CN1066662C - 具有改善圆角保持性能的溶胶-凝胶法氧化铝砂轮 - Google Patents

具有改善圆角保持性能的溶胶-凝胶法氧化铝砂轮 Download PDF

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CN1066662C
CN1066662C CN94108540A CN94108540A CN1066662C CN 1066662 C CN1066662 C CN 1066662C CN 94108540 A CN94108540 A CN 94108540A CN 94108540 A CN94108540 A CN 94108540A CN 1066662 C CN1066662 C CN 1066662C
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D·A·谢尔登
R·S·伦德贝里
晓明·李
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    • B24DTOOLS FOR GRINDING, BUFFING OR SHARPENING
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Abstract

本发明提供一种玻璃态结合磨料的砂轮,其中磨料颗粒是一种溶胶一凝胶法氧化铝磨料,砂轮的圆角或形状保持特性与机械性能获得了改善。本发明还包括提供一种结合剂组合物,它有助于含溶胶一凝胶法磨料的玻璃质结合砂轮的边缘或形状保持性能与机械性能的改善。

Description

具有改善圆角保持性能的溶胶-凝胶法氧化铝砂轮
本申请与颁布于1991年7月30日的美国专利5,035,723和颁布于1993年4月20日的美国专利5,203,886相关,这两个专利的全部说明书已被参考结合于本申请中。
本发明涉及砂轮,具体就是圆角(corner)保持性能有了改善,采用溶胶-凝胶法氧化铝作为磨粒的砂轮。本发明还包括一种能改善机械强度和圆角保持性能的结合剂组合物。
人们正在设计一些精密的运动部件在更高输出或产量、更高效率和更长寿命的情况下进行运转。这些部件例如有:发动机(内燃式、喷气式和电气式),传动系(一般传动装置和差动装置)以及支承面等。为满足这些要求,生产部件的质量应有所改善,包括其设计更好,强度更大,尺寸公差更严。为了获得很严的公差,部件应采用优质材料,并制成接近净的即最终的形状与尺寸。
砂轮时常用于整个部件的制造,即赋于其最终尺寸。玻璃质结合的砂轮大多用于金属部件的磨削。为了用砂轮获得这种精密度的部件,需用金刚石刀具将砂轮的表面修整成该部件的反象形状。因为被加工的部件是取砂轮的外形,所以砂轮尽可能长久地保持其形状是十分必要的。理想的情况就是磨削成具有精确尺寸公差的精密部件,同时并无材料损伤。
典型的情况是,砂轮的形状会走样,即在砂轮的圆角或曲线部位发生损坏。标准的电熔刚玉砂轮在磨削了二、三个工件后,在其边缘处会产生显著的变化。因此,为避免出废品,在每加工一个工件后,磨床工可能须对砂轮进行修整。采用性能较佳的溶胶-凝胶法氧化铝磨粒制造的砂轮,它磨削了四、五个工件后,砂轮边缘的形状才会有变化,因此磨床工在磨削了三个工件后才会要修整砂轮。溶胶-凝胶法氧化铝砂轮的修整频率与标准砂轮比较得以减少,这固然是一个改进,而目前的修整频率仍较大,而且溶胶-凝胶法氧化铝砂轮通过修整要产生损耗,因此人们仍希望能进一步降低修整频率以获得效益。
需要的是一种圆角或形状保持性能较好的溶胶-凝胶法氧化铝砂轮,以便延长两次修整之间的时间。因此,本发明的一个目的就是制造一种圆角或形状保持性能改善的溶胶-凝胶法氧化铝磨粒的砂轮。本发明的又一个目的是制造一种可用于溶胶-凝胶法氧化铝砂轮的结合剂。
本发明提供一种玻璃质结合磨料的砂轮,其中磨料颗粒包括一种溶胶-凝胶法氧化铝磨料,砂轮的圆角或形状保持特性与机械性能获得了改善。本发明还包括提供一种结合剂组合物,它有助于含溶胶-凝胶法磨料的玻璃质结合砂轮的圆角或形状保持性能与机械性能的改善。
图1是一个在圆角保持性能试验中用一个砂轮进行圆角磨削的示意图。
图2是在圆角保持性能试验中砂轮圆角半径与工件表面相接触的那部份的示意图。
本发明的玻璃质结合磨料体中含有溶胶-凝胶法氧化铝磨粒。溶胶-凝胶法氧化铝磨粒在本技术领域中是为人们所熟知的。溶胶-凝胶法氧化铝可以是放入晶种的或不放入晶种的。溶胶-凝胶法氧化铝指的是用下述方法制备的氧化铝,该方法是使氧化铝-水合物的溶胶产生胶溶作用,生成凝胶,然后干燥与煅烧形成α氧化铝。
