CN108148222B - 一种合金型材及其制备方法 - Google Patents
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Abstract
本发明涉及一种合金型材及其制备方法,包括由合金材料制成的型材基体,所述型材基体表面具有多孔微弧氧化层,所述微弧氧化层表面覆盖有碳纤维缠绕层。本发明的合金型材兼具轻质性、高强度和高耐热性;另外,本发明的方法适于工业生产,成本低,易于操作,适用于需要轻质、超高瞬时温度、高强度和高耐磨性的合金型材的制备,保证合金型材耐受高瞬时温度的同时具有内外一致的高强度,而不会造成型材基体与表面处理层分离的状态。
Description
技术领域
本发明属于合金领域,涉及一种合金型材及其制备方法,尤其涉及一种采用表面微弧氧化及碳纤维缠绕的方法制备的轻质高强度合金管材。
背景技术
Ti基合金具有高强度、高模量、轻质量、低密度、高热导性、高熔点、强抗氧化和抗腐蚀等优异的性能。作为最具前景的高性能轻质结构材料之一,Ti-Al合金被广泛运用于航空航天、高铁和汽车等行业。然而,由于其室温脆性大,延展性较差,且表面耐热性能不足,易磨损的缺点极大地阻碍了其实际应用。特别是在军工领域,制备管材材料时,需要接触面可耐受的屈服强度到达1000MPa以上,瞬时温度到达1000℃以上,并且要求在满足以上强度和耐受温度的前提下,其比重应尽量降低。
发明内容
针对现有技术的不足,本发明提供一种具有高强度和高耐热性的合金型材及其制备方法。
为了解决上述技术问题,本发明的技术方案如下:一种合金型材,包括由合金材料制成的型材基体,所述型材基体表面具有多孔微弧氧化层,所述微弧氧化层表面覆盖有碳纤维缠绕层。
所述碳纤维缠绕层包括碳纤维和粘接剂;优选地,所述粘接剂部分渗入微弧氧化层的空隙中,这样微弧氧化层中的粘接剂和碳纤维缠绕层中的粘接剂连成一体,形成连续相,大大增强碳纤维缠绕层与型材基体之间的结合力。
所述粘接剂包含热固性树脂,优选地,所述热固性树脂包括环氧树脂、不饱和聚酯树脂、乙烯基树脂、酚醛树脂中的一种或多种。
优选地,所述粘接剂为热固性树脂。进一步,所述热固性树脂部分浸入到微弧氧化层的孔隙中。
所述微弧氧化层的厚度为10-100微米,优选为20-80微米。
所述合金型材包括合金管材、合金棒材和合金块中的一种;优选地,所述型材为合金管材。
所述的合金为镁合金、铝合金、钛合金,优选的为钛合金。
所述合金型材为合金管材,所述碳纤维缠绕层的厚度为合金管材管壁厚度的5-50%。
如上所述的合金型材的制备方法,包括如下步骤:
1)对型材基体进行微弧氧化处理,获得表面具有微弧氧化层的型材坯体;
2)对步骤1)获得的型材坯体进行碳纤维缠绕处理,获得合金型材成品。
步骤1)之前,还包括对型材基体进行表面处理的步骤。
进一步地,所述表面处理步骤为本领域常规的表面清洁步骤,优选的,对型材基体依次进行机械抛光,清洗,脱脂和酸碱洗处理,最后将型材基体洗至中性后烘干备用,
优选的,步骤1)中,微弧氧化处理过程中进行恒电流控制,电流密度为10~15A/dm2,同时对电解溶液进行搅拌,氧化时间为10-60min,电解液温度大于65℃;优选的,所述电解液主要由5~25g/L的Na2SO4溶液、5~20g/L的NaCl溶液、3~10g/L的Na5P3O10溶液、1~3g/L的NaOH溶液、表面活性剂和去离子水配置而成;进一步地,所述表面活性剂为脂肪酸甲脂乙氧基化物、醇醚硫酸盐、醇醚磷酸盐、高碳脂肪醇聚氧乙烯醚中其中一种,其总添加量为1~3g/L。
进一步地,微弧氧化处理包括将经过表面处理的合金基管放入电解液中进行微弧氧化的过程;进一步地,对于合金管材,为了改善合金管材内壁的耐磨性能,优选地对合金管材内外、壁同时进行微弧氧化;优选的,在合金管材内外壁同时形成微弧氧化陶瓷膜,其膜厚为10-100μm,取出并水洗后干燥处理。
