CN110494234B - 包含用于减少铸造缺陷的添加剂的铸型材料混合物 - Google Patents
包含用于减少铸造缺陷的添加剂的铸型材料混合物 Download PDFInfo
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- CN110494234B CN110494234B CN201880023559.2A CN201880023559A CN110494234B CN 110494234 B CN110494234 B CN 110494234B CN 201880023559 A CN201880023559 A CN 201880023559A CN 110494234 B CN110494234 B CN 110494234B
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Abstract
本发明涉及用于金属铸造的模具或型芯的铸型材料混合物,其包括至少一种耐火铸型基础材料、粘结剂和基于油膏的添加剂。本发明还涉及一种组分体系、一种用于利用铸型材料混合物或组分体系分别制造模具和型芯的方法以及根据该方法制造的模具和型芯。
Description
技术领域
本发明涉及用于金属铸造的模具或型芯的铸型材料混合物,其包括至少一种耐火铸型基础材料、粘结剂和基于油膏的添加剂。本发明还涉及一种包括耐火铸型基础材料、粘结剂和油膏的组分体系、一种用于分别利用铸型材料混合物或组分体系制造模具和型芯的方法、以及根据该方法制造的模具和型芯。
背景技术
铸造模具基本上由模具或者模具和型芯构成,型芯为待生产的铸件的阴模。在此,模具和型芯通常由耐火铸型基础材料、例如石英砂和合适的粘结剂构成,该粘结剂在从铸型工具中取出模具时为铸造模具提供足够的机械强度。耐火铸型基础材料优选以自由流动的形式存在,使得铸型基础材料能够在与粘结剂混合之后倒入到合适的空心模具中、压实并随后固化。
在铸造时,模具形成用于铸件的外壁,型芯用于在铸件内形成空腔。在此,并不绝对必需的是:模具和型芯由相同材料构成。因此,例如在硬模铸造时,借助于金属的永久模具对铸件的外部铸型。由不同组成的铸型材料混合物且根据不同方法制造的模具和型芯的组合也是可行的。
为简单起见,在下文中仅提及型芯,该叙述同样也适用于基于相同铸型材料混合物的且根据相同方法制造的模具,反之亦然。(多个)模具和可能的型芯组合成型芯包,然后用液态金属,如铁、钢、铝、青铜或其他有色金属浇铸。
随后,液态金属填充空腔,从而形成期望的铸件。液态金属尤其例如在铁铸造(铸造温度在大约1300℃至1500℃之间)或钢铸造(铸造温度在大约1500℃至1700℃之间)时的高温,导致有机粘合剂的分解并且加热型芯。
随温度升高,石英砂由于热膨胀而膨胀,直至在573℃时进行从α时石英到β英石英的晶型变化,即所谓的石英相变(Qaurzsprung),这发生突然的体积增加。石英砂的进一步晶型变化发生在1470在、从β4石英到(α)-方石英,这同样伴随体积增加。当然,这种晶型变化不仅取决于相变温度,而且还明显地取决于其他参数,例如粒度或温度-时间梯度。
这种体积变化引起熔融金属-砂的界面附近的砂的微观结构中的机械应力,这会在模具/型芯中导致裂纹,裂纹使得熔融金属进入模具/型芯中进而在铸件表面处产生脉纹。
脉纹是不规则的、细丝状的、薄金属隆起,尤其在铸件的角或角落和边缘处难以将其去除。在使用化学增强铸型材料的情况下,脉纹更容易在铸造部件的内轮廓(型芯)处产生,并且穿过裂纹在液态金属能够渗入的铸型部件表面处形成。这些脉纹是不期望的并且必须费力且费时地将其去除,这与增加的成本相关。在具有窄的穿通部的关键应用中,脉纹可能封闭这些穿通部。在这些部位,很难检测到脉纹并且通常无法将其去除。
其他类型的砂,所谓的特种砂,例如铬矿砂、橄榄石砂、耐火粘土砂、铝土矿砂或者特制的砂,同样可用于制造模具和型芯。
这些砂在20℃至1700℃之间不呈现相变,具有更低的热膨胀且趋向于产生更小的脉纹缺陷。然而,它们也贵得多。公知的是,在砂混合物中使用砂添加剂以避免或减少脉纹缺陷。现有技术中已知四种不同类型的抗脉纹形成添加剂,这些抗脉纹形成添加剂的作用方式彼此不同:
第一种类型是如下的抗脉纹形成添加剂,这些抗脉纹形成添加剂与纯砂混合物相比,通过其自身低的热膨胀减少了石英砂-添加剂混合物的热膨胀。这些添加剂也称为砂替代物,并且基于铸型材料混合物以10至100重量%添加。属于此类的,包括例如硅酸铝,像莫来石珠或所谓的微球。
