CN1034347C - 纤维强化金属 - Google Patents

纤维强化金属 Download PDF

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CN1034347C
CN1034347C CN90103216A CN90103216A CN1034347C CN 1034347 C CN1034347 C CN 1034347C CN 90103216 A CN90103216 A CN 90103216A CN 90103216 A CN90103216 A CN 90103216A CN 1034347 C CN1034347 C CN 1034347C
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菅沼克昭
藤井浩之
水口博义
加田胜彦
长船晴夫
金丸训明
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Abstract

本发明涉及一种使纤维复合在金属中从而能获得金属单独不能达到之物性的纤维强化金属。以前的纤维强化金属使用碳素纤维，纤维作为复合纤维，但对金属的润湿性不好，因而不能得到高弹性纤维强化金属。而本发明是使用含氮量为8原子%以上的氧氮化物玻璃纤维作为复合纤维，因而解决了以前的问题。即本发明之纤维强化金属与原来的相比较，具有更高的拉伸强度和弹性模量。

Description

纤维强化金属
本发明涉及玻璃纤维强化金属。
纤维强化金属(FRM)由于在金属中复合了纤维，因而能获得金属单独不能达到的物性。这种纤维强化金属(FRM)，有代表性的可举出以前用碳素纤维、陶瓷纤维(Sic，Si-Ti-C-O(チラノ纤维)，氧化铝，硼)、玻璃纤维等强化铝合金，使基质金属具有高拉伸强度和刚性以及低的热膨胀系数。
但是，以前的纤维强化金属，例如用碳素纤维作强化纤维时，熔融铝和强化纤维反应而形成碳化铝Al C，以致纤维强化金属的强度不够高。陶瓷纤维中，采用SiC，Si-Ti-C-O(チラノ)纤维时，和铝的润湿性差，得不到具有足够强度的纤维强化金属。在氧化铝纤维中，A12O3中含SiO2的纤维与熔融铝反应；而不含SiO2的氧化铝纤维，虽然无反应性而且润湿性也行但强度却低(1.38GPa)。硼纤维的问题是纤维直径大而不能形成复杂形状，因此作为FRM用的强化纤维不能发挥充分机能等。此外，这些陶瓷纤维价格极贵，成本高也是很大问题。作为高强度的有机纤维缆绳(ケブラ-)，其耐热性低，而一般的玻璃纤维与熔融合金之间有反应性，弹性模量和强度也很低。
于是，将以前的强化纤维和金属组合起来形成的FRM，其强化纤维与熔融的基质金属在界面上发生反应，或者存在纤维对熔融金属的润湿性差等问题。也就是说，在FRM制造时，一旦金属基质和强化纤维在界面上发生反应，则制得的FRM其强度很低。如果基质和强化纤维的润湿性差，则两者之间的粘结不充分，这样得到的FRM的强度和弹性模量低，其复合法则也不成立，不能得到足够好的物性。
因此，制造以前的FRM时，采用的方法是在强化纤维表面上镀镍等金属，或用等离子镀敷SiC等无机化合物的方法进行表面处理后，再浸渍基质金属。这种方法需要很高的费用，工程也很繁杂。
本发明者们鉴于以上问题，对于采用高弹性纤维的氧氮化物玻璃作为FRM的强化纤维进行了研究，发现含氮在规定量以上的氧氮化物(オキシナイトライト)玻璃纤维即使不进行镀敷等前处理也不会与熔融金属发生反应，而且润湿性优良，制得的FRM其复合法则也大致成立，基于这种发现，完成了本发明。
本发明提供一种纤维强化金属，其特征在于，它是由含氮量为8原子％以上的玻璃纤维，以及含浸在该玻璃纤维中的基质金属构成。
本发明中是使用含氮量为8原子％以上的氧氮化物玻璃纤维作为强化用纤维。特别是，含氮量在12原子％以上时，纤维对金属的润湿性良好，FRM的强度高。此外，作为原料的Si3N4价格较贵，而且如果含氮量多则会降低其拉丝性，因此，出于这种观点，采用含氮量为8原子％以上的玻璃纤维。
用于本发明FRM的玻璃纤维，特别是具有Si-M-M-O-N系的氧氮化物玻璃纤维，SiO2、Si3N4及M1O的含量最好满足下式(按摩尔％)：
65≤(SiO2＋3Si3N4＋M1O)×100/(100＋2Si3N4)＜100 (a)