步骤2)中,进行碳纤维缠绕处理时,先将碳纤维与粘接剂混合,然后将碳纤维与粘接剂混合料缠绕于型材坯体上,固化。
进一步地,步骤2)中,碳纤维缠绕步处理时,将碳纤维从浸胶槽的粘接剂中通过,浸胶槽的温度控制在45-50℃;在合金型材的表面包覆浸胶过的碳纤维,缠绕时对纤维施加一定的张力,其张力为1.5~4kg,缠绕速度保持在200~400mm/s,同时相邻两层碳纤维的缠绕角度为45-90°,并使用压辊沿铺设方向赶压气泡,使粘接剂渗入由微弧氧化所形成的陶瓷孔隙中,加强结合力。
通过微弧氧化技术可以在合金(如钛合金)表面上原位生长多孔硬质陶瓷层(微弧氧化层),使得基底金属和表面硬质陶瓷层完美结合,使基板表面的平均耐受温度可达400°以上,瞬时耐受温度由600℃增加至1000℃以上。同时,这层硬质陶瓷层具有优异的性能,包括高耐磨、耐腐蚀性、良好的高温稳定性及在相当宽的温度范围内具有较高的硬度,对于在高温和腐蚀介质中的摩擦情况下,其摩擦性能远比其他金属材料优异。
碳纤维复合材料具有质轻、高强、高模、耐高温、抗氧化等特性,碳纤维具有极高的比强度,其密度为1.8g/cm3。通过减低合金基层的厚度,再进行碳纤维缠绕处理可以在保证不改变合金本身强度的情况下降低合金的用量。以一般钛合金为例,已知Ti合金密度为4.6g/cm3,使用同体积的碳纤维可降低60%的重量;并且在进行过微弧氧化的外表面进行碳纤维缠绕时,碳纤维缠绕所需的粘接剂也将渗入由微弧氧化所形成的的陶瓷孔隙中,增加碳纤维层与管材的结合力。类似地,可使得碳纤维缠绕层、微弧氧化层和型材基体形成一有机整体,解决传统碳纤维缠绕型材中碳纤维缠绕层易脱落的问题,从而获得轻质、高强、高耐热性能的合金型材。
此外,本发明提供的方法适于工业生产,成本低,易于操作,适用于需要轻质、超高瞬时温度、高强度和高耐磨性的合金型材的制备,可保证所制备的合金型材可耐受高瞬时温度的同时,具有内外一致的高强度,而不会造成型材基体与表面处理层分离的状态。
具体实施方式
以下结合发明人给出的具体实施例对本发明作进一步的说明
需要指出的是,按照本发明的技术方案,以下实施例还可以举出许多,本发明并不限于这些实施例,通过发明人大量的实验结果证明,在本发明提出的配方范围,均可以达到本发明的目的。
实施例1:
取一材质均一的厚度为9.5mmTi基合金基管,并对其依次进行机械抛光,清洗,脱脂和酸碱洗处理,最后将Ti基合金基管洗至中性后,烘干,备用;
将5g/L的Na2SO4溶液、20g/L的NaCl溶液、3g/L的Na5P3O10溶液、1g/LNaOH溶液、1g/L的脂肪酸甲脂乙氧基化物溶液和加入去离子水中配置成电解液;
将表面处理后的Ti基合金基管放入电解液中进行内外壁的微弧氧化,氧化过程中进行恒电流控制,电流密度为10A/dm2,同时对电解溶液进行搅拌,氧化时间为10min,电解液温度控制为65℃;取出内、外壁形成微弧氧化陶瓷膜(微弧氧化层)的Ti基合金基管,水洗后,干燥处理;
将碳纤维从浸胶槽的环氧树脂中通过,浸胶槽的温度控制在45℃;
在形成微弧氧化陶瓷膜的Ti基合金基管的外表面包覆浸胶过的碳纤维,缠绕时对纤维施加一定的张力,初层张力为4kg,每层逐步递减为1.5kg,缠绕速度保持在200mm/s,同时相邻两层碳纤维的缠绕角度为45°,并使用压辊沿铺设方向赶压气泡,使环氧树脂渗入由微弧氧化所形成的陶瓷孔隙中,加强结合力,得到0.5mm的碳纤维缠绕层,获得钛合金管材成品。
实施例2:
取一块材质均一的厚度为7mmTi基合金基管,并对其依次进行机械抛光,清洗,脱脂和酸碱洗处理,最后将Ti基合金基管洗至中性后烘干备用。