第二种类型的抗脉纹形成添加剂,包括所谓的“助溶剂”。助溶剂或者与砂表面反应并形成新的矿物,例如添加铁氧化物添加剂之后的铁橄榄石,其由于显著更小的膨胀而降低砂微观结构中的应力,或者其自身或结合其他材料形成粘稠相。这种粘稠相为砂微观结构提供一定的弹性,这有助于避免脉纹,并且这种粘稠相可以在与液态金属的界面处密封孔隙,从而使金属进入砂微观结构变得更难,同样能够避免铸件的表面缺陷。所使用的添加剂的添加量在1至15重量%之间,优选2至10重量%之间,更优选2至8重量%。
第三种类型的抗脉纹添加剂,由与石英砂混合的有机材料构成,并用作占位物。在熔融金属浇铸时加热砂期间,这些材料在500℃几乎无剩余地燃烧,留下间隙并为石英砂提供更大的热膨胀空间。由此,砂微观结构中的机械应力减小,进而也减小脉纹形成的趋势。这种类型的添加剂特别包括木屑、糊精和淀粉。在此,添加量为0.5至8重量%之间,优选0.5至6重量%之间,更优选0.5至5重量%之间。
煤尘或石墨也可用作抗脉纹形成添加剂(第四种类型的抗脉纹形成添加剂),但这些不能明确地将其分类作为已经提及的三种类型之一。虽然,煤或石墨也以一定方式作为占位物,但这些材料的主要作用方式有些不同。在煤和石墨燃烧或热解时,在孔隙空间中产生还原气氛,这种还原气氛能够作为在砂粒表面上的无烟煤形式沉积为过量的碳。这种薄的碳层使得熔融金属润湿砂粒变难,并防止液态金属渗入砂微观结构中。在此,添加量为0.01至10重量%之间,优选0.02至5重量%之间,特别优选0.02至3重量%之间。
对于硅酸钠结合的模具,已知为了改善铸造表面,当然不是与脉纹缺陷相关的情况,而将有机添加剂添加至铸型材料混合物。作为合适的有机添加剂,例如是酚醛树脂如酚醛清漆;环氧树脂如双酚A环氧树脂、双酚F环氧树脂或环氧化酚醛清漆;多元醇如聚乙二醇或聚丙二醇、甘油或聚甘油;聚烯烃如聚乙烯或聚丙烯;烯烃如乙烯和/或丙烯与其它共聚单体如乙酸乙烯酯或苯乙烯和/或二烯单体如丁二烯的共聚物;聚酰胺如聚酰胺-6、聚酰胺-12或聚酰胺-6,6;天然树脂如松香;脂肪酸酯如棕榈酸十六烷基酯;脂肪酸酰胺如乙二胺双硬脂酰胺;金属皂如二价或三价金属的硬脂酸盐或油酸盐;以及碳水化合物如糊精。在WO 2008/046651 A1中描述了合适的碳水化合物。有机添加剂既可以作为纯物质使用,也可以与各种其他有机和/或无机化合物混合使用。分别基于铸型材料,有机添加剂优选以0.01重量%至1.5重量%,特别优选0.05重量%至1.3重量%,更特别优选0.1重量%至1重量%进行添加。
同样,提出具有施胶剂的苯乙烯聚合物可用于改善表面质量,参见WO 2008135247A1。
典型的工业脱模剂例如在EP 2244870 B1中加以披露。其通常或者是硅氧烷的(聚结的)膜,作为溶液或作为乳液被涂覆到工具的内轮廓表面上,或者是固化的脱模漆。假定这种膜的脱模效果由它们对铸型材料混合物中的各组分的润湿性能所决定。
本发明的任务
尽管有大量可行的添加剂,但并未针对所有应用情况解决“脉纹”的问题。为了实现避免脉纹的期望效果,通常必须添加更大量的添加剂。其他的重要特性,如模具和型芯的强度或铸型材料混合物的加工时间通常会受到不利影响。偶尔也会产生其他的铸造缺陷。
添加剂的使用也会导致工具中,例如因红色氧化铁导致的,不期望的污染。于是,这种污染经常导致粘附趋势增加,并且需要更短的型芯盒清洁周期。
本发明人已经提出如下目的:提供新的添加剂,其可以用于所有的常规型芯制造方法中,并且以相对小的量就已经有效并且(附加地以及单独地)降低型芯盒中的粘附趋势。
发明内容
本发明的主题是一种根据独立权利要求的铸型材料混合物,其包括耐火铸型基础材料、粘结剂和油膏,或是一种根据独立权利要求的方法。有利的实施方案是从属权利要求的主题,或是在下文中描述的内容。
令人惊奇地发现:铸型材料混合物中的一部分油膏显著地降低脉纹形成趋势,特别在钢和铁铸造中的脉纹形成趋势。此外,令人惊奇地发现:通过使用油膏减少在铸型工具处的粘附趋势。这具有以下优点:在铸型工具,如射芯机中残留更少的砂粘附残留,从而减少清洁频率,这引起更小的时间损失进而节省成本。
也称为油性橡胶的油膏,是指交联的不饱和酯类,尤其是脂肪油,如不饱和植物油,比如菜籽油、蓖麻籽油、亚麻籽油、大豆油、大麻油、油桐籽油、腰果壳油、花生油、油菜籽油或鱼油。交联脂肪油的特征相应地在于,其是如下甘油三酯,这些甘油三酯分别具有至少两个,优选三个酯基团,其中至少两个、特别是三个酯基团在交联反应之前至少各自具有一个双键。用作初始材料的合适不饱和酯也包括部分氢化的甘油三酯或不饱和的合成脂肪酸酯。因此,在室温(25℃)下,油膏是可以通过一种或多种交联剂作用于不饱和酯或酯基团来制备的固体,特别是类橡胶物质。在交联之后,转化的酯形成三维网络聚合产物。不同油膏彼此混合的混合物也是可行的。油膏既不溶于所用的粘结剂,也不溶于所用的粘结剂的多元醇组分。根据一个优选的实施方式,每个油膏分子平均包括多于两个的交联甘油三酯。
