CN1092434A - 复合研磨长丝及其制造方法,其制品及使用该制品的方法 - Google Patents
复合研磨长丝及其制造方法,其制品及使用该制品的方法 Download PDFInfo
- Publication number
- CN1092434A CN1092434A CN93103075A CN93103075A CN1092434A CN 1092434 A CN1092434 A CN 1092434A CN 93103075 A CN93103075 A CN 93103075A CN 93103075 A CN93103075 A CN 93103075A CN 1092434 A CN1092434 A CN 1092434A
- Authority
- CN
- China
- Prior art keywords
- long filament
- multiple grinding
- thermoplastic elastomer
- coremaking
- grinding long
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/40—Yarns in which fibres are united by adhesives; Impregnated yarns or threads
- D02G3/404—Yarns or threads coated with polymeric solutions
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- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46D—MANUFACTURE OF BRUSHES
- A46D1/00—Bristles; Selection of materials for bristles
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- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46D—MANUFACTURE OF BRUSHES
- A46D1/00—Bristles; Selection of materials for bristles
- A46D1/02—Bristles details
- A46D1/023—Bristles with at least a core and at least a partial sheath
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D13/00—Wheels having flexibly-acting working parts, e.g. buffing wheels; Mountings therefor
- B24D13/02—Wheels having flexibly-acting working parts, e.g. buffing wheels; Mountings therefor acting by their periphery
- B24D13/10—Wheels having flexibly-acting working parts, e.g. buffing wheels; Mountings therefor acting by their periphery comprising assemblies of brushes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
- B24D3/20—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
- B24D3/28—Resins or natural or synthetic macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/06—Rod-shaped
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- B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
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- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
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- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
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- D07B5/005—Making ropes or cables from special materials or of particular form characterised by their outer shape or surface properties
- D07B5/006—Making ropes or cables from special materials or of particular form characterised by their outer shape or surface properties by the properties of an outer surface polymeric coating
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Abstract
包括至少一根至少部分涂覆硬化的、充填磨料的
热塑性弹性体的复合研磨长丝,显示出超过早先已知
的研磨长丝的研磨寿命,早先已知的充填磨料的尼龙
长丝具有有限的刚性,并在70℃左右失去其刚性,本
发明的复合研磨长丝比充填磨料的尼龙长丝更为有
效和更耐弯曲疲劳破坏,公开了制造这种长丝和在研
磨制品中应用这些长丝研磨各种工件的方法。
Description
本发明涉及用一种以磨料充填的热塑性弹性体涂覆的复合研磨长丝。
尼龙研磨长丝是五十年代后期开发的一种取代天然研磨长丝的人造研磨长丝,当时开发了一种把磨料颗粒均匀地分散于尼龙基质长丝内的挤压法加工工艺(美国专利No.3,522,342和No.3,947,169)。对尼龙研磨长丝的评论是Watts,J.H.于1988年提出的。这是作者于1988年3月21~24日在制造工程师技术协会举行的WESTEC会议上以“研磨单丝-影响刷具性能的决定性因素”为题的书面报告。正如Watts所说明的,由于这种研磨类型的长丝,新的研磨颗粒得以显露。以致用这种长丝制造的研磨长丝刷具在使用过程中是如此容易复原。尼龙研磨长丝的某些优点是安全、清洁、研磨迅速、成本低、优良的倒圆角和抛光控制、灵活性和便于设计制做。
尼龙和其他热塑性材料的主要性能是它的“记忆”性,对于研磨长丝,在其加工工艺中涉及到“弯曲恢复性”或者说有使弯曲的长丝恢复其最初的展开状态的趋向。尼龙的弯曲恢复一般在90%以上,也就是说在尼龙长丝受弯曲后,可恢复原来展开程度的90%。
