CN107033584B - 一种聚酰胺材料增强专用玄武岩纤维及其制备方法 - Google Patents
一种聚酰胺材料增强专用玄武岩纤维及其制备方法 Download PDFInfo
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- 229920002748 Basalt fiber Polymers 0.000 title claims abstract description 79
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 68
- 229920002647 polyamide Polymers 0.000 title claims abstract description 68
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- 230000002708 enhancing effect Effects 0.000 title claims description 10
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- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 7
- 239000007822 coupling agent Substances 0.000 claims abstract description 5
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000314 lubricant Substances 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims description 34
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 5
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- 238000004033 diameter control Methods 0.000 claims description 3
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
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- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 4
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- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- 241001163600 Bathylaco nigricans Species 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
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- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
本发明公开了一种聚酰胺材料增强专用玄武岩纤维及其制备方法,本发明玄武岩纤维是经过特殊浸润剂在生产过程中的处理而得到的,所述浸润剂包括以下重量份组分:40‑60份的成膜剂、5‑15份的偶联剂、1‑5份润滑剂、10‑20份的改性剂、30‑50份的水;改性剂包括质量比为2‑4︰1‑3︰1‑4的硝酸盐、强碱、季铵盐;该玄武岩纤维由于表面粗糙度大并接枝有大量活性基团,玄武岩纤维与聚酰胺材料之间的化学键合和机械铆合能力强,该玄武岩纤维与聚酰胺材料的相容性好,能在聚酰胺材料中大量添加和应用。