油膏不含有环氧乙烷基团,因而不会与环氧化的脂肪酸酯混淆,该环氧化的脂肪酸酯被用作用于制备作为粘结剂或粘结剂一部分的树脂的单体组成部分(参见,例如DE102013004663 A1和DE 4327292 A1),例如作为环氧树脂或醇酸树脂的一部分。油膏可以作为固体分散在粘结剂中,但其本身不是流体粘结剂。
基于所使用的耐火铸型基础材料,耐火铸型基础材料尤其包括20重量%的石英砂、尤其优选超过40重量%、最优选超过60重量%的石英砂。
根据本发明的铸型材料混合物包括至少:
a)耐火铸型基础材料,
b)粘结剂,和
c)油膏。
具体实施方式
耐火铸型基础材料为一种适合的耐火铸型基础材料或为由多种这种类型的耐火铸型基础材料构成的混合物,其主要包括石英砂,由此石英砂能够作为新砂或再生的旧砂存在或作为由这两者构成的任意混合物存在。根据本发明使用的铸型基础材料尤其包括基于耐火铸型基础材料大于20重量%的石英砂,尤其优选大于40重量%,特别优选大于60重量%的石英砂。
作为耐火铸型基础材料能够使用对于制造浇铸模具常见且已知的材料以及其混合物。适合的例如是石英砂、锆英砂或铬铁矿砂、橄榄石、蛭石、铝土矿、耐火粘土以及所谓的人造铸型基础材料,即通过工业铸型方法球形化的或类似球形的(例如椭圆形的)铸型基础材料。
为此的实例是玻璃珠、玻璃颗粒或人造的、球形的、陶瓷砂(所谓的),以及或“Carboaccucast”和中空微球,如其还可作为组分从飞灰中分离出来,例如硅酸铝空心球(所谓的微球)。上述铸型基础材料的混合物同样是可行的。
将耐火铸型基础材料理解为是指具有高熔点(熔融温度)的物质。优选地,耐火铸型基础材料的熔点或耐火铸型基础材料的组成部分的熔点高于600℃,优选高于900℃,更优选高于1200℃,特别优选高于1500℃。
耐火铸型基础材料优选占铸型材料混合物的大约70重量%、尤其大于80重量%、尤其优选大于85重量%。
耐火铸型基础材料的平均粒径通常为100μm至600μm之间、优选120μm至550μm之间,尤其优选150μm至500μm之间。粒径例如能够通过根据DIN ISO 3310的筛分法确定。尤其优选的是最大长度延伸与最小长度延伸(彼此成直角并且分别针对全部空间方向)为1:1至1:5或1:1至1:3的颗粒形状,即例如不是纤维状的颗粒形状。
耐火铸型基础材料优选具有自由流动的状态,尤其以能够在常规的射芯机中加工根据本发明的铸型材料混合物。
可将不同的无机的和有机的粘合剂体系用作为粘结剂。如下方法和其所属的粘合剂可被列举作为实例:
如在PU冷芯盒或环氧树脂SO2方法中使用的粘结剂更为优选。这一方面是多元醇化合物(特别是苄基醚树脂)和作为粘结剂的多异氰酸酯和作为固化剂的叔胺,另一方面是至少含有环氧树脂和丙烯酸酯的混合物(通过加入二氧化硫而使它们固化)或由其衍生的、胺气体固化的组合粘合剂体系。
将粘合剂添加到铸型基础材料中,并且铸型材料混合物可以包含其他的脉纹形成添加剂。
上述粘结剂的任一种都能够作为粘结剂分别基于铸型材料混合物以大约0.4重量%至大约7重量%,优选大约0.5重量%至大约6重量%,尤其优选大约0.5重量%至大约5重量%的量来使用。
为了制备铸型材料混合物,可首先将粘结剂体系的组分合并,然后加入到耐火铸型基础材料中。但也可行的是:将粘结剂的组分同时或依次以任意顺序添加至耐火铸型基础材料中。可以使用常规方法以实现铸型材料混合物的各组分的均匀混合。
根据本发明的添加剂或根据本发明的铸型材料混合物,含有来自称为“油膏(Faktis)”的物质组的一种或多种代表作为组成部分。
油膏是一种无色、黄色或棕色的类橡胶的物质,其能够通过交联剂(例如氯化硫或硫(硫-油膏)或热的(来自空气中的)氧(氧-油膏)、环氧化物或环氧乙烷(环氧化物-油膏)、四氯化硅(硅-油膏)或二异氰酸酯(异氰酸酯-油膏))对于不饱和脂肪酸酯、如脂肪油的作用来制备。
优选的酯是不饱和脂肪酸的天然甘油三酯,即所谓的脂肪油。合适的脂肪油的实例是菜籽油、油菜籽油、蓖麻油、妥尔油、鲸油、亚麻籽油,大豆油、桐油树油和鱼油,以及部分氢化的甘油三酯和不饱和的合成脂肪酸酯,或它们的混合物。
油膏是固体,或者作为粉末来提供或者作为含水的或含溶剂的分散体来提供,并用作颜料和漆中的添加剂,以改善触觉特性、如柔软感或防滑性。此外,油膏起弹性体构件(例如型材、压力辊或橡皮)中的填料的作用(参见EP 2570451 B1)。当前,优选使用粉末。