如对刷具进行超长时间的运转,大多数充填有磨料的聚合物长丝将形成一种固定的形状,如果刷具的长丝不能复原,则刷具将变软并失去其作用。弯曲恢复取决于长丝的直径、松弛时间、应变、挠曲时间和环境条件。迄今所制得的合成长丝中,尼龙可对长时间周期的变形提供最佳的弯曲恢复性。
发明者发现,不同种类的尼龙虽然可适用于许多用途,但在性质上具有局限性,从而使它们不适应应用于研磨长丝。尼龙研磨长丝具有有限的刚性,当温度接近70℃时可失去其刚性,当温度升高时,将不适宜于用来去除厚重的锈皮和毛刺,耐温性对保持长丝的刚性至关重要。一般来讲,升高温度对所有尼龙聚合物有相似的影响,当测定弯曲(正切)模量时温度升高刚性下降。当用研磨长丝缓慢地磨光时,一般热量产生没有多大问题,因为刷具的速度较慢;然而在短暂强力抛光时,刷具受压部分或在干燥环境下高速研磨,则在研磨长丝的尖端处产生高温。
尼龙研磨长丝的另一个局限性是湿度对尼龙长丝刷具的性能有明显影响,湿度能影响长丝的刚性和刷具的耐用性。尼龙6,12比其他尼龙材料能较好地保持其刚性,在高湿度或在浸透油、溶剂或有水存在的情况下,其刚挺度可是其他类型尼龙的2-3倍。
在所有含有磨料的聚合物长丝中,由于磨料和聚合物没有足够的粘结力,当磨料填充量增加时,其断裂强度和抗弯曲疲劳降低。长丝的弯曲模量可简单地定义为抗弯曲性,用以表征研磨长丝聚合物的内在性能,弯曲模量一般依赖于长丝的直径,由于用同样聚合物制得的一系列研磨长丝的弯曲模量相同,影响长丝刚度的主要特性是长丝的直径和长度。
当运转开始时,含有磨料的尼龙长丝的研磨能力显示出明显良好的研磨性能,其后不到1小时,研磨作用明显下降。图7表示了含磨料尼龙长丝研磨性能的下降情况,其充填的磨料为一般的氧化铝,当长丝连接于轮毂上制成刷具,轮毂旋转时长丝便接触(从而磨光)固定的工作,图7代表了扁碳钢板(1018)在1.36Kg负荷作用下其研磨作用与时间的关系。专门设计一种与刷具相反运转的装置,可使刷具的研磨作用恢复到原先的水平,例如将刷具逆向作用于一金属网,刷具经过这种“修整”,可使研磨得到急剧的增加,这一情况发生在图7中2小时15分的地方。另一个与含磨料尼龙长丝有关的问题是它很差的耐弯曲疲劳性,过长的运转周期,使长丝与轮毂连接处趋于断裂,给使用者带来麻烦,影响刷具的寿命和经济价值。
本发明在提供一种由一预制芯涂覆一种充填有磨料的热塑性弹性体组成的复合研磨长丝之前,提出上述与充填有磨料的尼龙和其他长丝有关的一些问题。这一方法的中心思想是将预制芯涂覆一层磨料外皮与充填有磨料的热塑性长丝比较,具有更高的初始弯曲模量,在时间、湿度、温度和化学环境中具有更为恒定的弯曲模量以及更高的拉伸强度。
与有充填磨料的尼龙长丝比较,复合研磨长丝可允许在其热塑性弹性体涂覆层中加入两倍的研磨颗粒,而其抗弯曲疲劳性不呈现明显下降,可以观察到比增加磨料加入量预期值要高的初始和持续研磨作用,这一特性与热塑性弹性体的结构状态以及复合研磨长丝的制备方法有关。
研磨长丝的试验与生产具有悠久的历史,有代表性的技术是美国专利Nos.2,328,998;2,643,945;2,793,478;2,920,947;3,146,560;3,260,582;3,522,342;3,547,608;3,669,850;3,696,563;3,854,848;4,097,246;4,172,440;4,507,361;4,627,950;4,585,464;4,866,888;和5,068,142。其他包括法国专利申请2,624,773和EPO公告0,282,243。
本发明涉及将预制芯至少部分涂覆有充填磨料的热塑性弹性体组合物组成的复合研磨长丝,该复合研磨长丝具有意外的性质,在粘合聚合物外壳中加入两倍磨料的情况下,显示出比先前已知长丝高出几倍的弯曲疲劳寿命,并可观察到比由于增加磨料加入量所预期的要高的研磨作用。
热塑性弹性体(TPE)是在N.R.Legge,G.Holden,H.E.Schroeder,Hanser Publisher 1987年于纽约所写的《热塑性合成橡胶综合述评》中所确定和论述的(这里以“Legge等”表示)。热塑性弹性体,下文也称为热塑性合成橡胶(由Legge等确定)一般是一种低当量多官能度单体与一种高当量多官能度单体的反应产物,其中低当量多官能度单体可聚合形成硬链段(并与其他硬链段,结晶硬链区或范围相连接),而高当量多官能度聚合物则聚合形成柔软可弯曲的链与硬链区相连接。这类材料未曾建议用于研磨长丝。“热塑性合成橡胶”不同于“热塑性塑料”和“合成橡胶”(对仿天然橡胶材料的一般定义为:在张力下拉伸,具有高拉伸强度,迅速缩回,大致上恢复其原来尺寸)。对于热塑性合成橡胶加热至硬链区熔点温度以上时,形成一均相熔体,这种熔体可用热塑技术(不同于合成橡胶)进行加工,诸如注塑、挤压、吹塑等。接着进行冷却,导致再次形成硬链和软链区,使材料具有弹性,这些情况都不会在热塑性塑料中发生。
一些商业化的热塑性合成橡胶包括嵌段聚酯热塑性合成橡胶,嵌段聚氨酯热塑性合成橡胶,嵌段聚氨酯热塑性合成橡胶与其他热塑性材料的混合物,嵌段聚酰胺热塑性合成橡胶以及离子键热塑性合成橡胶。
这里所用的“嵌段热塑性合成橡胶”是指由按聚合物构成的热塑性合成橡胶,这些聚合物是一种高当量多官能度单体与一种低当量多官能度单体的反应产物。
“离子键热塑性合成橡胶”是指一组由离子聚合物(离子键聚合物)构成的热塑性合成橡胶,离子键热塑性合成橡胶由二个或更多柔性聚合物链在许多位置上通过离子结合体或基团连接在一起而组成。离子键聚合物一般是用一种官能性的单体与一种烯烃类不饱和单体共聚或直接将一种聚合物官能化而制备的。羧基官能化离子键聚合物是用丙烯酸衍生物或甲基丙烯酸与乙烯、苯乙烯和类似的共聚用单体通过自由基共聚作用直接共聚得到的。制得的共聚物一般以游离酸的形式获得,可用金属氢氧化物、金属的醋酸盐及类似的盐类按中和反应达到所要求的程度。
本发明中的复合研磨长丝由预先制得的芯和充填磨料的热塑性合成橡胶涂覆物所组成,有很高的初始研磨水平,在达到平衡的条件下保持其较高的研磨能力,并且其耐弯曲疲劳比充填磨料的尼龙长丝要高。
本发明克服或减少了与先前已知的研磨长丝有关的许多问题。根据本发明提供了一种复合研磨长丝,包括至少一种预先制成的芯,该芯至少有一部分涂覆有一种热塑性合成橡胶,这种热塑性合成橡胶含有分散和固着在其中的研磨颗粒,该热塑性合成橡胶与研磨颗粒一起构成一种硬化组合物。可以认为,本发明范围中的硬化组合物中包含一种以上的热塑性合成橡胶。
此处所用的术语“硬化”指的是当热塑性合成橡胶的温度低于硬链区(嵌段热塑性合成橡胶)或离子束(离子键热塑性合成橡胶)的熔点或分解温度时,该热塑性合成橡胶的物理状态,这一温度是通过ASTM D2117标准测定的。这一术语也可用来描述该热塑性合成橡胶的室温(即10~40℃)硬度(肖氏硬度)。用于本发明的热塑性合成橡胶的室温肖氏硬度(用ASTMD790测定)至少为30,较适宜的范围为30~90。该术语不意味对热塑性合成橡胶/研磨颗粒混合物进行物理或化学处理来增加其硬度。
此处所用的术语“复合研磨长丝”指的是以上述硬化混合物至少涂覆预制芯的一部分,最好是涂覆至少是一种预制芯的整个表面,硬化混合物的横截面对预制芯的横截面的比率范围约为0.5∶1~300∶1,1∶1~10∶1较为可取,1∶1~3∶1更为合适。该横截面被定义为垂直于复合研磨长丝主轴的平面。复合研磨长丝可取任何要求的长度,其横截面的形状可以是圆形、椭圆形、正方形、三角形、矩形、多边形或多叶形(如三叶形、四叶形等)。