Description
技术领域
本发明涉及玄武岩纤维领域,具体涉及一种聚酰胺材料增强专用玄武岩纤维及其制备方法。
背景技术
玄武岩纤维是一种新出现的新型无机环保绿色高性能纤维材料,是未来我国重点发展的四大高性能纤维之一,它是由二氧化硅、氧化铝、氧化钙、氧化铁和二氧化钛等氧化物组成的玄武岩石料在高温熔融后,通过纺丝工艺制备而成的。玄武岩连续纤维不仅稳定性好,而且还具有电绝缘性、抗腐蚀、抗燃烧、耐高温等多种优异性能,而且,玄武岩纤维的生产工艺产生的废弃物少,对环境污染小,产品废弃后可直接转入生态环境中,无任何危害,因而是一种名副其实的绿色、环保材料。玄武岩连续纤维已在纤维增强复合材料、摩擦材料、造船材料、隔热材料、汽车行业、高温过滤织物以及防护领域等多个方面得到了广泛的应用。
聚酰胺是大分子主链重复单元中含有酰胺基团的高聚物的总称,聚酰胺材料具有良好的综合性能,包括力学性能、耐热性、耐磨损性、耐化学药品性和自润滑性,且摩擦系数低,易于加工;但由于聚酰胺分子具有强极性的特点,导致聚酰胺材料存在吸湿性强,尺寸稳定性差的缺陷,同时,聚酰胺材料阻燃性较差,因此,在某些特殊环境下,聚酰胺材料需要进行阻燃、防水或提高尺寸稳定性等改性处理后才能进行应用。现今对聚酰胺材料的纤维增强改性主要采用玻璃纤维材料进行改性处理,改性效果显著,但玻璃纤维生产成本高、环境污染大,严重限制了玻璃纤维在聚酰胺材料改性中的应用,开发一种成本低廉、绿色环保、性能优异的新型纤维材料替代玻璃纤维对聚酰胺材料进行改性处理的问题急需得到解决。因而,可以预见,将无毒、无污染、来源广泛、性能优异、稳定好的玄武岩纤维用于聚酰胺材料的增强必将是今后提高聚酰胺材料性能的新趋势。但由于现有玄武岩纤维自身结构和性能稳定,纤维表面光滑、表面活性位点少,造成玄武岩纤维在改性过程中难以与聚酰胺材料化学键合和机械铆合形成统一的、稳定的整体,即玄武岩纤维在聚酰胺材料中是独立存在,对聚酰胺材料的增强作用也相对减弱,增强效果不甚理想,玄武岩纤维添加量少。
发明内容
本发明的目的在于克服现有玄武岩纤维与聚酰胺材料相容性差的缺陷,提供一种聚酰胺材料增强专用玄武岩纤维及其制备方法;本发明玄武岩纤维是经过特殊浸润剂在生产过程中的处理而得到的,该玄武岩纤维由于表面粗糙度大并接枝有大量活性基团,玄武岩纤维与聚酰胺材料之间的化学键合和机械铆合能力强,该玄武岩纤维与聚酰胺材料的相容性好,能在聚酰胺材料中大量添加和应用。
为了实现上述发明目的,本发明提供了一种聚酰胺材料增强专用玄武岩纤维的制备方法,包括以下步骤:
(1)将玄武岩矿石进行粉碎处理,得到玄武岩矿石粉体;
(2)将步骤1得到粉体加热,熔融,形成纺丝熔液;
(3)将步骤2得到的纺丝熔液进行拉丝,得到玄武岩纤维原丝;
(4)将步骤3得到的玄武岩纤维原丝用浸润剂进行浸润改性处理;
(5)将步骤4得到的经过浸润改性处理的原丝进行退解、并捻,得到聚酰胺材料增强专用玄武岩纤维。
上述一种聚酰胺材料增强专用玄武岩纤维的制备方法,步骤4中所述浸润剂包括以下重量份组分:40-60份的成膜剂、5-15份的偶联剂、1-5份润滑剂、10-20份的改性剂、30-50份的水;所述浸润剂能快速对玄武岩纤维表面进行腐蚀、活化,形成粗糙表面,并接枝大量活性基团,从而提高玄武岩纤维与聚酰胺材料之间的化学键合和机械铆合能力,提高玄武岩纤维与聚酰胺材料的相容性;所述的机械铆合是指基体材料通过收缩应力包紧粗糙表面的纤维而产生的摩擦结合。
上述浸润剂,其中所述的改性剂包括硝酸盐︰强碱︰季铵盐按质量比2-4︰1-3︰1-4混合而成的混合物;优选的,所述的改性剂包括硝酸盐︰强碱︰季铵盐按质量比3︰2︰2混合而成的混合物。
上述浸润剂,其中所述的硝酸盐为硝酸钠、硝酸钾、硝酸铵中的一种或多种;其中所述的强碱为氢氧化钠、氢氧化钾、氢氧化钙中的一种或多种;其中所述的季铵盐为有机硅季铵盐中的一种或多种;其中所述的成膜剂为聚氨酯;其中所述的偶联剂为硅烷系偶联剂;其中所述的润滑剂为硬脂酸甲酯。