根据制备油膏的方法,脂肪油在约120℃至170℃下与5至20重量%的硫反应或在20至70℃下与二氯化二硫反应。在此,形成多硫化物,但硫的一部分也以游离状态存在。此外,存在如下油膏类型,在该油膏类型中双键的交联不通过硫进行,而是通过过氧化物以自由基的方式进行。粉末例如可通过研磨获得。颗粒趋于聚结。
根据EP 0121699 A1中已知的制备方法,获得环氧化物-油膏。在此,首先将不饱和酯环氧化并与交联剂反应以进行交联。
通过首先将不饱和酯(例如脂肪油)环氧化并随后借助于合适的与环氧基团反应的多官能交联剂(如多元羧酸、多胺、多羟基化合物或多硫醇化合物)使其交联,获得环氧化后交联的酯。合适的二元或多元羧酸例如是琥珀酸、邻苯二甲酸、对苯二甲酸和间苯二甲酸和偏苯三酸。合适的多胺例如是乙二胺、二亚乙基三胺、六亚甲基二胺和苯二胺。合适的多羟基化合物例如是甘油、乙二醇、二甘醇、季戊四醇、对苯二酚、连苯三酚和用多元醇酯化的羟基羧酸。合适的多硫醇化合物例如是乙硫醇-1,2-三羟甲基丙烷-三-3-巯基丙酸酯、四-3-巯基丙酸季戊四醇酯和二硫代磷酸。合适的交联剂还可以在分子中包含各种官能团。合适的、至少二价、优选三价的醇例如是甘油、乙二醇、季戊四醇、三羟甲基丙烷和/或山梨糖醇。优选的酯是不饱和脂肪酸的天然甘油三酯,即上述所谓的“脂肪油”。制备细节参见EP0121699 A1。
所使用的油膏不可熔化且不可溶解,在更长时间加热的情况下出现热分解。摩尔量能够在大约30000g/mol至150000g/mol之间,优选在30000至80000g/mol之间,尤其优选在30000至50000g/mol(平均分子量,相应的数均分子量)。
在根据本发明使用的油膏中,基于油膏,硫的总含量(包括S桥)在0至大约20重量%之间,优选在0至大约10重量%之间,尤其优选在0至大约5重量%之间,更尤其优选在0至0.2重量%之间。
根据另一定义方式,分别基于铸型材料混合物,硫的总含量(包括S桥)在0至大约5重量%之间,优选在0至大约3重量%之间,尤其优选在0至大约2重量%之间,更尤其优选在0至0.5重量%之间。
关于粒径,具有约30至约600μm平均直径的油膏用作砂添加剂是尤其适合的,优选约60至约300μm的和尤其优选约80至约200μm的平均直径(使用Horiba LA-950,RetschTechnology,根据DIN ISO 13320基于静态激光散射,在异丙醇中测量,流动池290ml,透射率R 80%至88%,透射率B 85%至90%,在循环和搅拌下,测量前超声1分钟,7级等级中的第3级,探针:130W,28kHz)。
根据本发明的抗脉纹形成添加剂包含油膏或油膏混合物。油膏也能够单独用作抗脉纹形成添加剂,而与其是否作为粉末或分散物存在无关。使用作为粉末的油膏是优选的。
根据本发明,油膏单独的添加量在约0.01至8重量%之间、优选在约0.05至5重量%之间、或在约0.04至5重量%之间,尤其优选在0.1至和3重量%之间,更尤其优选大于0.2且小于1.5重量%。所说明的量是指基于铸型材料混合物的油膏。
根据本发明,基于铸型材料混合物,油膏的添加量在0.01至8重量%之间、优选在约0.05至5重量%之间、尤其优选在0.1至3重量%之间,更尤其优选大于0.2且小于1.5重量%。
在另一实施方式中,能够为油膏添加在开始提出的已知抗脉纹形成添加剂的四种类型中的至少一种另外的抗脉纹形成添加剂(在权利要求中仅称作为添加剂),以基于所使用的抗脉纹形成添加剂的总量的1至98重量%、尤其1至95重量%的量来添加。
油膏和另外的脉纹形成添加剂的比例为1:100至100:1,优选1:90至90:1,尤其优选1:10至1:1。优选地,添加无机抗脉纹形成添加剂,尤其优选为铝硅酸和氧化物,特别优选为锂辉石、碱金属长石、碱土金属长石,以及铁、铝、钛和锰的氧化物。
用于避免脉纹形成的其他可行的抗脉纹形成添加剂例如包括:矿物、空心微球、木屑、有机纤维材料、碳水化合物、碳、天然油、矿物油、蜡、天然树脂和合成树脂等。适合的矿物例如是TiO2、氧化铁、云母、α母锂辉石、β辉锂辉石和蛭石。空心微球的实例是以Extendospheres或名称出售的硅酸铝或硼硅酸盐玻璃空心微球。合适的木屑例如是山毛榉木屑。聚乙烯纤维例如可以用作有机纤维材料而淀粉作为碳水化合物。如果碳用作添加剂组分,则这可以以焦炭和/或石墨的形式实现,以膨胀和未膨胀的形式实现,和/或以硬煤粉的形式实现。蓖麻油和亚麻籽油适合作为天然油而石油作为矿物油。例如考虑使用聚乙烯蜡和凡士林作为蜡。松香是合适的天然树脂组分的实例,而溶液或粉末形式的酚醛树脂或多元醇(甘油)可用作合成树脂。
尤其适合的其他的附加抗脉纹形成添加剂是:
分别基于铸型材料混合物,
-至少一种铝硅酸盐,尤其以1至15重量%、尤其优选1至10重量%的量;
-氧化铁,尤其以1至15重量%、尤其优选1至8重量%的量;