“预制芯”指的是在一个或多个涂覆步骤之前的单独步骤中制成的一根或多根芯丝,在第一个涂覆步骤中以充填磨料的热塑性合成橡胶涂覆该预制芯;换句话说,预制芯不是与硬化混合物同步制得的。预制芯的横截面形状不限,但以圆形或矩形截面最为适宜。
预制芯可以是连续单根金属丝,多种连续单根金属丝,多种非金属连续长丝,或者是后两种的混合物。
适宜的预制芯有单根和多股金属芯,亦即普通碳钢、不锈钢和铜芯。其他适用的预制芯包括多种非金属长丝即玻璃、陶瓷和合成有机聚合物材料如芳香族聚酰胺、尼龙、聚酯和聚乙烯醇。
嵌段热塑性合成橡胶最好是一个具有平均官能度不小于2、当量不小于350的高当量多官能单体与一个具有平均官能度不小于2、当量在300以下的低当量多官能单体经缩聚反应的产物,高当量多官能单体在聚合时可形成柔性链段,低当量多官能度单体聚合时可形成硬链段。用于本发明的嵌段热塑性合成橡胶包括聚酯TPEs,聚氨酯TPEs,聚酰胺TPEs,以及硅合成橡胶/聚酰胺嵌段共聚TPEs,可选择适当的具有低和高当量多官能度的单体生产相应的TPE。
该嵌段TPE最好包括“链增长剂”,一种具有2~8个活性氢官能团,在TPE工艺中常用的低分子量(一般来说,当量在300以下)化合物,特别可推荐的是乙二胺和1,4-丁二醇。
TPE和热塑性材料的混合物也用于本发明中,可使本发明中的复合研磨长丝更具有特有的弯曲性能。
本发明的另一方面是一种研磨制品至少包括一种复合研磨长丝,最好装在一个高速旋转的轮毂上,该长丝包括一个至少部分涂覆有热塑性合成橡胶的预制芯,该热塑性合成橡胶内分散和固着有研磨颗粒,由该热塑性合成橡胶和研磨颗粒一起组成为硬化混合物。
本发明的另一方面是制造复合研磨长丝(如上所述)的方法,该方法包含的步骤为:
(a)提供一种TPE熔体,同时与研磨颗粒相混合;
(b)用由熔融热塑性合成橡胶与研磨颗粒组成的一种涂覆物涂覆至少预制芯的一部分;
(c)将涂覆物冷却至足以使熔融的热塑性合成橡胶硬化而形成硬化组合物。
此处推荐的方法以TPE为嵌段聚合物,一台挤压机用于供给TPE熔体,预制芯为合股金属材料或合股非金属材料。这里所用的术语“熔融”指的是在高剪切混合条件下,TPE当加热至温度至少在TPE硬链区或离子束的分解温度以上时的物理状态。
图1~4,4个图中的每个图都是表示按照本发明的复合研磨长丝具体实例的放大透视图,每一个都除去一部分充填磨料的TPE硬化组合物,以显示出预制芯。
图5表示连接有本发明中复合研磨长丝的刷具(刷在旋转情况下)的一个具体化视图;
图6为一挤压模头的横截面图(缩小),剖面图中示出熔融的、充填磨料的TPE和预制芯;
图7以条块图示出用许多以前述工艺制备的尼龙研磨长丝制成的旋转刷具从加工工件上(指在“研磨”工艺中)磨去的重量克数与时间的关系;
图8,11,13,15,21和23以条块图比较用前述工艺加工的尼龙研磨长丝制作的刷具与用本发明复合研磨长丝制作的刷具对1018钢板进行研磨,其磨去量与时间的关系的试验结果;
图9,12,14,16,22和24条块图分别与图8,11,13,15,21和23相类似,比较1008钢网的磨去量;
图10中的曲线表示在本发明复合研磨长丝的TPE涂覆层中增加磨料量对用该复合研磨长丝制作的旋转刷具研磨钢板和钢网的研磨能力的影响;
图17~20条块图表示用本发明的在其硬化混合物中含有各种类型研磨颗粒的复合研磨长丝制作的旋转刷具的对比研磨试验结果;
图25~28条块图示出用本发明复合研磨长丝制作的柱形刷具研磨加工时,工件磨失量与功率水平关系的试验结果。
本发明的四个具体方案10,20,30,40表示在放大的图1~4中,每一个具体化复合研磨长丝都去掉包括TPE和磨料粒子的硬化混合物的一部分,以显示出预制芯。
图1表示复合研磨长丝10的放大透视图,图中的预制芯12,部分被硬化混合物14和研磨颗粒18所涂覆,在该具体化例子中,12是一根1×7的合股预制芯,由7根单根的不锈钢丝16所组成,该TPE硬化混合物14中遍布着许多研磨粒子18,诸如氧化铝研磨颗粒。
图2表示了另一个复合研磨长丝的实施方案,这里的预制芯12a是由许多平行的金属或非金属单丝16a组成。图3是第二种不同的实施方案,此处预制芯12b是由三股3×7结构的16b组成的,每一个1×7的股线是由7根如图1中的单独的金属或非金属的单丝构成的。复合研磨长丝20和30,每一根都具有热塑性合成橡胶的硬化混合物14,含有研磨颗粒18分散和固着在其中的热塑性合成橡胶分别部分地涂覆预制芯12a和12b。从图2中的实施方案可以看出固化混合物可存在于预制芯中的平行单丝之间,因此各单丝之间的间隔可以相等或不等。
图4表示了本发明的另一种复合研磨长丝具体实例的放大透视图。在该具体实例中,预制芯12C是一根单独的连续金属丝或单丝,例如不锈钢或玻璃纤维。如前面的具体实例,芯12C外面是在其中分散和固着了许多研磨颗粒18的TPE硬化混合物14。
用于一般手持工具的本发明的复合研磨长丝的预制芯直径一般不小于0.1mm,而该复合研磨长丝本身的直径范围约1.0~2.0mm。
直径为0.75~1.5mm的本发明复合研磨长丝具有一个临界断裂力(按下面所述的试验,用标准的张力试验仪TM型“Instron”进行测定),其值不小于2.0Kg,50%耐疲劳破坏(即在给定条件下,被测试的刷具上50%长丝从刷具上脱落所需的时间)不小于15分钟;在冷轧钢(1018)板上的研磨效率(单位重量长丝磨去的工件重量)不小于2。正如可在下面实例中看到的,可能要根据工件来权衡这些选择。
热塑性合成橡胶
适用于本发明复合研磨长丝的嵌段TPEs一般推荐用一个具有不少于2个官能度、当量不小于350、在聚合过程中可形成柔性链的高当量多官能度的单体,与一个具有至多2个官能度、当量不大于300、在聚合过程中可形成硬链的当量较低的多官能度单体的反应产物。
链增长剂一般用于嵌段热塑性合成橡胶以增加硬链段及硬链区域,这就可提供一个改变嵌段TPE最终产品物理性能的结构。实用于本发明中嵌段TPE的链增长剂应具有2~8个活性氢官能团,可推荐的是2~4个,2~3个则更为可取,其当量以小于300为宜,小于200更为可取。合适的链增长剂为线性二醇,如乙二醇,1,4-丁二醇,1,6-己二醇和对苯二酚对(2-羟乙基)醚。
适用于本发明复合研磨长丝的嵌段TPEs推荐由嵌段聚酯TPEs,嵌段聚氨酯TPEs以及嵌段聚酰胺TPEs组成,可选择不同的低和高当量多官能度单体,用以生产上述嵌段TPEs中的一种。例如,如果该TPE由一种嵌段聚酯所组成,诸如嵌段共聚(醚酯),其低和高当量多官能度单体可以分别是聚四甲撑对苯二甲酸酯和聚(氧化四甲撑)。如果该TPE由嵌段聚氨酯组成,其低当量多官能度单体可推荐多官能度的异氰酸盐,高当量的多官能度单体可推荐多官能胺类。
低当量多官能度单体占在反应中产生嵌段TPEs的单体总重量的百分比推荐范围为20~60%,20~40%更为可取。
适用于形成离子键TPEs的离子聚合物一般推荐由一种官能化的单体与一种不饱和烯烃单体的反应物组成,或由一种多官能化的预聚物组成。术语“离子键TPEs”和“离子聚合物”包括阴离子聚合物、阳离子聚合物和阴阳离子聚合物。
适用于本发明复合研磨长丝的TPEs(嵌段的和离子键的),其推荐的肖氏硬度值范围为30~90,而50~80更为可取。
嵌段热塑性合成橡胶的机械性能(如断裂强度和断裂伸长)取决于几个因素。组成TPEs的聚合物中硬链段的比例,其化学成分,分子量分布,制备方法以及TPE的热历史都可影响其硬链区形成的程度。增加低当量多官能度单体的比例,能使最终成品TPE的硬度和模量增加,而断裂伸长降低。