最初的溶胶还可以含有总重达15%的尖晶石、富铝红桂石、二氧化锰、二氧化钛、氧化镁、稀土金属氧化物、氧化锆或一种氧化锆的前体(此前体的加入量可较多,例如40重量%或以上)、或其它的相容添加物或其前体。溶胶时常含有这些添加物,是为了改进诸如断裂韧度、硬度、脆性、断裂力学以及干燥性能等性质。
凝胶一旦形成后,可用例如压制、模制或挤压等任何一种适宜方法使之成形,然后仔细干燥以生成所需形状的不开裂坯体。
这种凝胶如上成形后,可以再切成合适的供煅烧的尺寸;这种凝胶或者还可直接铺展成任一合适形状,然后干燥,干燥的温度一般低于凝胶的起沫温度。也可以采用任一种去水方法包括溶剂提取法来将凝胶中的自由水分去掉,形成固体。
当固体干燥后,它可切割或加工成所需的某种形状,或用任一种合适设备,例如锤磨机或球磨机进行粉碎,生成颗粒。磨碎固体的任何一种方法都可采用。
成形之后,此干燥凝胶可再经焙烧,基本上去除所有挥发物质,并将颗粒的诸种组分转变成陶瓷物质(金属氧化物)。干燥凝胶一般是加热直至自由水分和绝大部分化合水分都去除掉。经焙烧的材料再经加热煅烧,其保温是在一适当的温度范围内直至所有的α氧化铝-水合物基本上转变为α氧化铝。
如前所述,溶胶-凝胶法氧化铝可以是放入晶种的或不放晶种的。对放入晶种的溶胶-凝胶法氧化铝,是将成核部位物质有意地引入氧化铝-水合物分散体系或在其中就地产生。在分散体系中有成核部位的存在,就降低了α氧化铝随后形成的温度,因此产生极细的结晶结构。
在本技术领域中,人们是很熟悉合适的晶种物质的。它们一般应具有与α氧化铝尽量接近的结晶结构和点阵参数。可用的晶种包括例如颗粒状的α氧化铝、α氧化铁(FewO3)、α氧化铝前体或α氧化铁前体,后两种物质在低于氧化铝-水合物转变成α氧化铝的温度以下的某个温度会分别转变成α氧化铝和α氧化铁。但是,在这里给出这些晶种类型,只是提供说明而已,并不构成什么限制。有效的晶种颗粒在其粒度上应是亚微米的。
如果用晶种溶胶-凝胶法氧化铝,晶种物质的重量最好应不超过水合氧化铝重量的10%,一般来说,超过约5重量%并无好处。如果晶种是足够细的话(最好为60米2/克或以上),其使用量宜为0.5-10重量%,1-5重量%则更适宜。所加入的晶种可以是一种前体形式,它在α氧化铝形成的温度以下的某一个温度会转变为活性晶种。
某些情况下,也可采用非晶种溶胶-凝胶法氧化铝磨料。这种磨料的制法与上述制法相同,只是不引入晶种颗粒。可以在溶胶或凝胶中加入足量的稀土金属氧化物或它们的前体,以便在煅烧后含有至少0.5重量%或最好约1-30重量%稀土金属氧化物。
本发明的砂轮除含有溶胶-凝胶法磨料颗粒外,并可任选地含有一种或多种辅助磨料颗粒。砂轮中有磨料、结合剂、孔隙,可能还有其它填料和添加物。砂轮中磨料包括辅助磨料的用量可能变化很大。本发明砂轮的组成,含有约34至约56体积%磨料较佳,约40至约54体积%磨料更佳,约44至约52体积%磨料则最佳。
在砂轮磨料的总量中,溶胶-凝胶法氧化铝磨料占约5至约100体积%较佳,约30至约70体积%更佳。
在砂轮磨料的总量中,辅助磨料占约0至95体积%较佳,约30至约70体积%更佳。可用的辅助磨料包括例如电熔刚玉、碳化硅、立方氮化硼、金刚石、燧石、石榴石、气泡氧化铝。但是给出这些辅助磨料的例子仅供说明,并非限制。
在砂轮中经常有孔隙存在。本发明砂轮的孔隙度约0至约68体积%较佳,约28至约56体积%更佳,约30至约53体积%最佳。孔隙的形成是由于材料颗粒的自然填充中存在空间间隙,以及由于含有通常的致孔介质材料,例如空心玻璃微珠、核桃壳粉、塑料等有机材料微珠,泡沫玻璃颗粒和气孔氧化铝的缘故。这些致孔材料也不过是示例说明,并不限于此。
本发明的砂轮是用一种玻璃态结合剂结合的。所用的玻璃态结合剂对本发明砂轮的圆角或形状保持特性的改善起着很大作用。此种结合剂的原料较好地是包括6号Kentucky球土、霞石、硅酸钠粉、碳酸锂、燧石、硅灰石和钴尖晶石。这些原料一起含有下列氧化物:SiO2,Al2O3,Fe2O3,TiO2,CaO,MgO,Na2O,K2O,Li2O,B2O3和CoO。砂轮组成中所含的结合剂,约3至25体积%较佳,约4至约20体积%更佳,约5至约18.5体积%最佳。
