火材料製成之玻璃熔爐以熔化本發明該玻璃批。通常此等玻璃熔爐包括另外的起泡器及/或電輔電極(一合適玻璃熔爐揭示在各稱為“Method of Manufacturing High Performance Glass Fibers in a Refractory Lined Melter and Fiber Formed Thereby”之美國專利申請案第20070105701號內,其在此併入本案以為參考資料)。該等起汽器及/或電輔電極可增加整體玻璃之溫度並增加在爐蓋下之熔態玻璃循環。
將該熔態玻璃自前爐送至襯套總成。該襯套包括具有數個噴嘴之端板,各噴嘴可排出熔態玻璃物料流,其等係經機械性拉伸以形成連續長絲。典型上,該等長絲係經保護性漿紗塗覆,聚集成為單一連續股並捲繞至捲繞機裝置之旋轉筒夾上以形成一捲裝。亦可將該等長絲加工成為其它形式,其包括,但不限於:濕使用之短切束纖維、乾使用之短切股纖維、連續長絲墊、短切股墊、濕形成墊或氣流鋪置墊。
由於已一般性地描述本發明,可藉參考下文闡明之特定實例而進一步瞭解本發明,其中該等特定實例僅用以闡明且除非另有指定,並無意全部包括或限制本發明。
使列示在表IIA-IID內之實例中的玻璃熔化在鉑坩堝內或連續鉑襯裏之熔化器內以測定該玻璃及自其製成之纖維的機械及物理性質。用於該等物理性質之測量單位為:黏度(℉)、液相線溫度(℉)及ΔT(℉)。在某些實例中,該等玻璃經纖維化且測定其強度(KPsi)、密度(克/立方厘米)、模數(KPsi)。
使用旋轉桿黏度計測定該纖維化溫度。該纖維化黏度之定義為1000泊。藉將裝填玻璃之鉑容器放在熱梯度爐內,費時16小時而測定該液相線。存在晶體之最高溫度被視為該液相線溫度。使用音波技術在單一玻璃纖維上測定該模數。在原始單一纖維上測定抗拉強度。
本發明該組成物亦可包括鏈改質劑,諸如Na2
O、CaO及B2
O3
。此等組成物係示於下表II-D內。
本發明該等纖維具有優異模數及強度特性。實例1之纖維具有12.71MPsi之測定模數、及688MPsi之測定強度。實例3之纖維具有12.96MPsi之測定模數、及737KPsi之測定強度。實例17之纖維具有12.75MPsi之測定模數、及734KPsi之測定強度。
如本項技藝所瞭解,由於統計學的慣例(諸如捨入及平均)及某些組成物可包括未列示之雜質的事實,所以上述代表性本發明組成物未必總是含總共100%所列示組份。當然,組成物內所有組份(其包括任何雜質)的實際含量經常總共100%。而且,應瞭解若小含量之組份詳細在該等組成物內,例如大約0.05重量或更小之含量,則這些組份可以以存在於該等原料中之微量雜質的形式,而非故意添加的形式存在。
另外,其後可排除例如添加至該分批組成物以幫助加工之組份,藉以形成基本上無此等組份之玻璃組成物。因此,例如微量組份,諸如氟及硫酸鹽,可以以微量雜質存在於該等原料中以得到用於本發明之商業實踐的氧化矽、氧化鈣、氧化鋁、及氧化鎂組份或其等可以是在製造期間基本上可經移除之加工佐劑。
自上述實例明顯可知本發明之玻璃纖維組成物具有有益性質,諸如低纖維化溫度、及該等液相線溫度與纖維化溫度間之廣差異(高ΔT值)。自上述及進一步經由本發明之實踐,技術人員可瞭解本發明之其它優點及明顯的修飾。本發明之高效能玻璃可以於相當低的溫度下熔化並精煉,在相當低溫度的廣範圍內具有可加工黏度、及低液相線溫度範圍。
上文已一般性且參考特定實施例描述本申請案之發明。雖然已在咸信為較佳實施例中揭示本發明,但是可選擇屬於該一般揭示內容範圍之為熟悉本項技藝已知之多種可替代的方式。自上述及進一步經由本發明之實踐,該技術人員可瞭解本發明之其它優點及明顯的修飾。除了下文所揭示之申請專利範圍之詳述外,本發明並未另外受限。
Claims (13)
- 一種用於可自直接熔化方法形成之高強度玻璃纖維的組成物,其包含:64-75重量% SiO2 ;16-24重量% Al2 O3 ;8-12重量% MgO;0.25-3重量% Li2 O;及不超過2重量%的CaO,其中自該組成物所製成的玻璃纖維具有低於2650℉(1454℃)的纖維化溫度,及高於約700KPSI的強度。
- 如申請專利範圍第1項之用於高強度玻璃纖維之組成物,其中該組成物包含小於5重量%之選自由以下所組成之群組的化合物總含量:P2 O5 、ZnO、ZrO2 、SrO、BaO、SO3 、F2 、B2 O3 、TiO2 及Fe2 O3 。
- 如申請專利範圍第1項之用於高強度玻璃纖維之組成物,其所製成之玻璃具有至少80℉(44.44℃)之△T。