-木屑,尤其以0.3至5重量%、尤其优选0.3至3重量%的量;和
-糊精和淀粉,尤其以0.5至5重量%之间、优选0.5至4重量%之间、尤其优选0.5至3重量%的量。
根据本发明,能够单独地或与常规的添加剂组合使用如上描述的油膏。
在使用两种或更多种抗脉纹形成添加剂的情况下,能够将油膏分开地、同时与其余组分或与其余组分预混地添加至铸型材料混合物中。
优选地,添加剂或添加剂组分与耐火铸型基础材料预混合,然后与粘结剂混合,但也可以改变添加顺序,例如最后添加添加剂。在根据本发明的铸型材料混合物混匀之后,将其转移到铸型工具中,在那里根据相应所用的方法进行固化,并将由此获得的模具和型芯从工具中取出。
在射芯机中,经由压缩空气压实铸型材料混合物,以便预设模具或型芯的期望尺寸。
附图说明
实验部分
如果没有另作说明,下面的%数据都是基于所使用的耐火铸型基础材料的量和重量(=100GWT)的GWT(重量份)。
开始的附图说明试样模具的几何形状。
图1示出制造的台阶型芯的侧视图,其在附图之内以mm为单位给出台阶高度和在其右侧的台阶的外径(第一值=下面台阶的直径,第二值=上面台阶的直径)。
图2是从上方示出的台阶型芯。
图3示出具有多个圆顶型芯的底部的俯视图。
图4示出贯穿具有圆形的头部面的圆顶型芯的截面。
具有铸造台阶型芯的脉纹形成测试实例
借助所谓的台阶型芯,研究了油膏对脉纹形成趋势的影响。为此借助于射芯机以冷芯盒方法制造台阶型芯。
包括:100重量份的Grube Haltern的石英砂H 32、
加上根据表1的添加剂的铸型材料混合物借助于Hobart公司的混合器均匀地制备(每种组分的混合时间为1分钟,混合物总重量为5kg),并借助于压缩空气(4巴)引入到铸型工具中,并且用KATALYSATOR 706(ASK Chemicals GmbH,二甲基丙胺)2.0ml在2巴冲洗压力下供气20秒以固化。然后,将台阶型芯如下地粘入模具中,使得它们在模具中倒置(窄边朝下)并在浇铸时缓慢地从底部到顶部用熔融金属填充。
浇铸借助灰铸铁熔体GGJL在铸造温度约为1410℃、铸造高度为55cm且铸造时间约为12秒的情况下进行。铸造重量约为12kg,砂:铁的比例在台阶1(直径128-126mm)中约为1:3而在台阶7(直径25至23mm)中约为1:30。在铸造模具冷却后,将铸件从模具中取出,并借助于喷砂除去粘附的砂。随后,在脉纹形成方面评估铸件,参见表1。
使用:
根据表1的结果显示:测试的油膏RQ 20和NQ、DEOGRIP WPF和RHENOPREN EPS,即使在添加量低的情况下,也实现了比由木屑构成的标准添加剂更好的抗脉纹形成作用。据信:油膏不仅根据占位原理起作用,而且还像煤或石墨那样在燃烧时由还原气氛将无烟煤沉积在砂粒上,进而使得通过金属熔融物浸润变得更难。
具有圆顶型芯的浇铸实例的脉纹形成测试
为了评估脉纹形成趋势,利用不同类型的油膏制造另外的圆顶型芯的浇铸件。为此,铸型材料混合物(如上的铸型材料混合物的制备):将
100重量份的Grube Haltem的石英砂H 32、
0.8重量份的ECOCURE 300WM 10、
0.8重量份的ECOCURE 600WM 11,
加上根据表2的添加剂混合并制造圆顶型芯(h=50mm,d=50mm)。
为此,利用4巴的压缩空气将铸型材料混合物引入合适的铸型工具中,并用2.0mlKATALYSATOR 706(ASK Chemicals GmbH,DMPA)以2巴的冲洗压力固化20秒。通过首先将圆顶型芯固定粘附在主型芯空腔的底部上并用盖型芯封闭该空腔的方式,来组装模具。在盖型芯中设有直径20mm的圆形开口。然后,将漏斗形的浇口型芯以如下方式固定在盖型芯上:漏斗通向盖型芯的浇口开口。铸造过程借助于重力进行。浇铸温度约为1410至1430℃。铸造时间约为10秒,铸造重量约为15千克。
在此,也在脉纹形成方面评估结果,并总结在表2中。
再次与标准添加剂木屑相比,借助该实验也显示出:利用油膏实现了比借助标准添加剂更干净的铸造表面,而与使用是否含硫的或无硫的油膏无关。
同样测量了这些混合物的抗弯强度并且发现其足够好。
粘着趋势的测定
使用砂添加剂的另一重要标准是在型芯工具的内壁处的所谓的粘着趋势。将其理解为:在工具壁部处射出型芯时,添加剂的趋势有助于砂粘附。工具中的大量砂粘附导致清洁耗费的提高进而导致成本提高。
为了确定粘附趋势进行如下操作。在Hobart公司的混合器(如上的铸型材料混合物的制备)中,将由石英砂H 32、添加剂(如表3和4中所示)、0.80%的ECOCURE 300WM 10和0.80%的ECOCURE构成的砂混合物均匀混合。