嵌段TPEs的最高使用温度取决于组成硬链段的低当量多官能度单体的软化点和熔点。由于长时间应用引起老化,组成柔性链的高当量多官能度单体的稳定性也是很重要的。当增高温度以及降低对硬链区产生影响的硬链段百分比的情况下,TPE的弯曲模量和断裂强度通常会下降。
具有上述性能和推荐用于本发明的TPEs包括那些以Ⅰ式表示的嵌段聚酯及其混合物
式中d和e是2~6范围内的整数,此处的d和e可以相同或不同,但其差别不超过整数1;
X和Y选用的整数应使最终的嵌段聚酯TPE的肖氏硬度范围为30~90
式Ⅰ中嵌段聚酯的总分子量(数均分子量)范围约为20,000~30,000,X约为110~125,Y约为30~115,以5~70最为可取。
本发明中推荐用于形成离子键TPEs的离子聚合物是由一种多官能度的单体与一种不饱和烯烃单体共聚反应的产物及其混合物组成的,该离子聚合物可用式Ⅱ表示
式中R1,R2和R3可以相同或不同,可从由氢、烷基、取代烷基、芳基和取代芳基组成的一组基团中选择;
m和n是相同或不同的整数,其选择应使官能化单体的重量是离子聚合物总重量的3~25%,并使最终离子键TPE产品的肖氏硬度范围为30~90;
D是从由COO和SO3组成的一组基团中选择的官能团;
M是从由Na,Zn,K,Li,Mg,Sr和Pb组成的一组基团中选择的官能团。
式Ⅱ中所表示的离子聚合物,推荐R1=R2=R3=CH3,D=COO,最为可取的离子聚合物是当R1=CH3,D=COO,M=Na的情况,这种已商业化的离子聚合物,例如已知商品名为“Surlyn 8550”(杜邦公司)的产品。
m和n值一般不由制造厂商设定,而是要使选择的数值能使离子键TPE在室温下的肖氏硬度范围为30~90。或者,m和n值可以这样来规定,使离子键TPE熔体流速(称之为“熔融指数”)范围为1g/10min~10g/10min(按ASTM试验D1238-86,规则190/2.16,以前为D1238-79,规则E)。简单地说,该试验包括把试样装入一垂直的气缸圆筒中,加热这个在底部配备有小孔的圆筒,把一个已称重的活塞放入该气缸筒中,然后测定10分钟内从小孔流出的熔融聚合物的克数。
该官能化单体可从丙烯酸、甲基丙烯酸、醋酸乙烯酯等及其共聚物中选择,这里特别推荐丙烯酸和甲基丙烯酸。
烯烃单体可从乙烯、丙烯、丁二烯、苯乙烯等及其共聚物中选择,由于乙烯易于得到,成本低,选择以乙烯作为烯烃单体。
该官能单体和烯烃单体一般推荐采用自由基直接共聚,这是众所周知的工艺,此处不做进一步解释。
制备应用于本发明的嵌段聚酰胺TPEs,特别推荐的是式Ⅲ中表示的那些嵌段聚酰胺类及其混合物
式中PA=一种当量小于300的双官能度聚酰胺;
PE=当量不小于350的双羟基聚醚以及从由双羟基聚氧化乙烯,双羟基聚氧化丙烯和双羟基聚氧化四甲撑组成的一组聚合物中选择的聚合物所组成;
Z=一个整数,该整数的选择应使最终的嵌段聚酰胺TPE的肖氏硬度范围为30~90。
式Ⅲ中的嵌段聚酰胺已经商品化,诸如商品名为“Pebax”的产品,是由Elf Aquitaine Atochem集团生产的,本发明中特别推荐的是肖氏硬度为63和70的该产品。
尽管Z值是制造厂商的专利,且式Ⅲ中的聚合物可由硬度表示其特征,另一方面也可以根据它们的熔体流动速率(如前所述)来表示其特征,其推荐值的范围为1cjm/10min~10cjm/10min(ASTM1238-86,190/2.16)。
特别推荐的应用于制造本发明中聚氨酯TPEs的嵌段聚氨酯是式Ⅳ中表示的那些嵌段聚氨酯及其混合物,式中
多元醇=具有平均分子量范围为600~4000的聚酯多元醇或聚醚多元醇
t=一个整数,该整数的选择应使最终的嵌段聚氨酯的肖氏硬度D范围为30~90
“t”值是根据多元醇的分子量来选择的,一般推荐式Ⅳ中表示的嵌段聚氨酯的数均分子量范围为35,000~45,000。
通常,嵌段聚氨酯是将第一和第二多官能度聚合物和链增长剂于80℃温度以上进行混合来制造的。异氰酸酯官能团对异氰酸酯反应基团的比率推荐范围为0.96~1.1。如比率小于0.96,则聚合物达不到足够大的分子量,而大于1.1,则由于过多的交联反应使热塑性加工困难。
如前所述,TPEs与其他聚合物的混合物已被证实是适用的,如聚氨酯/丙烯腈-丁二烯-苯乙烯的混合物,已知商品名为“Prevall”牌号为3050,3100和3150的产品均是Dow Chemical公司生产。牌号3050产品的熔体流速(ASTM-1238-86,230/2.16)为26g/10min,肖氏硬度约为62。
在那些塑料加工工艺技术中提及的嵌段共聚物如包括有机硅和聚酰亚胺合成橡胶共聚物的TPEs,同样被证实适用于本发明的复合研磨长丝。
已经工业化的热塑性有机硅和聚酰亚胺合成橡胶共聚物包括那些GE Silicones公司生产的已知商品名为“Siltem STM-1500”的产品。
上面式Ⅰ-Ⅳ中的每一种聚合物都将进行详细的讨论。
嵌段聚酯类
如上面所提到的,如果TPE是以嵌段聚酯为基础的,诸如式Ⅰ中的嵌段共聚醚酯)则分别推荐基于在聚合过程中形成硬链段的聚(对苯二甲酸二丁酯)和在聚合过程中形成柔性链段的聚(氧化四甲撑)的低和高当量多官能度单体。共聚(醚酯)的聚(醚)成分推荐数均分子量范围为1000~2000的α-氢化-ω-羟基齐聚物(氧化四甲撑)的衍生物。共聚(醚酯)中聚(酯)成分推荐基于数均分子量范围为600~3000,在聚合过程中形成硬链段的聚(对苯二甲酸二丁酯)。式Ⅰ中共聚醚酯的分子量范围为,20,000~40,000。
离子聚合物类
在离子键TPEs中起作用以及适用于本发明的离子聚合物,诸如商品名为“SURLYN”(式Ⅱ)的那些离子聚合物推荐用一种官能化单体和一种不饱和烯烃单体进行共聚,或如上所述对一种制成的聚合物直接官能化来制取。特别推荐用式Ⅱ中的离子聚合物来制取本发明复合研磨长丝中用于硬化混合物的离子键TPEs。大量工业用的乙烯/甲基丙烯酸共聚物,例如含有5至20重量百分比的甲基丙烯酸成分,使这些离子聚合物特别适用于本发明。
式Ⅱ中的M一般推荐从钠(Na)和锌(Zn)中选择,虽然采用钾(K)、锂(Li)、镁(Mg)、锶(Sr)和铅(Pb)的离子聚合物也在式Ⅱ的考虑范围之内。
嵌段聚酰胺类
式Ⅲ中以及适用于形成本发明中嵌段聚酰胺TPEs的聚酰胺类一般被称作聚醚嵌段酰胺类(或“PEBA”),后者可通过双羟基聚醚链段和二羧酸聚酰胺链段在熔融状态下的缩聚反应制得,如式Ⅲ(这里PA表示“聚酰胺”,PE表示“聚酯”)所示。二羧基聚酰胺链段可通过聚酰胺母体与一种二羧酸链限制剂反应制得,该反应推荐在高温(230°以上)和压力(达2.5MPa)下进行。该聚酰胺链段的分子量由适当的链限制剂来控制。
该聚酰胺母体可从氨基酸(诸如氨基十一[烷]酸和氨基十二[烷]酸);内酰胺(如己内酰胺,十二烷基内酰胺等);二羧酸(如己二酸,壬二酸,十二烷酸等)以及二元胺(如己二胺-1,6,十二甲撑二胺等)中选择。
双羟聚醚链段可用下列两种不同的反应之一形成的聚醚母体来生产:环氧乙烷和环氧丙烷离子聚合生成双羟聚氧化乙烯和双羟聚氧化丙烯聚醚母体;四氢呋喃阳离子聚合制取双羟聚氧化四甲撑聚醚母体。
然后该聚醚嵌段酰胺通过聚酰胺母体和双羟聚醚母体的嵌段共聚来制取。该嵌段共聚是一个聚酯化作用,一般在高温(230~280℃)和真空(10~1,400Pa)下进行,并应用一种适当的催化剂,如Ti(OR)4,此处R是一个短链烷基,聚合时尚需加入如抗氧剂和/或光学增白剂这类添加剂。