0.7≤(SiO2＋3Si3N4)/MO≤2.3                     (b)
(式中，M1是Ca或Ca＋Mg；M2是选自于Al，Sr，La，Ba，Y，Ti，Zr，Ce，Na，K，Sb，B，Cr，Pb，V及Sn中的一种或两种以上的金属)。
因比本发明中用的氧氮化物玻璃具有Si-Ca-M2-O-N或Si-Ca-Mg-M2-O-N玻璃系。金属M可以是单独的，也可以是两种以上组合使用。
该玻璃最好是含SiO2 0-40摩尔％，CaO 26-70摩尔％，MgO 0-20摩尔％以及M2在22原子％以下。
因此，本发明中使用的强化纤维即氧氮化物玻璃的最佳组成应满足下式(按摩尔％)。
(SiO2＋3Si3N4＋CaO＋MgO)×100/(100＋2Si3N4)＝65～100  (a′)
(SiO2＋3Si3N4)/(CaO＋MgO)＝0.7～2.3                   (b′)
式中，CaO是添加的CaO，或能变换成CaO的化合物的摩尔％，而MgO是添加的MgO，或能变换成MgO的化合物的摩尔％。
这种玻璃纤维的纤维直经为3-50μm，而且，可以是连续纤维，也可以是0.5～100mm的短纤维。
作为基质金属，可采用铝、钛、镁、镍、铜以及这些金属的合金。
使基质金属含浸在强化纤维中的方法有多种，但较好的方法是将氧氮化物玻璃纤维放入金属模，将熔融的基质金属注入其中，加压后使之凝固。具体说，将强化纤维放入加热至500～600℃的金属模中，并将加热至800℃左右的熔融铝合金等注入其中，然后以1-数百MPa左右的压力加压，使之冷却凝固从而得到FRM。若按这种方法，则可以在高达约900℃的高温下在空气中制造。
制造本发明之FRM的方法，除上述铸造法外，还可以采用公知的FRM制造方法，例如粉末冶金法，双金属丝法，等离子喷射法，喷镀法，蒸镀法，阴模铸造法，热压法等任何一种方法，制造合适形状的FRM。
按照本发明，则强化纤维和基质金属不会发生反应，且强化纤维能均匀地被基质金属润湿。
以下根据实施例进一步具体地说明本发明。实施例中，％是指摩尔％。
实施例1
(强化纤维的制备)
混合玻璃原料粉(SiO2：8.6％，Si3N4：19.4％，CaO：59.8％，MgO：6.9％，Al2O3：5.2％；含氮量23.4原子％，式(a)＝96.2，式(b)＝1.00)，然后装入钼制坩埚中，用石墨制加热器加热，并从坩埚下部拉出玻璃纤维并拉丝。所谓拉丝，是在1780℃下经过1小时将玻璃熔融后，保持在1570℃，从设在坩埚底的喷咀中使玻璃下落并纤维化，以1000m/分的绕卷速度，绕在绕卷器上。得到的纤维，其拉伸弹性模量为205GPa，拉伸强度：3.62GPa、纤维直径：12μm，密度：2.89g/cm3。
(FRM的制造)
将金属模(5mm×5mm×20mm)保持在550℃，将理顺成一个方向的上述玻璃纤维束0.72g放入其中，保持10分钟。向该模内注入在800℃中熔融的铝合金6061(Al-Mg-Si系的样板材料)，以23MPa加压，在加压下冷却使之凝固。图1是制得的FRM之剖面组织显微镜照片，可以清楚地看到纤维和金属的界面上不发生反应，而纤维之间均匀地浸渍着金属且润湿性良好。进而用EPMA测定，测定结果表明没有元素的移动，没发现纤维和基质金属反应，纤维上也不见损坏。
所得之FRM含氧氮化物纤维50(体积)％，其弯曲弹性模量为137GPa，弯曲强度为1.76GPa。作为基质金属的铝合金6061本身的拉伸弹性模量为68.6GPa，拉伸强度为309MPa。
实施例2
使用的玻璃原料为SiO2 30.5，Si3N4 9.5％，CaO 49.4％，MgO 6.0％，Al2O3 4.6％(含氮量12.6原子％，式(a)＝96.1，式(b)＝1.06)，采用同于实施例1的方法制备玻璃纤维。但是，熔融温度为1700℃，拉丝温度为1510℃。制得之玻璃纤维，其拉伸弹性模量为113GPa，拉伸强度3.43GPa，纤维直径12μm，密度2.85g/cm3。
使用0.71g这种纤维，用实施例1同样的方法制造FRM。制得之FRM的剖面组织显微镜照片示于图2。与图1相同，确认纤维和铝合金的界面上无反应层，纤维之间均匀地浸渍着金属且润湿性也很好。FRM中强化纤维的含量为50(体积)％。制得之FRM，其弯曲弹性模量为88.2GPa，弯曲强度1.67GPa，复合法则也成立。