将该砂混合物转移到射芯机中,并且利用压缩空气以4巴的射压在射模中制造尺寸(l×b×h)为11cm×5cm×1.2cm的型芯。射模由钢构成,并在第一次使用前用丙酮脱脂,且不用外来的脱模剂处理。利用KATALYSATOR 706(二甲基丙胺)(1ml,在2巴冲洗压力下供气10秒),将射入模具中的型芯固化。在固化后,将型芯从模具中取出。用同一种砂混合物重复该过程总共20次,其间没有清洗金属模具或者没有用外部脱模剂进行处理。在20次射芯过程之后,取出射模并机械地移除形成的砂粘附物(直接在两个喷射喷嘴下方)并称重。以毫克为单位的砂粘附物(表3和4)表示的砂粘附量是测试的砂混合物粘附趋势的量度。
分别基于铸型基础材料,将具有1.8%SphereOx和0.2%油膏的砂混合物对照具有2%SphereOX的砂混合物进行测试。粘合剂量(冷芯盒系统)被选择为,使得用混合物制造的试样的强度近似相同。在20次射芯后,包含油膏的铸型材料混合物的粘附在工具处的砂量比无油膏的混合物低40%。
从实践中已知:石墨具有非常低的粘附趋势,进而基于添加剂混合物,石墨也更倾向作为添加剂组分以5至20%的量混入。出于该理由,在粘附趋势测试中,执行将5%、10%和15%的油膏或石墨混入到中的直接比较。该添加剂混合物基于铸型材料混合物以各2%的量添加到砂中。
在表3和4中列举粘附趋势测试的结果(在20次注射后的平均值)。从表3和表4可见:与含石墨的混合物相比,含有油膏的混合物的粘附趋势(经由砂粘附评估)显著更小。
但是,在较低混入的情况下,包含油膏的固化铸型材料混合物的砂粘附相对于石墨混合物减小多于70%。
表3和4的铸型材料混合物分别相对于100重量份的耐火铸型基础材料各自包含如下添加剂或冷芯盒粘合剂。这是Grube Haltem的石英砂H 32。
A3:0.8重量份ASKOCURE 388,0.8重量份ASKOCURE 688,
A4:0.8重量份ASKOCURE 388,0.8重量份ASKOCURE 688,2重量份SphereOX,
A5:0.7重量份ASKOCURE 388,0.7重量份ASKOCURE 688,2重量份SphereOX,
A6:0.65重量份ASKOCURE 388,0.65重量份ASKOCURE 688,2重量份SphereOX,
A7:0.8重量份ASKOCURE 388,0.8重量份ASKOCURE 688,1.9重量份SphereOX+0.1重量份石墨,
A8:0.8重量份ASKOCURE 388,0.8重量份ASKOCURE 688,1.8重量份SphereOX+0.2重量份石墨,
A9:0.8重量份ASKOCURE 388,0.8重量份ASKOCURE 688,1.7重量份SphereOX+0.3重量份石墨,
B8:0.8重量份ASKOCURE 388,0.8重量份ASKOCURE 688,1.8重量份SphereOX+0.2重量份DEOGRIP WPF,
B9:0.8重量份ASKOCURE 388,0.8重量份ASKOCURE 688,1.9重量份SphereOX+0.1重量份DEOGRIP WPF,
B10:0.8重量份ASKOCURE 388,0.8重量份ASKOCURE 688,1.8重量份SphereOX+0.2重量份DEOGRIP WPF,
B11:0.8重量份ASKOCURE 388,0.8重量份ASKOCURE 688,1.7重量份SphereOX+0.3重量份DEOGRIP WPF。
表1
台阶0:150-148mm,粘入到模具中,台阶1:128-126mm,台阶7:25-23mm,参见图1
表2
表3
表4
S=SphereOx
G=石墨
F=DEOGRIP WPF。
Claims (46)
1.一种铸型材料混合物,包括至少
耐火铸型基础材料,
粘结剂,和
包含油膏或由油膏构成的添加剂,其中,所述油膏以粉末形式使用或以分散体形式使用,基于所述铸型材料混合物,所述油膏以0.01至8重量%之间的量包含在所述铸型材料混合物中。
2.根据权利要求1所述的铸型材料混合物,其中,所述油膏是经由硫或氧交联的或者始于环氧乙烷/环氧基团交联的不饱和酯。
3.根据权利要求1所述的铸型材料混合物,其中,所述油膏是经由氧桥交联的不饱和酯。
4.根据权利要求1所述的铸型材料混合物,其中,所述油膏具有在30000g/mol和150000g/mol之间的数均分子量。
5.根据权利要求1所述的铸型材料混合物,其中,所述油膏具有在30000g/mol至50000g/mol的数均分子量。
6.根据权利要求1所述的铸型材料混合物,其中,所述油膏以干燥的粉末形式使用。
7.根据权利要求1所述的铸型材料混合物,其中,所述油膏具有30μm至600μm平均直径的粒径。