- 如申請專利範圍第3項之用於高強度玻璃纖維之組成物,其所製成之玻璃具有至少120℉(66.67℃)之△T。
- 如申請專利範圍第1項之用於高強度玻璃纖維之組成物,其所製成之玻璃具有小於2600℉(1427℃)之纖維化溫度。
- 如申請專利範圍第1項之用於高強度玻璃纖維之組成物,其中該組成物包含:68-69重量% SiO2 ; 20-22重量% Al2 O3 ;9-10重量% MgO;及1-3重量% Li2 O。
- 一種藉在耐火材料襯裏之玻璃熔化器內熔化玻璃批而形成之高強度玻璃纖維,其包含:64-75重量% SiO2 ;16-24重量% Al2 O3 ;8-11重量% MgO;1.0-3.0重量% Li2 O;及不超過2重量%的CaO。
- 如申請專利範圍第7項之高強度玻璃纖維,其中該纖維具有大於12.0MPSI之模數。
- 如申請專利範圍第7項之高強度玻璃纖維,其中該纖維具有大於12.7MPSI之模數。
- 如申請專利範圍第7項之高強度玻璃纖維,其包含:68-69重量% SiO2 ;20-22重量% Al2 O3 ;9-10重量% MgO;及1-3重量% Li2 O。
- 如申請專利範圍第1項之組成物,其中Li2 O係以約1.75至3.0重量%的量存在於該組成物中。
- 如申請專利範圍第7項之高強度玻璃纖維,其中該Al2 O3 係以約17至約22重量%的量存在於該組成物中;該MgO係以約9至約11重量%的量存在於該組成物中;以 及該Li2 O係以約1.75至3.0重量%的量存在於該組成物中。
- 如申請專利範圍第1項之組成物,其中所述組成物之該等組份於一耐火材料襯裏之熔化器中係可熔融的。
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- 2009-12-21 KR KR1020117016946A patent/KR101652139B1/ko active IP Right Grant
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Also Published As
Publication number | Publication date |
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MA32986B1 (fr) | 2012-01-02 |
KR101652139B1 (ko) | 2016-08-29 |
CA2747993A1 (en) | 2010-07-01 |
US8338319B2 (en) | 2012-12-25 |
CA2747993C (en) | 2019-09-24 |
EP2379461A1 (en) | 2011-10-26 |
AU2009330199B2 (en) | 2015-08-27 |
ES2837456T3 (es) | 2021-06-30 |
RU2011126895A (ru) | 2013-01-27 |
BRPI0923555A2 (pt) | 2016-01-26 |
RU2531951C2 (ru) | 2014-10-27 |
JP2012513362A (ja) | 2012-06-14 |
CN102317225A (zh) | 2012-01-11 |
SA109310015B1 (ar) | 2013-10-03 |
CN107021639A (zh) | 2017-08-08 |
EP2379461B1 (en) | 2020-09-23 |
TN2011000312A1 (en) | 2012-12-17 |
AU2009330199A1 (en) | 2011-07-14 |
JP5667578B2 (ja) | 2015-02-12 |
KR20110097974A (ko) | 2011-08-31 |
TR201106170T1 (tr) | 2012-02-21 |
US20100160139A1 (en) | 2010-06-24 |
MX2011006712A (es) | 2011-09-01 |
TW201031613A (en) | 2010-09-01 |
WO2010075262A1 (en) | 2010-07-01 |
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