一种聚酰胺材料增强专用玄武岩纤维材料的制备方法,本发明方法将生产过程中得到的中间产物玄武岩纤维原丝用特殊组份的浸润剂进行处理,使纤维表面粗糙度增加并接枝大量活性基团,有助于聚酰胺材料在玄武岩纤维表面进行化学键合和机械铆合,从而直接得到与聚酰胺材料相容性很好的玄武岩纤维;该玄武岩纤维能在聚酰胺材料中大量添加和应用。
上述一种聚酰胺材料增强专用玄武岩纤维的制备方法,其中步骤1中所述的玄武岩矿石粉体粒径为0.1-2mm,粒径越小,加热熔融时速度越快,耗能越低,但粉碎成本增加优选的,所述玄武岩矿石粉体粒径为0.5-1mm。
上述一种聚酰胺材料增强专用玄武岩纤维的制备方法,其中步骤2中所述的熔融温度为1100-1500℃,温度过低,熔融速度慢,耗时长,耗能高,温度过高,对设备要求高,设备成本增加;优选的,所述熔融温度为1250-1350℃。
上述一种聚酰胺材料增强专用玄武岩纤维的制备方法,其中步骤3中所述的拉丝的速度为1500-3000m/min,拉丝速度过快,拉伸张力过大,会造成纤维断裂;拉丝速度过慢,得到的玄武岩纤维直径较大,不利于玄武岩纤维的应用。
上述一种聚酰胺材料增强专用玄武岩纤维的制备方法,其中步骤3中所述的玄武岩纤维原丝直径控制在1-20μm,原丝直径过大,冷却慢,造成纤维内外应力分布不仅,纤维缺陷大,不利于实际应用,原丝直径过小,拉丝工艺操作困难,容易断裂;优选的,所述的玄武岩纤维原丝直径控制在5-10μm。
上述一种聚酰胺材料增强专用玄武岩纤维的制备方法,其中步骤4中所述的浸润剂温度控制在40-70℃,温度越高,反应速度越快,处理效果越好,但温度过高,表面处理程度控制困难,产品质量不稳定;优选的,所述的表面处理温度控制在50-60℃。
为了实现上述发明目的,进一步的,本发明提供了一种聚酰胺材料增强专用玄武岩纤维,所述聚酰胺材料增强专用玄武岩纤维是通过上述制备方法制备得到的;通过上述制备方法制备的得到的聚酰胺材料增强专用玄武岩纤维,表面粗糙度大并接枝有大量活性基团,玄武岩纤维与聚酰胺材料之间的化学键合和机械铆合能力强,与聚酰胺材料的相容性好,能在聚酰胺材料中大量添加和应用。
与现有技术相比,本发明的有益效果:
1、本发明聚酰胺材料增强专用玄武岩纤维的制备方法,利用浸润剂对玄武岩纤维原丝进行快速改性处理,使纤维表面粗糙度增加并接枝大量活性基团,有助于聚酰胺材料在玄武岩纤维表面进行化学键合和机械铆合,提高了玄武岩纤维与聚酰胺材料的相容性。
2、本发明聚酰胺材料增强专用玄武岩纤维的制备方法,直接采用浸润剂对纤维原丝进行改性处理,将纤维的生产和改性合二为一,简化了生产步骤,节约了生产成本,缩短了生产周期。
3、本发明聚酰胺材料增强专用玄武岩纤维,表面粗糙度大并接枝有大量活性基团,玄武岩纤维与聚酰胺材料之间的化学键合和机械铆合能力强,与聚酰胺材料的相容性好,能在聚酰胺材料中大量添加和应用。
具体实施方式
下面结合试验例及具体实施方式对本发明作进一步的详细描述。但不应将此理解为本发明上述主题的范围仅限于以下的实施例,凡基于本发明内容所实现的技术均属于本发明的范围。
实施例1
(1)将玄武岩矿石进行粉碎处理,得到粒径为0.5mm的玄武岩矿石粉体;
(2)将步骤1得到粉体加热,在1250℃温度下进行熔融,形成纺丝熔液;
(3)将步骤2得到的纺丝熔液在2000m/min的速度下进行拉丝,得到直径为5μm的玄武岩纤维原丝;
(4)将步骤3得到的玄武岩纤维原丝在温度为50℃的浸润剂中进行浸润处理;浸润剂组成为:15重量份含有硝酸钠︰氢氧化钠︰甲基二乙氧基硅烷季铵盐按质量比3︰2︰2混合而成的改性剂、50重量份的聚氨酯、40重量份的水、10重量份的硅烷偶联剂和3重量份的硬脂酸甲酯;
(5)将步骤4得到的经过浸润处理的原丝进行退解、并捻,得到聚酰胺材料增强专用玄武岩纤维。
实施例2