将10g/L的Na2SO4溶液,10g/L的NaCl溶液、10g/L的Na5P3O10溶液、1g/LNaOH溶液、3g/L的醇醚硫酸盐溶液加入去离子水中配置成电解液。
将表面处理后的Ti基合金基管放入电解液中进行内外壁的微弧氧化,氧化过程中进行恒电流控制,电流密度为15A/dm2,同时对电解溶液进行搅拌,氧化时间为30min,电解液温度控制为70℃;取出内外壁形成微弧氧化陶瓷膜的Ti基合金基管,水洗后,干燥处理。
将碳纤维从浸胶槽的酚醛树脂中通过,浸胶槽的温度控制在48℃;
在形成微弧氧化陶瓷膜的Ti基合金基管的外表面包覆浸胶过的碳纤维,缠绕时对纤维施加一定的张力,初层张力为4kg,每层逐步递减为1.5kg,缠绕速度保持在300mm/s,同时相邻两层碳纤维的缠绕角度为60°,并使用压辊沿铺设方向赶压气泡,使酚醛树脂渗入由微弧氧化所形成的的陶瓷孔隙中,加强结合力,得到3mm的碳纤维缠绕层,获得钛合金管材成品。
实施例3:
取一块材质均一的厚度为5mmTi基合金基管,并对其依次进行机械抛光,清洗,脱脂和酸碱洗处理,最后将Ti基合金基管洗至中性后烘干备用;
将25g/L的Na2SO4溶液、5g/L的NaCl溶液、3g/L的Na5P3O10溶液、3g/LNaOH溶液、2g/L的高碳脂肪醇聚氧乙烯醚溶液加入去离子水中配置成电解液;
将表面处理后的Ti基合金基管放入电解液中进行内外壁的微弧氧化,氧化过程中进行恒电流控制,电流密度为15A/dm2,同时对电解溶液进行搅拌,氧化时间为60min,电解液温度控制为75℃。取出内外壁形成微弧氧化陶瓷膜的Ti基合金基管,并水洗后干燥处理;
将碳纤维从浸胶槽的不饱和聚酯树脂中通过,浸胶槽的温度控制在50℃;
在形成微弧氧化陶瓷膜的Ti基合金基管的外表面包覆浸胶过的碳纤维,缠绕时对纤维施加一定的张力,初层张力为4kg,每层逐步递减为1.5kg,缠绕速度保持在400mm/s,同时相邻两层碳纤维的缠绕角度为90°,并使用压辊沿铺设方向赶压气泡,使不饱和聚酯树脂渗入由微弧氧化所形成的的陶瓷孔隙中,加强结合力,得到5mm的碳纤维缠绕层,获得钛合金管材成品。
实施例4:
取一块材质均一的厚度为4mmTi基合金基管,并对其依次进行机械抛光,清洗,脱脂和酸碱洗处理,最后将Ti基合金基管洗至中性后烘干备用;
将25g/L的Na2SO4溶液、5g/L的NaCl溶液、3g/L的Na5P3O10溶液、3g/LNaOH溶液、2g/L的高碳脂肪醇聚氧乙烯醚溶液加入去离子水中配置成电解液;
将表面处理后的Ti基合金基管放入电解液中进行内外壁的微弧氧化,氧化过程中进行恒电流控制,电流密度为15A/dm2,同时对电解溶液进行搅拌,氧化时间为60min,电解液温度控制为75℃。取出内外壁形成微弧氧化陶瓷膜的Ti基合金基管,并水洗后干燥处理;
将碳纤维从浸胶槽的不饱和聚酯树脂中通过,浸胶槽的温度控制在50℃;
在形成微弧氧化陶瓷膜的Ti基合金基管的外表面包覆浸胶过的碳纤维,缠绕时对纤维施加一定的张力,初层张力为4kg,每层逐步递减为1.5kg,缠绕速度保持在400mm/s,同时相邻两层碳纤维的缠绕角度为90°,并使用压辊沿铺设方向赶压气泡,使不饱和聚酯树脂渗入由微弧氧化所形成的陶瓷孔隙中,加强结合力,得到6mm的碳纤维缠绕层,获得钛合金管材成品。
将以上实施例1~4中处理完毕的Ti基合金基管及未处理的10mmTi合金基管进行屈服强度、瞬时耐受温度及重量测试。
屈服强度试验:将Ti合金基管放入300kN拉力测试机(济南凯锐),按照室温拉伸试验的国家标准(GB/T228-2002)进行拉伸,测量其屈服强度。
瞬时耐受温度测试:将Ti基合金基管作为烟花发射管进行发射试验,已知烟花发射时瞬时温度高达1000℃,平均温度350℃以上,发射完毕后进行损耗检查。