8.根据权利要求1所述的铸型材料混合物,其中,所述油膏具有80μm至200μm平均直径的粒径。
9.根据权利要求1所述的铸型材料混合物,其中,所述油膏具有在0至20重量%之间的硫含量。
10.根据权利要求1所述的铸型材料混合物,其中,所述油膏具有在0至5重量%之间的硫含量。
11.根据权利要求1所述的铸型材料混合物,其中,所述油膏不包含硫。
12.根据权利要求1所述的铸型材料混合物,其中,
a)基于所述铸型材料混合物,所述油膏以0.05至5重量%之间的量包含在所述铸型材料混合物中,和/或
b)基于所述耐火铸型基础材料,所述油膏以0.01至8重量%之间的量包含在所述铸型材料混合物中。
13.根据权利要求1所述的铸型材料混合物,其中,
a)基于所述铸型材料混合物,所述油膏以大于0.2且小于1.5重量%的量包含在所述铸型材料混合物中,和/或
b)基于所述耐火铸型基础材料,所述油膏以大于0.2且小于1.5重量%的量包含在所述铸型材料混合物中。
14.根据权利要求1所述的铸型材料混合物,其中,所述添加剂包含用于避免脉纹形成的另外的添加剂,所述另外的添加剂选自以下组分中的一种或多种:矿物、空心微球、木屑、有机纤维材料、碳水化合物、碳、天然油、矿物油、蜡、天然树脂和合成树脂。
15.根据权利要求14所述的铸型材料混合物,所述矿物包括云母、蛭石、硅铝酸盐、碱金属长石、碱土金属长石、铁氧化物、铝氧化物、钛氧化物和锰氧化物。
16.根据权利要求15所述的铸型材料混合物,所述矿物包括锂辉石。
17.根据权利要求15所述的铸型材料混合物,所述矿物包括氧化铝。
18.根据权利要求1所述的铸型材料混合物,其中,所述添加剂包含用于避免脉纹形成的另外的添加剂,所述另外的添加剂选自硅铝酸盐、铝氧化物、碱金属长石、碱土金属长石、铁氧化物、钛氧化物和锰氧化物,及其混合物。
19.根据权利要求18所述的铸型材料混合物,所述硅铝酸盐包括锂辉石。
20.根据权利要求1所述的铸型材料混合物,还包含用于避免脉纹形成的另外的添加剂,所述另外的添加剂选自以下组分中的一种或多种:
分别基于所述铸型材料混合物
-至少一种硅铝酸盐,以1至15重量%的量;
-氧化铁,以1至15重量%的量;
-木屑,以0.3至5重量%的量;和
-糊精或淀粉或两者,以0.5至5重量%之间的量。
21.根据权利要求1所述的铸型材料混合物,还包含用于避免脉纹形成的另外的添加剂,所述另外的添加剂选自以下组分中的一种或多种:
分别基于所述铸型材料混合物
-至少一种硅铝酸盐,以1至10重量%的量;
-氧化铁,以1至8重量%的量;
-木屑,以0.3至3重量%的量;
-糊精或淀粉或两者,以0.5至3重量%的量。
22.根据权利要求14至19中任一项所述的铸型材料混合物,其中,所述油膏与一种或多种所述另外的添加剂的重量比为1:100至100:1。
23.根据权利要求20或21所述的铸型材料混合物,其中,所述油膏与一种或多种所述另外的添加剂的重量比为1:100至100:1。
24.根据权利要求14至19中任一项所述的铸型材料混合物,其中,所述油膏与一种或多种所述另外的添加剂的重量比为1:10至1:1。
25.根据权利要求20或21所述的铸型材料混合物,其中,所述油膏与一种或多种所述另外的添加剂的重量比为1:10至1:1。
26.根据权利要求1所述的铸型材料混合物,其中,所述粘结剂选自以下组分中的一种或多种:
-用叔胺固化的至少一种多元醇和多异氰酸酯;
-含有用CO2固化的硼化合物的碱性酚醛树脂;
-用酯或甲酸甲酯固化的碱性甲阶酚醛树脂;
-分别热固化的甲阶酚醛树脂、呋喃树脂、尿素树脂或混合树脂;
-热固化或用CO2固化的硅酸盐类粘合剂;
-用六亚甲基三胺固化的酚醛清漆;
-分别酸固化的甲阶酚醛树脂、呋喃树脂或混合树脂;
-使用SO2固化的环氧树脂和丙烯酸酯构成的混合物。
27.根据权利要求1所述的铸型材料混合物,其中,所述粘结剂选自以下组分中的一种或多种:
-用叔胺固化的至少一种多元醇和多异氰酸酯;
-含有用CO2固化的硼化合物的碱性酚醛树脂;
-热固化或用CO2固化的硅酸盐类粘合剂;和
-使用SO2固化的环氧树脂和丙烯酸酯构成的混合物。
28.根据权利要求1所述的铸型材料混合物,其中,所述粘结剂包含用叔胺固化的至少一种多元醇和多异氰酸酯。
29.根据权利要求1所述的铸型材料混合物,其中,基于所述铸型材料混合物,所述粘结剂以0.4重量%至7重量%包含在所述铸型材料混合物中。
30.根据权利要求1所述的铸型材料混合物,其中,基于所述铸型材料混合物,所述粘结剂以0.5重量%至5重量%包含在所述铸型材料混合物中。