所得到的聚醚嵌段酰胺的结构为刚性聚酰胺链段和柔性聚醚链段组成的线性规整链。由于聚酰胺和聚醚链段不是可混合的聚醚嵌段酰胺,即诸如式Ⅲ中表示的一种表现为“两相”结构,每一链段对聚合物贡献其自身的性质。
嵌段聚氨酯类
用于本发明的嵌段聚氨酯TPEs,可按式Ⅳ中的嵌段聚氨酯制取,如前所述,它由一种高当量的多官能度单体和一种低当量的多官能度单体组成,它还可以包含一种低分子量的链增长剂。在热塑性聚氨酯合成橡胶中,其硬链段是通过把链增长剂(例如1,4-丁二醇)加入到二异氰酸酯(例如4,4′-二苯甲烷二异氰酸酯(MDI))中形成的。其柔性链包括长柔性聚醚或聚酯聚合链,该聚合链连接二个或二个以上的硬链段。在室温下,该低熔点的柔性链与极性的高熔点的硬链互不相容,可导致一种微相分离。
适用于形成嵌段聚氨酯TPEs的聚氨酯一般是由具有平均分子量600~4,000(高当量多官能度单体)的长链多元醇,分子量60~400的链增长剂和聚异氰酸酯类(低当量多官能度单体)制取的。推荐的长链多元醇为羟基封端聚酯和羟基封端聚醚。
一种推荐的羟基封端聚酯是从己二酸和过量的多元醇,诸如乙烯多元醇,1,4-丁二醇,1,6-己二醇,新戊基多元醇,或这些二醇的混合物制取的。
式Ⅳ中适用于制造本发明复合研磨长丝的嵌段聚氨酯TPEs用的聚氨酯的长链聚醚多元醇,推荐以下两种:聚(氧化丙烯)二醇和聚(氧化四甲撑)二醇。前一种二醇可在碱催化作用下把环氧丙烷和/或环氧乙烷加成为双官能度的引发剂如丙二醇或水制成;后者可通过四氢呋喃的阳离子催化聚合作用制备。这两类聚醚都具有2个官能度,四氢呋喃和环氧乙烷或环氧丙烷的混合聚醚可有效地用作聚氨酯TPE中的柔性链段。
与其他聚氨酯比较,只有少数异氰酸酯适合于生产热塑性聚氨酯合成橡胶。最实用的可推荐的为上面提到的MDI,其他有1,6-己二异氰酸酯(HDI),1-异氰酸根合-3-异氰酸根合甲基-3,5,5-三甲基环己烷(IPDI);2,4和2,6-甲苯二异氰酸酯(TPI);1,4-苯二异氰酸酯和反式-环己烷-1,4-二异氰酸酯。
预制芯
适用于本发明的预制芯材料可视为研磨涂覆层的基质,该基质的表面特性、机械性能及其环境稳定性是可以选择或改变的。推荐那种通过选择、并可以改性以使其表面和热塑性合成橡胶之间具有粘合能力的芯材,其重要的机械性能是它在各种化学剂、热和大气条件下的拉伸强度和耐弯曲疲劳性。
适用于本发明复合研磨长丝的预制芯有金属丝诸如不锈钢、铜等;无机纤维如玻璃和陶瓷纤维;合成纤维如聚酰亚胺、粘胶纤维等;天然纤维如棉及其混合物。虽然可以用连续长丝,但还是推荐用上述材料的股线、绳和纱的其他各种型式。这里所用的“股线”指的是捻合在一起的金属丝,而“纱”指的是捻合在一起的非金属单丝。一般采用1×3,1×7,1×19和3×7的结构,其中第一个数字表示股线或纱的根数,第二个数表示每根纱或股线中捻合在一起的各单丝或金属丝的数目。“绳”是指二根或二根以上股线捻合在一起;而“股纱”是指二根或二根以上的纱捻合在一起,其捻向推荐与绳的捻向相反(例如,如果绳为“右手向”捻,则股纱为“左手向”)。另外,预制芯也可以是未加捻的连续金属丝或单丝。推荐的纱线包括玻璃纤维、陶瓷纤维、聚酰亚胺纤维、尼龙纤维、聚对苯二甲酸乙二酯纤维、棉纤维及其股线和混合线。
尽管除了已知制造复合研磨长丝的方法规定范围以外,实际上对直径没有上限要求,而预制芯的推荐直径以不小于0.01mm为宜,更为推荐的直径范围为0.1~0.7mm。
研磨颗粒
研磨颗粒应该是普遍分散和固着于硬化的TPE涂覆层内,用于本发明复合研磨长丝中的研磨颗粒可以是各个单独的研磨颗粒或者是各个单独研磨颗粒的集聚体。适宜的集聚研磨颗粒在美国专利No.4,652,275和No.4,799,939中作了描述,这些研磨颗粒可以是通常用于研磨工艺中的任何已知研磨材料。推荐的研磨颗粒具有大于7Mohs(莫氏)的硬度,大于9Mohs更为可取。适宜的研磨颗粒的例子包括单独的碳化硅金刚砂研磨颗粒(包括高熔点包覆有碳化硅的研磨颗粒),熔凝的氧化铝,热处理熔凝氧化铝,氧化铝氧化锆,立方晶格的一氮化硼,石榴石,浮石,砂子,金刚砂,云母,刚玉,石英,钻石,碳化硼,熔凝氧化铝,烧结氧化铝,α-载氧化铝陶瓷材料。
存在于硬化TPE涂覆层中的研磨颗粒推荐的重量百分比(对TPE和研磨颗粒的总重量)范围是0.1~65,3~60重量百分比更为可取。
加入硬化TPE涂覆层中的研磨颗粒大小根据该复合研磨长丝的用途而定,对于需要剧烈或粗磨的应用,推荐用较大的研磨颗粒,尺寸较小的研磨颗粒推荐用于精加工。推荐的研磨颗粒的平均直径以不超过1/2复合研磨长丝的直径为宜,不超过复合研磨长丝直径的1/3更为可取。
研磨颗粒的表面(或其表面的一部分,或是一部分颗粒的整个表面)可用偶联剂处理,以增加它们在熔融TPE中的固着及分散能力。适宜的偶联剂的例子包括硅烷,锆-铝酸盐以及钛酸盐偶联剂。
研磨制品
本发明的复合研磨长丝可用于连接在各种各样的刷具上,或装备成一开口的、高耸的研磨垫,或固定在各种基片上。图5示出一个本发明的具体装置,是一个具有许多复合研磨长丝51胶着或用其他方法连结在旋转轮毂轴52上的轮刷50。有关这种刷具的结构在以下“试验刷具结构Ⅱ”中进行描述。
本发明的复合研磨长丝可以连续在各种型式和用于各种用途的刷具上,诸如用于清洁,清理毛口,倒圆,对金属、塑料和玻璃基质进行装饰整理等用途。刷具型式包括轮刷,柱形刷(如印刷电路的清洁刷),微型磨床刷,地板擦洗刷,杯刷,轴端刷,漏斗杯底刷,圆形漏斗底杯刷,涂覆杯刷和各种修整用底刷,密封底刷,导向轴焊接刷,各种形状的管刷,蛇管弹簧刷,烟道清洁刷,烟囱及通风管道刷等,在任何一种刷中所用的长丝可能相同或不同。
制造复合研磨长丝的方法
本发明涉及的复合研磨长丝可以用各种不同的加工方法制造,包括将一根或一根以上预制芯通过一模头,当它们通过该模头时,熔融的、充填磨料的TPE就涂覆在这些预制芯上;喷涂充填磨料的、熔融的TPE到预制芯上或将预制芯通过一熔融TPE浴,随即把研磨颗粒施加到熔融的TPE涂覆层上(换言之,研磨颗粒可在熔融的TPE浴中)。研磨颗粒可通过一种力将研磨颗粒喷射到涂覆有TPE的预制芯上,例如用静电力。然而推荐的方法是上述第一种方法,该方法是把一根或一根以上的预制芯通过一模头,至少有一部分预制芯涂覆了熔融的充填磨料的TPE,然后,熔融的TPE冷却形成硬化混合物。
在涉及本发明的一个推荐的方法中,如图6所示,模头60连接在挤压机的出口。挤压机是一种推荐的使TPE熔融并把研磨颗粒混合到熔融TPE中的技术设备。Nungesser等人在美国专利No.3,522,342中的设备和方法是一个可以推荐的方法。图6示出,在剖面图的62中是熔融的充填磨料的TPE(或如已所述的充填磨料的TPE/热塑性聚合物的混合物),单根的预制芯61也在剖面图中。熟悉该工艺的人可以看出聚合物熔体和预制芯如图所示,其流向是从左向右。如图所示,充填磨料的、涂覆TPE的预制芯63从模头60中出来,64是一个螺纹套管接头,用于把模头连接到挤压机上(未示出)。适当的改进模头60就可以做成通过多根预制芯的型式。这些改进取决于技工的熟练技术。
对于每种TPE,挤压机的各区温度和模头的温度是按每种TPE在工业上使用的温度设定的(见表A),其主要限制范围为TPE硬化区或离子束的熔融或分解温度。表A中列出的是挤压区和模头的推荐温度。挤压机(或其他TPE熔体供给方式,如加热罐等)建议将TPE加热到其硬化区或离子束的熔融或分解温度以上(根据TPE种类和牌号而定的范围),同时将熔融的TPE挤压到加热的模头。