(1)将玄武岩矿石进行粉碎处理,得到粒径为1.0mm的玄武岩矿石粉体;
(2)将步骤1得到粉体加热,在1350℃温度下进行熔融,形成纺丝熔液;
(3)将步骤2得到的纺丝熔液在2500m/min的速度下进行拉丝,得到直径为10μm的玄武岩纤维原丝;
(4)将步骤3得到的玄武岩纤维原丝在温度为60℃的浸润剂中进行浸润处理;浸润剂组成为:10重量份含有硝酸钾︰氢氧化钾︰聚硅氧烷季铵盐按质量比2︰1︰1混合而成的改性剂、60重量份的聚氨酯、40重量份的水、15重量份的硅烷偶联剂和1重量份的硬脂酸甲酯;
(5)将步骤4得到的经过浸润处理的原丝进行退解、并捻,得到聚酰胺材料增强专用玄武岩纤维。
实施例3
(1)将玄武岩矿石进行粉碎处理,得到粒径为0.1mm的玄武岩矿石粉体;
(2)将步骤1得到粉体加热,在1100℃温度下进行熔融,形成纺丝熔液;
(3)将步骤2得到的纺丝熔液在3000m/min的速度下进行拉丝,得到直径为1μm的玄武岩纤维原丝;
(4)将步骤3得到的玄武岩纤维原丝在温度为70℃的浸润剂中进行浸润处理;浸润剂组成为:20重量份含有硝酸铵︰氢氧化钙︰三烷氧基硅烷季铵盐质量比4︰3︰4混合而成的改性剂、40重量份的聚氨酯、50重量份的水、5重量份的硅烷偶联剂和5重量份的硬脂酸甲酯;
(5)将步骤4得到的经过浸润处理的原丝进行退解、并捻,得到聚酰胺材料增强专用玄武岩纤维。
实施例4
(1)将玄武岩矿石进行粉碎处理,得到粒径为2mm的玄武岩矿石粉体;
(2)将步骤1得到粉体加热,在1500℃温度下进行熔融,形成纺丝熔液;
(3)将步骤2得到的纺丝熔液在1500m/min的速度下进行拉丝,得到直径为20μm的玄武岩纤维原丝;
(4)将步骤3得到的玄武岩纤维原丝在温度为40℃的浸润剂中进行浸润处理;浸润剂组成为:10重量份含有硝酸钠︰氢氧化钠︰甲基二乙氧基硅烷季铵盐按质量比3︰2︰2混合而成的改性剂、40重量份的聚氨酯、30重量份的水、5重量份的硅烷偶联剂和5重量份的硬脂酸甲酯;
(5)将步骤4得到的经过浸润处理的原丝进行退解、并捻,得到聚酰胺材料增强专用玄武岩纤维。
对比例1
(1)将玄武岩矿石进行粉碎处理,得到粒径为0.5mm的玄武岩矿石粉体;
(2)将步骤1得到粉体加热,在1250℃温度下进行熔融,形成纺丝熔液;
(3)将步骤2得到的纺丝熔液在2000m/min的速度下进行拉丝,得到直径为5μm的玄武岩纤维原丝;
(4)将步骤3得到的玄武岩纤维原丝在温度为50℃的浸润剂中进行浸润处理;浸润剂组成为:50重量份的聚氨酯、40重量份的水、10重量份的硅烷偶联剂和3重量份的硬脂酸甲酯;
(5)将步骤4得到的经过浸润处理的原丝进行退解、并捻,得到玄武岩纤维。
对比例2
(1)将玄武岩矿石进行粉碎处理,得到粒径为0.5mm的玄武岩矿石粉体;
(2)将步骤1得到粉体加热,在1250℃温度下进行熔融,形成纺丝熔液;
(3)将步骤2得到的纺丝熔液在2000m/min的速度下进行拉丝,得到直径为5μm的玄武岩纤维原丝;
(4)将步骤3得到的玄武岩纤维原丝在温度为50℃的浸润剂中进行浸润处理;浸润剂组成为:15重量份含有硝酸钠︰氢氧化钠︰甲基二乙氧基硅烷季铵盐按质量比3︰5︰2混合而成的改性剂、50重量份的聚氨酯、40重量份的水、10重量份的硅烷偶联剂和3重量份的硬脂酸甲酯;
(5)将步骤4得到的经过浸润处理的原丝进行退解、并捻,得到玄武岩纤维。
对比例3
(1)将玄武岩矿石进行粉碎处理,得到粒径为0.5mm的玄武岩矿石粉体;
(2)将步骤1得到粉体加热,在1250℃温度下进行熔融,形成纺丝熔液;
(3)将步骤2得到的纺丝熔液在2000m/min的速度下进行拉丝,得到直径为5μm的玄武岩纤维原丝;
(4)将步骤3得到的玄武岩纤维原丝在温度为50℃的浸润剂中进行浸润处理;浸润剂组成为:15重量份含有硝酸钠︰氢氧化钠︰甲基二乙氧基硅烷季铵盐按质量比3︰2︰6混合而成的改性剂、50重量份的聚氨酯、40重量份的水、10重量份的硅烷偶联剂和3重量份的硬脂酸甲酯;