煅烧后的结合剂中,所含的SiO2大于约47重量%,约52至约62重量%较佳,约54至约60重量%更佳,约57重量%最佳;所含的Al2O3少于约16重量%,约12至约16重量%较佳,约13至约15重量%更佳,14.4重量%最佳;所含的Na2O约7至约11重量%较佳,约8至约10重量%更佳,约8.9重量%最佳;所含的K2O少于约2.5重量%,约0.5至约2.5重量%较佳,约1至约2重量%更佳,约1.6%最佳;所含的Li2O大于约2.0重量%,约2.0至约3.4重量%较佳,约2.0至约2.7重量%更佳,约2.2重量%最佳;所含的B2O3少于约18重量%,约9至约16重量%较佳,约11至约14重量%更佳,约12,6重量%最佳;所含的CoO约0至约2重量%较佳,约0.5至约1.3重量%更佳,约0.9重量%最佳,氧化钴(CoO)对本发明砂轮并不是必需的,其加入只是作为一种着色剂。玻璃态结合剂中的其它氧化物,例如Fe2O3,TiO2,CaO,MgO,都是对构成结合剂并非必需,存在于原料中的一些杂质。此种结合剂还使溶胶-凝胶法氧化铝制备的砂轮的机械强度有所提高。
对砂轮采用本领域技术人员熟知的一些方法进行煅烧。煅烧条件主要取决于实际所用的结合剂材料和磨料。所得玻璃质结合体还可按通常方式用一磨削助剂例如硫或-赋形剂例如环氧树脂来浸渍,令磨削助剂进入磨轮的孔隙中。
所制得的砂轮出乎意料地具有改善的圆角或形状,保持性能,该性能既可定量地,又可定性地测量。虽然砂轮的边缘形状变化被认为是砂轮损坏的判据,但这并不是个定量试验,因为形状变化只能在显微镜下观察得到,而且是用指甲或铅笔尖定性地感触到的。因此,人们研究出了为砂轮圆角损坏模式进行界定和定量化的试验。
这个试验是在一设定的进给速率条件下测量“径向磨损”和“磨损面积”。为了进一步规定砂轮的试验条件以及确定类似砂轮可赖以测量和比较的标准,所用的试验条件如下:
磨床:Bryant LectralineTMLL3 I.D./O.D.,10匹马力磨床;
湿磨法:有水的5-7%Trim Master ChemicalTM VHP E200;
被磨削的工件材料:4330V曲轴钢,Rc为28至32;
工件尺寸:外径4英寸;
距工件边缘的磨削宽度:0.009英寸;
砂轮的圆角半径:0.110英寸;
工件圆周速度:200英尺/分;
进给速率:0.0133英寸/秒;
轮面修整:用金刚石滚轮(RPC2993),其转速为4600转/分,修整速率为0.002英寸/秒以获得0.110英寸半径;
砂轮圆周速度:12,000英尺/分;
每个试验的磨削次数:最多达12次;
每次磨削进给量:0.04英寸;
这个圆角保持性能试验是设计来测量在磨削操作中,砂轮的圆角保持其形状的程度的。形状保持性能用两个量,“径向磨损”和“磨损面积”来衡量。图1简示了用一磨轮10对一工件12例如曲轴进行圆角磨削的情况。
此图中,21-26代表砂轮通过工件的一系列递进行程。21-22代表一次磨削。距工件边缘的磨削宽度14是0.009英寸。进给量是每次磨削0.04英寸。砂轮10的圆角半径18是0.110英寸。图2表示圆角保持试验中,砂轮10的圆角半径30与工件12表面相接触的部分。图2中,磨削宽度即A与C之间的水平距离是试验工件材料要去除的材料厚度。图2中,接触高度32即A与B之间的垂直距离是一个磨削进程结束时与试验工件材料相接触的砂轮部分的高度。在所述磨削条件下,进行两个测量以定量表示砂轮的圆角保持性能。这两个测量的量是“磨损面积”和“径向磨损”。
测量磨损面积就是测量砂轮在磨削了工件以后其圆角的轮廓面积的变化。图2中,对于一给定接触高度32、砂轮半径18、切削宽度14,磨损面积由AEBDA所限定的面积表示。测量径向磨损就是测量在点A和点B之间砂轮半径18的最大改变。这一测量也在图2中表示,径向磨损就等于DE,E就是对于接触高度32,在点A和点B之间砂轮半径发生最大改变达到的位置。砂轮的磨损面积和径向磨损测量的方法是先用该砂轮在每次磨削后对一片样再进行磨削。然后用一个光学比较仪在50倍放大条件下对经此磨削的片样描绘其轮廓。用一面积测量仪测量轮廓线上的磨损面损,用一游标卡尺测量轮廓线上最大的径向磨损作为径向磨损。
在下面的实施例中提供了一些数据,这些数据表明,在达到与标准溶胶-凝胶法氧化铝砂轮可比的径向磨损和磨损面积之前,本发明的新砂轮可以进行出乎意料多的磨削次数,这就定量说明了本发明溶胶-凝胶法磨轮的圆角保持性能有了改善。
为使本技术领域的人员更好地理解本发明的实践,现提供下列实施例以供说明,但并非作为限制。在本说明书中引述到的参考文献和专利中,可以查找到本技术领域中的进一步背影资料,这些资料也参考结合于本发明中。
实施例
实施例1