比较例1
使用的玻璃原料为SiO2 39.3％，Si3N4 4.0％，CaO 46.0％，MgO 5.0％，A12O3 5.0％(含氮量为5.6原子％，式(a)＝95.4，式(b)＝0.99)，用实施例1同样的方法制造玻璃纤维。但是，熔融温度为1600℃，拉丝温度1430℃。所得玻璃纤维的物性是拉伸弹性模量100GPa，拉伸强度3.43GPa，纤维直径12μm，密度2.82g/cm3。
将0.70g这种纤维，用实施例同样方法制造FRM。FRM中强化纤维的含量是50(体积)％，制得的FRM，其弯曲弹性模量66.6GPa，弯曲强度392MPa，铝合金几乎不被强化。
实施例3
(强化纤维的制备)
将玻璃原料粉末(SiO2：35.29％，Si3N4：10.38％，CaO：36.23％，MgO：6.04％，Al2O3：12.08％；含氮量8.1原子％，式(a)＝90，式(b)＝0.83)混合，放入钼制坩埚并用石墨制加热器加热，从喷嘴下部拉出玻璃纤维并纺出丝。纺丝是在1670℃经过2小时将玻璃熔融后，保持在1500℃，从设在坩埚底部的喷嘴将玻璃落下并纤维化，以1000m/分的绕卷速度绕在卷绕器上。所得之纤维其拉伸弹性模量为103GPa，拉伸强度3.43MPa，纤维直径12μm。
(FRM的制造)
用镍制网格箍(35mm×20mm×5mm)将理顺成一个方向的上述玻璃纤维(约5g)包裹起来，连同这种箍放入金属模内，在500℃中保持10分钟，将800℃中熔融的1000系铝熔料注入其中并用6.86GPa加压，在加压下冷却使之凝固。
图3是所得之FRM的剖面组织显微镜照相，可清楚地看出纤维和金属的界面上没有反应，在纤维间均匀地浸渍着金属且润湿性良好。
所得之FRM含有30(体积)％氧氮化物玻璃纤维，其弯曲弹性模量为63.7GPa，弯曲强度为833MPa。作为基质金属的铝(1000系)的弯曲弹性模量为49GPa，弯曲强度为49MPa。
本发明之FRM不必在强化纤维上进行表面处理等特别的前处理，而能得到高拉伸强度和弹性模量。
图1、图2和图3是表示FRM剖面的纤维形状的显微镜照相(1000倍)。

Claims (1)

1.一种纤维强化金属，其特征在于，它是由含氮量为8原子％至23.4原子％的玻璃纤维，以及浸渍在该玻璃纤维中的铝合金所构成。
CN90103216A 1989-06-27 1990-06-26 纤维强化金属 Expired - Fee Related CN1034347C (zh)

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TWI396268B (zh) * 2006-05-25 2013-05-11 Taiwan Semiconductor Mfg 複合連結線與其製造方法
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DE102012011264A1 (de) * 2012-06-07 2013-12-12 Technische Universität Dresden Metallgussverbundbauteil
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TWI648081B (zh) 2016-12-05 2019-01-21 美商愛康運動與健康公司 跑步機中的拉繩阻力機構

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DE69025991D1 (de) 1996-04-25
JPH03103334A (ja) 1991-04-30
KR910001080A (ko) 1991-01-30
CN1048413A (zh) 1991-01-09
DE69025991T2 (de) 1996-08-29
EP0405809B1 (en) 1996-03-20
EP0405809A1 (en) 1991-01-02
JPH0672029B2 (ja) 1994-09-14
KR960001715B1 (ko) 1996-02-03

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