研磨颗粒可从挤压机的喂入孔加入到TPE中,推荐及早加入,足以使研磨颗粒充分分散于熔融的TPE中;另一种方法,研磨颗粒可经第二步骤(即在预制芯已涂覆熔融TPE之后)分布于熔融TPE涂覆层内,如静电涂层内。
冷水骤冷装置紧挨着模头的下端,已涂覆熔融TPE的预制芯经骤冷,熔融TPE迅速冷却,在预制芯上形成一个由TPE和研磨颗粒组成的硬化混合物,然后将已涂覆的预制芯卷绕在卷绕辊上。从批量生产复合研磨长丝的观点来看,一种多根预制芯同步涂覆的加工是值得推荐的,这种加工可以用一分配管结构来实现,在这种情况下需要一个以上的卷绕辊。
一般的模头需要一个设置在紧接冷水骤冷装置下端的具有垂直和水平调节功能的滑轮机构,以达到对准模头中预制芯中心及同心涂覆的目的。最近一种已经工业化的模头无需采用单独的调节机构就能提供对准中心的功能。一种由佛罗里达州Genca Die,Clearwater公司制造,已知商品名为“LOVOL”的模头具有四个螺旋体固定的中心结构,使磨粒在熔融TPE中达到令人满意的分散,并达到真正的同心涂覆,而且在改变预制芯材料时,易于把预制芯材料重新穿入。
充填磨料TPE涂覆层的厚度可用在模头中加入机械制作的衬套的方法来改变,涂覆层的厚度也可用加快预制芯通过模头的速度稍加调整,较高的速度可形成较薄的TPE涂覆层,对于试验规模的运转,预制芯的推荐速度约为30~100re/min,30~45re/min更为可取;对于大规模生产运转,生产速度可明显提高,可达300re/min。
以硬化的充填磨料的TPE涂覆的预制芯可以切成具有要求长度的单根复合研磨长丝,在使用前无需使长丝取向提高其拉伸强度。
对制造复合研磨长丝以及用它研磨平板、平网工件的方法的更详细的描述以及性能试验结果将在下面的实例中提供。
实例
提出下列实例作为本发明的例证,但并不只局限于这些实例。在所有的实例中,如果没有其他符号规定,所有分数和百分数都按重量计。“P”指的是经热处理的研磨颗粒,连同研磨颗粒的牌号一起使用,研磨颗粒的“品级”指的是Grinding Wheel研究所(ANSI ASC B74.18-1984)所采用的,“CRS”指的是冷轧钢。
试验方法
耐疲劳破坏
该试验用于评价复合研磨长丝的疲劳破坏,其试验结果可用来预测用本发明复合研磨长丝制作的刷具的使用寿命,所采用的试验步骤发表和公布于杜邦公司塑料产品和树脂部1978年2月发表的标准号为#E-19743的技术报告No.6“耐疲劳以及影响刷具装配材料弯曲寿命的某些因素”中。试验完全按照该试验步骤进行,所不同的是测试仪器上长丝夹持装置改为4个夹具,每个夹具都可进行调整,以便牢固地夹住一根复合研磨长丝。在该试验中,四个夹具接在一个驱动轴上,每一个夹具用于夹紧各单独的复合研磨长丝或用来控制长丝,这些夹具的装配呈90°间隔,每一个与驱动轴中心隔开50mm距离,该驱动轴以500rpm速度旋转,按照每一个试验步骤,根据长丝的直径调节长丝与冲击杆之间的干扰,对于直径为1.02mm的长丝,其干扰为12.22mm;对于直径为1.14mm的长丝,干扰为13.21mm;对于直径为1.27mm的长丝,干扰为16.51;对直径为1.40mm的长丝,干扰则调节至18.16mm。在把四根同样的试验长丝固定在驱动轴上以后,驱动轴开始转动,记录50%长丝断裂所需的时间,该值见表4中实例1~27和对比实例A-F。
试验刷具结构Ⅰ
通过将复合研磨长丝的一端连结到用浇注铝机加工而成的由两部分组成的轮毂上制成研磨刷具。浇注铝机加工毂的第一部分是由一个5mm厚的铝盘组成的,该盘有一32mm的中心孔,外径为102mm,在其周边有一高出4mm的、横截面为正方形的平面。浇注铝机加工毂的第二部分是以一个19mm厚的浇注铝的圆盘加工的,也具有一个32mm的中心孔和102mm的外径。浇注铝毂的第二部分除去在圆盘的一侧有三个环形凸起的平面外,加工成5mm厚,每个园环都与中心孔同心,外圈的、当中的和最里边的三个凸起的环形平面都平行于圆盘的主平面。其最外圈的环形凸起平面具有4×4mm的正方形横截面,其外缘直径为102mm;当中的环形凸起平面的外缘直径为73mm,内缘直径为68mm,该环形平面高出圆盘主平面13mm。由圆盘的一个主平面和中间凸起的平面之间形成的环状面上加工8个大小和距离相等的通过该环状面径向延伸的孔道,每个孔的直径为9mm,相邻孔之间的距离约为3mm。这些孔确定了孔道,复合研磨长丝可随后放进孔道内。最里面的环形凸起平面的内缘直径为32mm,当毂的两部分拼合时就确定了毂的中心孔,该里面的凸起平面的外缘直径(从轴的中心测量)为44mm,高出圆盘主平面13mm。第二毂盘内圈的凸起平面和中间的凸起平面确定了一个平面,第一毂件贴着这个平面安装,第一和第二毂件的凸起的方形横截面相互对置。
大约125~150根长度为83mm的复合研磨长丝的一端放置于八个孔中的每一个孔,足够根数的长丝放置到每个孔内,基本上填满了每一个孔,以两个组分环氧树脂液体树脂混合物(由Rhore Poulenc公司生产的环氧树脂“Epi-Rez”WD-510和美国得克萨斯州Bellaire的Texaco化学公司生产的胺类“Jeffamine”D-230组成)涂在长丝伸进孔内的一端,机加工铝毂的第一部分通过4个与加工铝毂中心距离为42mm的大小相等的孔用4个直径为4mm的螺丝固定在第二部分上,这就使得修剪成约50mm长的复合研磨长丝稍稍形成扇形分布。在室温下(约25℃,以便环氧树脂硬化)经24小时后,随之在60℃下固化约1小时,该复合研磨长丝刷具即制成以待鉴定,该刷具具有一个32mm的中心孔和近200mm的外径。
试验刷具结构Ⅱ
图5示出的是为了用本发明复合研磨长丝制造研磨刷具而制作的模型,一个圆形基板做成为直径3.18Cm的中孔件,该孔可接受一外径略小于3.18Cm的实心圆柱形芯件,基板的一面加工成辐射形槽沟,以便嵌入薄片金属垫,该槽沟呈辐射状延伸,从距离中孔件5Cm处的一个点开始延伸至圆盘周边,一个垂直的圆筒(内径为200mm)固定在具有槽沟的圆盘表面,以使基板的孔与圆筒同心。
然后将垫片置于槽内,该实心的圆柱形芯件插入孔内,然后把许多比槽沟长5Cm的复合研磨长丝排齐,放进垫片之间的空间,这些垫片提供了一个可使预定长度的复合研磨长丝呈辐射状均匀而紧密排列的方法,然后这些长丝朝向中心穿孔的一端被一夹紧环牢固地夹持。
一个聚合物的浇注毂是这样制成的,在50℃温度下把一种液态的两组份环氧树脂(3M公司生产的商品名为“DP-420”的产品)注入实心圆柱形芯件与夹紧环之间形成的中心孔穴中,当树脂完全固化后,将制成的刷具从装置上取下来,然后在实例25-27以及对比实例F中进行试验。
平板研磨试验
含有复合研磨长丝的刷具经称重后分别安装在一个与2.24KW(3hp)电动机相连接、转速为1750rpm的轴上,将一块100mm见方、6mm厚的1018CRS钢板称重后,使之与每个刷具以13.3Pa的压力接触,经15分钟后,将试验刷具与钢板再次称重,以确定钢板与试验刷具减轻的重量。在8个15分钟的试验周期后(总计120分钟),每个刷具的试验结束,计算出其总磨失(钢板减轻的重量),将该值除以2,得到每小时被每个刷具磨失的平均克数。刷具效率(η)以钢板磨失的总重量除以复合研磨长丝磨失的总重量来计算,其结果见表4。
多孔筛网的研磨试验