对晶种溶胶-凝胶法磨料,分别用本发明的新结合剂与Norton标准商用结合剂制备了试样,测量比较了它们的断裂模数。新结合剂的煅烧前组成为:30.3重量%玻璃料粉末(料的组成为41.2重量%SiO2,39.9重量%B2O3,5.1重量%Al2O3,10.3重量%Na2O,1.3重量%Li2O,2.1重量%MgO/CaO,痕量K2O),27.7重量%霞石正长岩,20重量%6号Kentucky球土,10重量%硅酸钠,4.7重量%燧石(石英),4.3重量%碳酸锂,1重量%硅灰石和2重量%纯铝酸钴尖晶石。所用霞石正长岩、6号Kentucky球土、硅酸钠、燧石、碳酸锂和硅灰石的化学组成列在表Ⅰ中。
                           表Ⅰ.氧化物    霞石正长岩    6号    硅酸钠    燧石    碳酸锂    硅灰石(重量%)                Kenfucky
                    球土SiO2     60.2          64.0    76.2     99.6              50.9Al2O3   23.2          23.2             0.2               0.3Na2O     10.6          0.2     23.8             0.2K2O      5.1           0.4Li2O                                            40.1MgO                     0.3                                0.1CaO       0.3           0.1                                46.9杂质      0.1           3.4              0.1     0.1       0.9烧失量    0.4           8.7              0.1     59.6      0.9
制备结合剂是将其原料在一个Sweco振动磨中干混3小时。将此制成的结合剂与60粒度号的晶种溶胶-凝胶法氧化铝和高纯电熔白氧化铝的1比1混和磨料进行混合。再将它在-Hobart N-50揉面机(其容量为2千克混料)中以低速与糊精结合剂粉末、液体动物胶和作为润湿剂的0.1%乙二醇进一步进行混合。然后将混过的料过14目筛以破碎结块,在一个三腔式棒模装置中压制成尺寸为4英寸×1英寸×1/2英寸的棒。将这些棒样煅烧,条件为:在一间歇窑中以每小时40℃的速度由室温升至1000℃,在该温度保持8小时,然后冷却至室温。
采用上述步骤用Norton标准商用结合剂也制备了一些试样棒。
这些试样棒在一Instron Model 4204机械性能试验机上进行了无切口弯曲试验,用一个支承跨距为3英寸的4点式弯曲试验夹具,负荷跨距为1英寸,负荷施加速率为每分钟十字头移动0.050英寸。对煅烧后结合剂含量由10重量%至30重量%的一些磨料试样棒,进行了试验。结果示于表Ⅱ。
表Ⅱ
强度测量结果
断裂模数与煅烧后结合剂含量的关系
煅烧后结合剂含量    (重量%)    标准结合剂(psi)    新结合剂
0.100                9.1        6070               6336
0.150                13.0       6813               6881
0.200                16.7       6737               7298
0.250                20.0       2776               6723
0.300                23.1       --                 7262
实施例2
对晶种溶胶-凝胶法磨料分别用本发明新结合剂与Norton标准商用结合剂制备了砂轮,测量比较了它们的磨损面损和径向磨损。新结合剂的组成与用于实施例1的新结合剂相同。制备结合剂是将其原料在一个Sweco振动磨中干混3小时。将此结合剂与磨料等再进行混合。所得磨料混料含有76.56重量%磨料(它本身是含50重量%的120粒度号晶种溶胶-凝胶法丝料、43.54重量%的70粒度号高纯电熔白氧化铝、6.46重量%的尺寸细于36目的气泡氧化铝)、18.47重量%结合剂、1.38重量%糊精、3.06重量%液体动物胶、0.34重量%水、0.18重量%乙二醇。将此磨料混料模压成10英寸-3/16英寸×0.580英寸×5.025英寸的砂轮,其生坯密度为2.190克/毫升。将此砂轮生坯在一间歇密中以每小时40℃的升温速度由室温升至1000℃,保温8小时进行煅烧,然后冷却至室温。