(5)将步骤4得到的经过浸润处理的原丝进行退解、并捻,得到玄武岩纤维。
将上述实施例1-4和对比例1-3中所制备得到的玄武岩纤维进行性能测试和聚酰胺塑料(PA66 101F拉伸强度83MPa,缺口冲击强度53 J/m,成型收缩率1-2%)增强(玄武岩纤维用量为聚酰胺质量的20%)实验,记录实验结果,记录数据如下:
编号 | 拉伸强度(MPa) | 断裂伸长率(%) | 改性后聚酰胺塑料缺口冲击强度(J/m) | 改性后聚酰胺塑料拉伸强度(MPa) | 改性后聚酰胺塑料成型收缩率(%) |
实施例1 | 3760 | 2.7 | 78 | 118 | 0.2-0.8 |
实施例2 | 3750 | 2.5 | 76 | 115 | 0.2-0.8 |
实施例3 | 3720 | 2.6 | 75 | 116 | 0.2-0.8 |
实施例4 | 3750 | 2.6 | 76 | 117 | 0.2-0.8 |
对比例1 | 3840 | 2.7 | 63 | 96 | 0.7-1.5 |
对比例2 | 3180 | 1.8 | 65 | 101 | 0.4-1.0 |
对比例3 | 3590 | 2.4 | 70 | 105 | 0.5-1.2 |
对上述实验数据分析可知,实施例1-4中采用本发明技术方案制备得到的玄武岩纤维拉申强度和断裂伸长率好,与PA66塑料相容性好,对PA66塑料增强效果显著;而对比例1制备方法中使用的浸润剂为常规浸润剂,制备得到的玄武岩纤维表面光滑、活性基团少,与聚酰胺材料相容性差,与聚酰胺材料的化学键合和机械铆合能力差,对聚酰胺材料增强作用显著减弱;对比例2制备方法中使用的浸润剂不是本发明中所保护的浸润剂组分配比,氢氧化钠用量过大,浸润剂对玄武岩纤维表面侵蚀过渡,对玄武岩纤维结构造成破坏,导致玄武岩纤维的拉伸强度和断裂伸长率显著降低,从而对聚酰胺纤维的增强作用也显著下降;对比例3制备方法中使用的浸润剂不是本发明中所保护的改性剂组分配比,甲基二乙氧基硅烷季铵盐用量过大,浸润剂对玄武岩纤维表面活化作用减弱,玄武岩纤维表面活性基团少,与聚酰胺材料的化学键合能力差,对聚酰胺材料增强作用显著减弱。
Claims (7)
1.一种聚酰胺材料增强专用玄武岩纤维的制备方法,其特征在于,包括以下步骤:
(1)将玄武岩矿石进行粉碎处理,得到玄武岩矿石粉体;
(2)将步骤1得到粉体加热,熔融,形成纺丝熔液;
(3)将步骤2得到的纺丝熔液进行拉丝,得到玄武岩纤维原丝;
(4)将步骤3得到的玄武岩纤维原丝用浸润剂进行浸润改性处理;
(5)将步骤4得到的经过浸润改性处理的原丝进行退解、并捻,得到聚酰胺材料增强专用玄武岩纤维;
所述浸润剂包括以下重量份组分:40-60份的成膜剂、5-15份的偶联剂、1-5份润滑剂、10-20份的改性剂、30-50份的水;改性剂包括质量比为2-4︰1-3︰1-4的硝酸盐、强碱、季铵盐;
所述硝酸盐为硝酸钠、硝酸钾、硝酸铵中的一种或多种;
所述强碱为氢氧化钠、氢氧化钾、氢氧化钙中的一种或多种;
所述季铵盐为有机硅季铵盐;
所述的成膜剂为聚氨酯。
2.根据权利要求1所述的制备方法,其特征在于,步骤1中所述的玄武岩矿石粉体粒径为0.1-2mm。
3.根据权利要求1所述的制备方法,其特征在于,步骤2中熔融温度控制在1100-1500℃。
4.根据权利要求1所述的制备方法,其特征在于,步骤3中拉丝的速度控制在1500-3000m/min。
5.根据权利要求1所述的制备方法,其特征在于,步骤3中玄武岩纤维原丝直径控制在1-20μm。
6.根据权利要求1所述的制备方法,其特征在于,步骤4中浸润剂温度控制在40-70℃。
7.一种聚酰胺材料增强专用玄武岩纤维,其特征在于,是通过权利要求1-6任一项所述的制备方法制备得到的。
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