一些刷具用于多孔钢的研磨试验。在该试验中,用50×150mm16号1008CRS钢制多孔筛网,该筛网带有46%开口的、直径为4mm的交错排列的孔,标准结构号401,已经由美国伊利诺斯州芝加哥Harrington和King冲孔股份公司工业化。这种钢制多孔筛网以研磨刷进行研磨试验,每一试验都采用双层筛网,其结果见表4。
复合研磨长丝的拉伸强度
本发明的复合研磨长丝可按其拉伸强度来评价,拉伸强度是测定拉断100mm长的复合研磨长丝的力,该长丝的每一端被标准张力测试仪(TM型“Instron”)两个夹具中的一个夹住,两个夹具最初距离为25mm,然后以50mm/min的速度拉开,拉断每根长丝所需要的力以千克力表示。
复合研磨长丝挤压加工
根据本发明的各种复合研磨材料是用熔体挤压加工制备的,每一加工位置装有一台内装2个直径为30mm,L/D(长丝比)比为30∶1(Werner-Pfleiderer公司制造,ZSK-30型)正转螺杆的双螺杆挤压机,所采用的热塑性合成橡胶首先由挤压机熔融(各TPE在加热区和模头温度高于表A所载的温度),从挤压机螺杆套筒的喂入孔,经控制加入研磨颗粒。按照实例,不锈钢、芳族聚酰胺、玻璃纤维纱预制芯通过挤压模头拉出来,以使熔融的含磨料的TPE涂覆在预制芯上。所用的挤压模头是美国佛罗里达州Genca Die,Clearwater公司制造的,其商品名为“LOVOL”,从挤压机模头出来的熔融TPE在面对挤压机模头150mm处以水流冷却使涂覆的预制芯固化,然后,以充填磨料的TPE涂覆的预制芯卷绕在各个预制芯/TPE复合物的卷绕辊上,复合研磨长丝从每个辊上切断。值得注意的是,所有用上述方法制备的涂覆预制芯在其缠绕于辊上、切断成长丝以及制成刷具装置之前都不需要进行定向。
所用的TPEs,包括其某些物理性能都列于表1。表2中列出了所采用的各种预制芯,表3为复合研磨长丝实例(1~27)。表4为对比实例A-F,其中列出TPE,研磨颗粒的类型、尺寸大小等。研磨颗粒的含量用标准热熔技术进行测定。
采用上述试验刷具结构Ⅰ的五种充填磨料的尼龙长丝A-E用以与实例1~24相对比。该对比实例长丝A-E的组成列于表4。除了对比实例B长丝是由日本旭化学公司商业化外,所有的对比实例长丝A-E都由杜邦公司商业化(商品名“TYNEX”)。
三个刷具是按试验刷具结构Ⅱ制作的,采用由聚氨酯TPE和ABS三元共聚物的混合物组成的复合研磨长丝(实例25~27)。“对比”实例F用于检验研磨试验。实例F采用与实例8A相类似的复合研磨长丝,所不同的是采用试验刷具结构Ⅱ。实例F的组成列于表4,尽管这种长丝归在本发明之内。
上述研磨试验的结果列于表5,该复合研磨长丝(实例1~27)是根据本发明制造的。表6表示的是对比实例长丝A-F的研磨结果。
结果讨论
图8以条块形式表示用于对比实例A和B与本发明实例1-3工件磨失与时间关系的试验。显而易见,研磨长丝实例A(充填磨料的尼龙,商品名“TYNEX”)开始研磨良好,然而在该试验条件下经1小时后,其研磨能力迅速降至其初始研磨能力的5%以下。对比实例B(充填磨料的尼龙,商品名“ASAHI”)运行良好,但不如实例1-3的复合研磨长丝,复合研磨长丝以较高的研磨水平(克数)开始,较之对比实例能明显地保持其研磨能力。这在对1018CRS钢板的研磨试验(图8)和多孔筛网1008CRS研磨试验(图9)中可以明显地看出来。使用肖氏硬度较高的TPES的聚酯TPE复合研磨长丝对钢板和筛网显示出较好的研磨作用。
耐疲劳试验结果(表4)显示出,充填磨料尼龙长丝(实例A)在10~15分钟内即超过其极限。用较软的聚酯TPE涂覆复合研磨长丝(实例1和4),其可用性可保持2小时以上,而最硬的聚酯涂覆的复合研磨长丝(实例3,7-9)可用时间很短。用涂覆聚酯TPE的复合研磨长丝研磨钢板和钢筛网,以用肖氏硬度为63的聚酯TPE涂覆的复合研磨长丝可获得耐疲劳和研磨效果的最佳平衡。
图10表示实例4(334磨料)复合研磨长丝在1018CRS板(+)和1008CRS筛网(*)上的研磨能力小于实例5(50%磨料)。显示出复合研磨长丝允许较高磨料量而更增加工件的磨失量。
图11和12比较了实例A,4和5在1018CRS板和1008CRS筛网上研磨与时间的关系的试验结果,显示出复合研磨长丝的性能明显优于在很大程度上增加磨料百分含量的充填磨料的尼龙研磨长丝的性能。
图13和14对表3中研磨长丝A,C,2和6的研磨性能进行了比较。本发明的以充填磨料聚酯TPE涂覆的不锈钢预制芯的复合研磨长丝,含氧化铝磨料的复合研磨长丝在1018CRS板和1008CRS筛网上的研磨性能大大优于含碳化硅磨料的复合研磨长丝。实例A,7-9是又一组复合长丝,是用熔凝氧化铝磨粒、热处理氧化铝磨粒和铝陶瓷磨粒(后者商品名“Cubitron”)制备的。图15和16分别表示在类似的钢板和钢筛网上的研磨试验结果。实例7-9中为玻璃股纱预制芯上涂覆充填磨料的肖氏硬度D为72的聚酯TPE,其商品名为“Hytrel7246”。从对充填磨料的尼龙长丝的实验来看,它并不象所预期的那样,也就是说,与用氧化铝或碳化硅充填的热塑性合成橡胶所涂覆的本发明的复合研磨长丝之间在研磨方面并没有任何明显的差异。然而,非常意外的是充填氧化铝和碳化硅磨粒的复合研磨长丝要比充填氧化铝的尼龙研磨长丝对钢板的研磨能力高2~4倍(比较图13和图15),而以热处理氧化铝充填的本发明的复合研磨长丝在钢筛网上表现出明显的优越性(图14,16)。图15和16显示出,当在本发明的复合研磨长丝中使用高牌号的磨粒时,其研磨作用明显增加。
图17-20以条块形式表示,用长丝实例D,E进行对比研磨试验,实例10-13是对比采用P320和P220氧化铝和碳化硅研磨颗粒长丝的性能。实例10-13中的每一个实例,都是用商品名为“Hytrel6356”的嵌段聚酯TPE涂覆于Owens Corning公司生产的产品编码为“OCF G75PY”的玻璃芯纱上。图17表示长丝对铜板的研磨试验结果,图18-20表示用长丝分别对钛,304不锈钢和铝6061 T6的研磨试验结果。
这些数据显示出,当研磨各种不同的工件时,其最终的研磨性能不同。采用320号碳化硅的复合研磨长丝其研磨性能较差,而两种牌号的氧化铝对铜显示出较高的研磨能力。
所提供的钛是一种不寻常的金属工件,在控制充填磨料的尼龙长丝中使用的碳化硅和氧化铝研磨颗粒对这种金属的研磨值最大。
在304不锈钢工件上,其结果明显不同。这种商业化的充填磨料尼龙长丝研磨效率相当低,而在“Hytrel 6356”嵌段聚酯TPE中使用同样研磨颗粒的本发明的复合研磨长丝则非常有效。
最后,在研磨T6061铝制工件时可看到一个非常意外的结果,含有220和320号碳化硅和氧化铝相间的研磨颗粒的复合研磨长丝明显地优于商业化的充填磨料的尼龙长丝。
图21-22以条块形式表示了用实例复合研磨长丝14-16分别对1018CRS板(图21)和1008CRS筛网(图22)的研磨试验结果。这些实例是采用在玻璃股纱预制芯上涂覆充填P120氧化铝磨料的聚酰胺TPE。图21显示出这些长丝应用于钢板上效果并不好,而用于钢筛网上则效果突出(图22)。
图23和24与图21~22相类似,实例长丝17~22对1008CRS筛网(图24)研磨性能好,而对1018CRS板(图23)则效果不佳。
图25~28以条块图形式表示用在毂上装有稠密长丝的圆柱形刷具(外径10.2Cm)的研磨试验结果。长丝E和10~13采用一商品名为“Chemcut”的印刷电路板刷具设备进行比较,该柱形刷以2500rpm的旋转速度按指定的功率水平研磨1018钢,304不锈钢,铜,6061T6铝(分别见图25~28)。本发明的复合研磨长丝明显优于充填磨料的尼龙研磨长丝对1018CRS钢,304不锈钢的研磨作用,而对于铜和T6061铝的研磨则稍稍优于尼龙研磨长丝。