采用Norton标准商用结合剂也制造了一些砂轮,该结合剂是将其原料在Norton生产设备中用标准生产方法制备的。用此结合剂也制成磨料混料。所得磨料混料含有76.27重量%磨料(它本身是含50重量%的120粒度号晶种溶胶-凝胶法丝料、43.54重量%的70粒度号高纯电熔百氧化铝,6.46重量%的尺寸细于36目的气泡氧化铝)、20.34重量%结合剂、0.92重量%糊精、2.30重量%的一种混合物(含40重量%液体动物胶、30重量%苹果酸粉末、30重量%水)、0.18重量%乙二醇。制造这种标准砂轮是为了同81重量%磨料与19重量%玻璃质结合剂的试验砂轮作对照。砂轮的煅烧都是采用一种煅烧均热温度为900℃的生产循环进行的。砂轮在-Bryant Lectraline LL3 I.D./O.D.(10匹马力)磨床上按说明书所述的条件用湿圆柱形全面进磨法进行了试验。结果(表Ⅲ和表Ⅳ.)表明,圆角保持性能有了改善。
表Ⅲ
径向进给量与磨损面积关系径向进给量                   磨损面积(英寸2)
                标准结合剂            新结合剂(英寸)    #1         #2         #30.36     .000062    .000043    .000053    .000038.40      .000078    .000066    .000062    .000048.44      .000084    .000071    .000067    .000051.48      .000097    .000084    .000080    .000059
表Ⅳ
径向进给量的径向磨损的关系径向进给量                径向磨损(英寸)
              标准结合剂        新结合剂(英寸)    #1       #2       #30.36     .0024    .0021    .0022    .00140.40     .0027    .0024    .0022    .00180.44     .0032    .0027    .0022    .00190.48     .0034    .0026    .0024    .0020
实施例3
对晶种溶胶-凝胶法磨料分别用本发明新结合剂与Norton标准商用结合剂制备了砂轮,测量比较了它们的磨损面积和径向磨损。新结合剂的组成与用于实施例1的新结合剂相同。制备结合剂是将其原料在一个Sweco振动磨中干混3小时。将此结合剂与磨料等再进行混合。所得磨料混料含有83.56重量%磨料(它本身是含25重量%的70粒度号晶种溶胶-凝胶法氧化铝、25重量%的80粒度号晶种熔胶-凝胶法氧化铝50重量%的70粒度号高纯电熔白氧化铝)12.47重量%结合剂、0.84重量%糊精、2.97重量%液体动物胶、0.17重量%乙二醇。将此磨料混料模压成10英寸-3/16英寸×0.580英寸×5.025英寸的砂轮,其生坯密度为2.341克/毫升。将此的砂轮生坯在一间歇窑中以每小时40℃的升温速度由室温升到1000℃,保温8小时进行煅烧,然后冷却至室温。
采用Norton标准商用结合剂也制造了一些砂轮,该结合剂是将其原料在Norton生产设备中用标准生产方法制备的。用此结合剂也制成磨料混料。所得磨料混料含有83.68重量%磨料(它本身是含25重量%的70粒度号晶种溶胶-凝胶法氧化铝、25重量%的80粒度号晶种溶胶-凝胶法氧化铝、50重量%的70粒度号高纯电熔血氧化铝)13.82重量%结合剂、0.50重量%糊精、1.82重量%的一种混合物(含40重量%液体的动物胶、30重量%苹果酸粉末、30重量%水)、0.18重量%乙二醇。这种混料也压制成砂轮(其尺寸与上述新结合剂的情况相同,并采用一煅烧均热温度为900℃的生产循环进行煅烧。制造这种标准砂轮是为了同87.4重量%磨料与12.6重量%玻璃质结合剂的试验砂轮作对照。砂轮在-Bryant Lectra-line LL3 I、D./O.D.(10匹马力)磨床上按说明书所述的条件用湿圆柱形全面进磨法进行了试验。结果(表Ⅴ和表Ⅵ)表明,边缘保持性能有了改善。