31.根据权利要求1所述的铸型材料混合物,其中,所述耐火铸型基础材料选自以下组分中的一种或多种:石英砂、锆英砂、铬矿砂、橄榄石、蛭石、铝土矿、耐火粘土、玻璃颗粒、硅酸铝中空微球,及其混合物。
32.根据权利要求31所述的铸型材料混合物,所述玻璃颗粒包括玻璃珠。
33.根据权利要求1所述的铸型材料混合物,其中,基于所述耐火铸型基础材料,所述耐火铸型基础材料由超过20重量%的石英砂构成。
34.根据权利要求1所述的铸型材料混合物,其中,所述铸型材料混合物的大于70重量%是所述耐火铸型基础材料。
35.根据权利要求1所述的铸型材料混合物,其中,所述铸型材料混合物的大于等于85重量%是所述耐火铸型基础材料。
36.根据权利要求1所述的铸型材料混合物,其中,所述耐火铸型基础材料通过筛分分析测定具有100μm至600μm之间的平均粒径。
37.根据权利要求1所述的铸型材料混合物,其中,所述耐火铸型基础材料通过筛分分析测定具有120μm至550μm之间的平均粒径。
38.根据权利要求1所述的铸型材料混合物,其中,所述粘结剂包含至少一种多元醇和多异氰酸酯并且所述粘结剂能够利用叔胺进行固化。
39.一种用于制造根据权利要求1至38中任一项所述的铸型材料混合物的组分体系,彼此分开地至少包含如下组分:
组分A),包含耐火铸型基础材料或由耐火铸型基础材料构成;
组分B),包含具有或不具有固化剂/活化剂/催化剂的粘结剂或由具有或不具有固化剂/活化剂/催化剂的粘结剂构成;以及
组分C),包含油膏或由油膏构成,其中所述油膏以粉末形式使用或以分散体形式使用,基于所述铸型材料混合物,所述油膏以0.01至8重量%之间的量包含在所述铸型材料混合物中。
40.根据权利要求39所述的组分体系,其中,所述组分C)包含用于避免脉纹形成的其他的另外添加剂。
41.根据权利要求39所述的组分体系,其中,所述组分C)包含用于避免脉纹形成的至少一种氧化铁,所述至少一种氧化铁呈1:100至100:1的油膏与氧化铁的重量比。
42.根据权利要求39所述的组分体系,其中,所述组分C)包含用于避免脉纹形成的至少一种氧化铁,所述至少一种氧化铁呈1:10至1:1的油膏与氧化铁的重量比。
43.一种用于制造型芯或模具的方法,包含如下步骤:
将根据前述权利要求1至38中任一项所述的铸型材料混合物引入铸型工具中;
在所述铸型工具中使所述铸型材料混合物固化;以及
从所述铸型工具中取出固化的所述型芯或模具。
44.一种用于金属铸造的模具或型芯,所述模具或型芯能够根据权利要求43所述的方法制造。
45.根据权利要求44所述的模具或型芯,所述模具或型芯用于铁铸造和/或钢铸造。
46.一种油膏作为用于避免脉纹形成的添加剂和/或作为用于金属铸造的型芯和/或模具中的脱模剂的应用,其中,所述油膏以粉末形式使用或以分散体形式使用,基于铸型材料混合物,所述油膏以0.01至8重量%之间的量包含在所述铸型材料混合物中。
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PCT/DE2018/100290 WO2018177480A1 (de) | 2017-03-28 | 2018-03-28 | Formstoffmischung enthaltend additive zur reduzierung von gussfehlern |
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CN112371901B (zh) * | 2020-09-14 | 2022-06-28 | 盐城仁创砂业科技有限公司 | 一种用于铸造的防脉纹添加剂、制备方法及使用方法 |
CN112846069A (zh) * | 2020-12-31 | 2021-05-28 | 东风汽车有限公司 | 一种无机砂芯模具粘砂抑制剂、添加剂及应用 |
CN113976828A (zh) * | 2021-11-19 | 2022-01-28 | 桂林中铸机械科技有限公司 | 消失模采用高温陶瓷化涂料气化空壳无碳精密铸造方法 |
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US10919085B2 (en) | 2021-02-16 |
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EP3600717B1 (de) | 2021-05-12 |
CN110494234A (zh) | 2019-11-22 |
MX2019011615A (es) | 2019-11-18 |
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