Claims (10)
1、一种复合研磨长丝,其特征在于,不少于一根的预制芯至少部分涂覆其中有磨料颗粒分散和固着的热塑性弹性体,该热塑性弹性体与磨料颗粒一起组成硬化的混合物。
2、根据权利要求1所述的复合研磨长丝,其又一特征在于,该预制芯至少是一种选自金属丝、玻璃纤维、陶瓷纤维、天然纤维、有机合成纤维、无机合成纤维及其混合物的金属丝或纤维材料。
3、根据权利要求1所述的复合研磨长丝,其又一特征在于,该热塑性弹性体选自嵌段热塑性弹性体、离子键热塑性弹性体、热塑性弹性体与热塑性聚合物的共混物及它们的混合物。
4、根据权利要求1所述的复合研磨长丝,其又一特征在于,该预制芯是一种选自玻璃纤维、陶瓷纤维、天然纤维、有机合成纤维、无机合成纤维及其混合物的纤维股纱。
5、根据权利要求3所述的复合研磨长丝,其又一特征在于,该热塑性弹性体的肖氏硬度范围为30~90。
6、一种研磨制品,包括至少一种复合研磨长丝,该复合研磨长丝的特征在于,它具有至少一种至少部分涂覆一种其中分散和固着有研磨颗粒的热塑性弹性体,该热塑性弹性体和研磨颗粒一起组成硬化混合物,其附带条件为,如果有一根以上的复合研磨长丝,这些复合长丝可以是相同的或是不相同的。
7、根据权利要求6所述的研磨制品,其又一特征在于,该预制芯是至少一种选自金属丝、玻璃纤维、陶瓷纤维、天然纤维、合成纤维及其混合物的金属丝或纤维材料。
8、根据权利要求6所述的研磨制品,其又一特征在于,该热塑性弹性体选自嵌段热塑性弹性体、离子键热塑性弹性体、热塑性弹性体与热塑性聚合物的共混物及它们的混合物。
9、一种制造复合研磨长丝的方法,该复合研磨长丝包括至少一种至少部分涂覆其中分散和固着有研磨颗粒的热塑性弹性体,该热塑性弹性体和研磨颗粒一起组成硬化组合物,该方法的特征在于以下步骤:
(a)使热塑性弹性体熔融,并在其中混合研磨颗粒;
(b)用含有熔融的热塑性弹性体和研磨颗粒的涂覆物涂覆至少一部分预制芯;以及
(c)冷却该涂覆层达到足以使熔融热塑性弹性体硬化的温度,如此,形成硬化的组合物。
10、根据权利要求9所述的方法,其又一特征在于,步骤(a)包括使该预制芯和熔融的热塑性弹性体同步通过一个模头。
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- 1993-02-11 JP JP51654893A patent/JP3683581B2/ja not_active Expired - Lifetime
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- 1993-02-11 DE DE69320375T patent/DE69320375T2/de not_active Expired - Fee Related
- 1993-02-11 ES ES93905895T patent/ES2119892T3/es not_active Expired - Lifetime
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- 1993-02-18 ZA ZA931149A patent/ZA931149B/xx unknown
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1995
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Cited By (9)
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CN100358661C (zh) * | 2001-11-13 | 2008-01-02 | 西亚研磨料工业股份公司 | 锯线 |
CN100519084C (zh) * | 2005-10-14 | 2009-07-29 | 广东奔朗超硬材料制品有限公司 | 尼龙增强碳化硅磨块的制作方法 |
US9610670B2 (en) | 2013-06-07 | 2017-04-04 | Apple Inc. | Consumable abrasive tool for creating shiny chamfer |
CN103552002A (zh) * | 2013-11-08 | 2014-02-05 | 谢泽 | 一种基于纤维砂绳涂附磨具的抛光轮 |
CN105098605A (zh) * | 2014-05-21 | 2015-11-25 | 日本特殊陶业株式会社 | 火花塞的制造方法 |
CN104127025A (zh) * | 2014-07-15 | 2014-11-05 | 慈溪市洁达纳米复合材料有限公司 | 一种多股复合研磨用工业刷丝及其制造方法 |
CN107614201A (zh) * | 2015-09-10 | 2018-01-19 | 株式会社伊原合成 | 玻璃纤维增强塑料制的表面加工用线材 |
CN111411432A (zh) * | 2020-03-31 | 2020-07-14 | 江苏工程职业技术学院 | 一种复合结构剑麻包芯多股线及其生产工艺 |
CN111411432B (zh) * | 2020-03-31 | 2022-03-04 | 江苏工程职业技术学院 | 一种复合结构剑麻包芯多股线及其生产工艺 |
Also Published As
Publication number | Publication date |
---|---|
EP0739261B1 (en) | 1998-08-12 |
TW222668B (zh) | 1994-04-21 |
EP0739261A1 (en) | 1996-10-30 |
DE69320375T2 (de) | 1999-05-06 |
US5616411A (en) | 1997-04-01 |
JP3683581B2 (ja) | 2005-08-17 |
AU658494B2 (en) | 1995-04-13 |
DE69320375D1 (de) | 1998-09-17 |
US5460883A (en) | 1995-10-24 |
US5571296A (en) | 1996-11-05 |
US5737794A (en) | 1998-04-14 |
ATE169545T1 (de) | 1998-08-15 |
WO1993018890A1 (en) | 1993-09-30 |
AU3664493A (en) | 1993-10-21 |
JPH07504852A (ja) | 1995-06-01 |
KR950700811A (ko) | 1995-02-20 |
ZA931149B (en) | 1994-08-18 |
BR9306055A (pt) | 1997-11-18 |
CA2128092A1 (en) | 1993-09-30 |
US5518794A (en) | 1996-05-21 |
ES2119892T3 (es) | 1998-10-16 |
MX9301242A (es) | 1993-09-01 |
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