重量测试:将Ti基合金基管进行重量测量。
其实验数据如表1所示:
表1实施例1-4及未处理的钛合金基管相关实验数据表
实施例1-4中,通过微弧氧化技术在Ti基合金表面上原位生长硬质陶瓷层,使得基底金属和表面氧化陶瓷层完美结合,是一种较为理想的表面处理工艺。这层陶瓷膜具有优异的性能,包括高耐磨、耐腐蚀性、良好的高温稳定性及在相当宽的温度范围内具有较高的硬度,对于在高温和腐蚀介质中的摩擦情况下,其摩擦性能远比其他金属材料优异。
碳纤维具有极高的比强度和高比模量的特性。碳纤维复合材料具有质轻、高强、高模、耐高温、抗氧化等特性,这些特性使其在各个领域被广泛地应用。通过减低合金基层的厚度,再进行碳纤维缠绕处理可以在保证不改变合金本身强度的情况下降低合金的用量,进而降低同体积下的比重。并且在进行过微弧氧化的外表面进行碳纤维缠绕时,碳纤维缠绕所需的粘接剂也将渗入由微弧氧化所形成的陶瓷孔隙中,增加碳纤维层与合金管的粘结力。
从表1的实验结果可明显看出,本发明的合金管材强度明显高于普通合金管材,耐热能力强,高温条件下,表面损耗较小;相比相同尺寸规格的普通合金管材,本发明的合金管材重量明显下降。
上述实施例阐明的内容应当理解为这些实施例仅用于更清楚地说明本发明,而不用于限制本发明的范围,在阅读了本发明之后,本领域技术人员对本发明的各种等价形式的修改均落入本申请所附权利要求所限定的范围。
Claims (8)
1.一种合金型材的制备方法,其特征在于,所述合金型材包括由合金材料制成的型材基体,所述型材基体表面具有多孔微弧氧化层,所述微弧氧化层表面覆盖有碳纤维缠绕层;所述合金型材为合金管材;所述合金为钛合金;所述合金管材内、外壁同时进行微弧氧化;
所述合金管材的厚度为5mm,所述碳纤维缠绕层的厚度为5mm;或者,所述合金管材的厚度为7mm,所述碳纤维缠绕层的厚度为3mm;
包括如下步骤:
1)对型材基体进行微弧氧化处理,获得表面具有微弧氧化层的型材坯体;
2)对步骤1)获得的型材坯体进行碳纤维缠绕处理,获得合金型材成品;
所述步骤1)中微弧氧化处理过程中电流密度为10~15A/dm2,同时对电解溶液进行搅拌,氧化时间为30-60min,电解液温度大于65°C;所述电解液由5~25g/L 的Na2SO4溶液、5~20g/L的NaCl溶液、3~10g/L的Na5P3O10溶液、1~3g/L的NaOH溶液、表面活性剂和去离子水配置而成;
步骤2)中,碳纤维缠绕处理时,在合金型材的表面包覆浸胶过的碳纤维,缠绕时对纤维施加1.5~4kg的张力,缠绕速度保持在200~400mm/s,同时相邻两层碳纤维的缠绕角度为45-90°,并使用压辊沿铺设方向赶压气泡,使粘接剂渗入由微弧氧化所形成的陶瓷孔隙中。
2.根据权利要求1所述的制备方法,其特征在于,步骤1)之前,还包括对型材基体进行表面处理的步骤。
3.根据权利要求1所述的制备方法,其特征在于,步骤2)中,进行碳纤维缠绕处理时,先将碳纤维与粘接剂混合,然后将碳纤维与粘接剂混合料缠绕于型材坯体上,固化。
4.根据权利要求1所述的合金型材的制备方法,其特征在于,所述碳纤维缠绕层包括碳纤维和粘接剂。
5.根据权利要求4所述的合金型材的制备方法,其特征在于,所述粘接剂部分渗入微弧氧化层的空隙中。
6.根据权利要求4所述的合金型材的制备方法,其特征在于,所述粘接剂包含热固性树脂。
7.根据权利要求6所述的合金型材的制备方法,其特征在于,所述热固性树脂包括环氧树脂、不饱和聚酯树脂、乙烯基树脂、酚醛树脂中的一种或多种。
8.根据权利要求1所述的合金型材的制备方法,其特征在于,所述微弧氧化层的厚度为10-100微米。
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