表Ⅴ
径向进给量与磨损面积的关系径向进给量          标准结合剂 新结合剂(英寸)    #4        #50.20     ----       .000066    ----0.24     .000049    .000080    ----0.28     .000069    .000084    ----0.32     .00000069  ----       ----0.36     .00000074  .000100    .0000450.40     .000084    .000130    .000054
0.44    .000099    .000140    .000075
0.48    .000100    .000170    .000100
表Ⅵ
径向进合量与径向磨损的关系
径向进给量      标准结合剂  新结合剂
(英寸)  #4      #5
0.20    ----    .0025       ----
0.24    .0018   .0031       ----
0.28    .0019   .0037       ----
0.32    .0025   .----       ----
0.36    .0024   .0036       .0015
0.40    .0029   .0044       .0021
0.44    .0027   .0043       .0022
0.48    .0034   .0048       .0027
可以理解,本领域的技术人员不难知道并且能够进行那些在不背离本发明的范围和精神条件可作的各种各样的修改。因此,所列举的权利要求的范围并非限于上面的叙述,这些权利要求应被认为覆盖本发明的所有可授予专利的新颖特征,包括那些本发明领域技术人员可视为与这些新颖特征等当的特征在内。

Claims (4)

1.一种砂轮,其特征在于:它含有溶胶-凝胶法氧化铝磨料和玻璃质结合剂,经煅烧后,此玻璃质结合剂含有:2.0-3.4重量%Li2O,7-11重量%Na2O,0.5-2.5重量%K2O,52-62重量%SiO2,12-16重量%Al2O3,9-16重量%B2O3
2.如权利要求1所述的砂轮,其特征在于:其中的溶胶-凝胶法氧化铝在制备过程中是使用晶种的。
3.如权利要求2所述的砂轮,其特征在于:其中的溶胶-凝胶法氧化铝在制备过程中是使用α氧化铝晶种的。
4.一种用于溶胶-凝胶法氧化铝砂轮的玻璃质结合剂,其特征在于它含有:2.0-3.4重量%Li2O,7-11重量%Na2O,0.5-2.5重量%K2O,52-62重量%SiO2,12-16重量%Al2O3,9-16重量%B2O3
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CN1115706A (zh) 1996-01-31
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AU6596594A (en) 1995-02-09
US5401284A (en) 1995-03-28
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CA2127328C (en) 1999-03-23
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HUT70361A (en) 1995-10-30
RU2139181C1 (ru) 1999-10-10
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EP0636457A1 (en) 1995-02-01
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US5573561A (en) 1996-11-12
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AU671912B2 (en) 1996-09-12
EP0636457B1 (en) 2003-09-24
ATE250484T1 (de) 2003-10-15
HU9402246D0 (en) 1994-09-28
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