CN118139956A - 塑性加工用无硼水基润滑剂 - Google Patents
塑性加工用无硼水基润滑剂 Download PDFInfo
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- CN118139956A CN118139956A CN202280071120.3A CN202280071120A CN118139956A CN 118139956 A CN118139956 A CN 118139956A CN 202280071120 A CN202280071120 A CN 202280071120A CN 118139956 A CN118139956 A CN 118139956A
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- composition
- lubricating composition
- aqueous lubricating
- group
- water
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 39
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- 239000004033 plastic Substances 0.000 title claims description 15
- 239000000203 mixture Substances 0.000 claims abstract description 150
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 64
- 239000002184 metal Substances 0.000 claims abstract description 64
- 239000007787 solid Substances 0.000 claims abstract description 61
- 239000000758 substrate Substances 0.000 claims abstract description 57
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 238000000518 rheometry Methods 0.000 claims abstract description 22
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- 229910052796 boron Inorganic materials 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 11
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- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 4
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 4
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
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- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
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- 239000011787 zinc oxide Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/02—Water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/084—Inorganic acids or salts thereof containing sulfur, selenium or tellurium
-
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
本公开涉及一种在金属基材的冷加工中具有实用性的含水润滑组合物,所述含水润滑组合物基于组合物的重量包含:1‑20wt%的a)至少一种水溶性无机盐,所述一种或多种无机盐处于溶解状态;b)至少一种颗粒状固体润滑剂;0.1‑5wt%的c)至少一种流变控制剂;0.1‑5wt%的d)至少一种碱;和0.1‑5wt%的e)至少一种选自以下组的表面活性剂:阴离子表面活性剂、非离子表面活性剂、阳离子表面活性剂、两性表面活性剂和两性离子表面活性剂,其中所述组合物不含硼和硼化合物,并且其特征还在于b)所述至少一种固体润滑剂与a)所述至少一种水溶性无机盐的重量比[(b):(a)]为0.1:1至1:1。
Description
技术领域
本公开涉及一种用于金属基材冷加工的含水润滑组合物。更具体地,本公开涉及一种含水润滑组合物,其中分散有待沉积在金属基材表面上的颗粒状固体润滑剂,该含水润滑组合物不含硼化合物。
背景技术
冷加工的实践是指在低于再结晶温度下进行的金属的塑性变形。在大多数制造环境中,这种冷加工在室温下进行,但采用稍高的温度(但仍低于再结晶温度)可在待加工的金属中提供增加的延展性和降低的强度。
概括地说,主要的冷加工操作可以分为四个标题:挤压;弯曲;剪切;和拉伸,所述拉伸包括管、棒、线和壳拉伸和纺丝和熨烫。集中于挤压工艺,因为这些工艺占加工产品的最大吨位,所以这些工艺通常是具有热加工对应物的工艺,并且包括:冷轧;旋锻;冷锻;和挤出。
与热加工相比,这些冷加工工艺确实具有许多优点。最明显地,不需要加热的能量消耗,但额外的益处包括:加工后金属获得更好的表面光洁度;加工后金属的卓越尺寸控制;加工后金属的定向特性最小化;加工后金属的提高的强度;和冷加工过程的优越再现性。
然而,存在与冷加工方法相关的缺点,包括:产生用于金属变形的强力的需要(特别是在可获得有限的金属延展性的情况下)促进了对更重和更强大的加工设备的需要;金属表面必须清洁且无垢;可能发生应变硬化;并且不希望的残余应力可能存在于加工后金属中。
鉴于这些缺点,在本领域中,在金属和冷加工工具之间的界面处提供具有润滑膜的待冷加工的金属是有些常见的。有效施加的润滑膜(其没有缺陷且具有一致且足够的厚度)可用于降低该界面处的摩擦并抑制咬合(seizures)的发生。本领域的经验表明,润滑油难以以在金属基材上提供有效膜的方式施加和处理。因此,固体润滑膜的使用变得普遍。这些膜可以由其中分散有固体润滑剂的溶剂基或水基组合物沉积。
GB2003923A(Foseco公司)公开了一种金属加工润滑剂组合物,其包含:(i)水溶性金属皂;和(ii)碱金属氯化物、碱金属硫酸盐和碱金属硼酸盐。
WO00/63324A1(Chevron Chemical公司)公开了一种具有润滑粘度的基础油、分散的水合碱金属硼酸盐和聚亚烷基琥珀酸酐或其非氮衍生物的润滑剂组合物。
EP917559A(Henkel公司)描述了一种用于金属的冷塑性加工的水基润滑剂,所述水基润滑剂除了水之外包含:(a)水溶性无机盐的组分;(b)固体润滑剂的均匀分散组分;(c)至少一种选自以下组的物质的均匀乳化组分:矿物油、动物和植物油和脂肪、和合成油;和(d)表面活性剂,其中固体润滑剂与水溶性无机盐的重量比((b)/(a))为0.05:1至2:1,并且油性组分与水溶性无机盐和固体润滑剂的总和的重量比((c):(a+b))为0.05:1至1:1。
EP2450423A(Henkel AG&Co.KGaA)公开了一种用于塑性加工的水基润滑剂,其包含含有具有烯属不饱和键的单体的共聚物或均聚物的树脂组分,包括至少马来酸酐(a)、无机组分(b)、和固体润滑组分(c),其中树脂组分(a)的马来酸酐部分用含氮化合物以10-80%的封端比例封端,并且用碱性组分以40%至100%的中和度中和马来酸酐部分的解封端。
JP2011246684A(Nihon Parkerizing)公开了一种用于金属材料塑性加工的含水润滑剂,所述润滑剂包含:碱金属硼酸盐(a),其中碱金属硼酸盐(a)含有硼酸锂,并且其中碱金属硼酸盐(a)中锂与所有碱金属的摩尔比为0.1至1.0;并且其中碱金属硼酸盐(a)中硼(b)与碱金属M的摩尔比(B/M)为1.5至4.0。
CN107805541A(Maanshan Tuori Metal Surface Tech有限公司)提供了一种用于塑性加工的润滑剂,所述润滑剂包含按重量计:10-50%的硬脂酸;1-10%的硼酸盐;1-10%的防锈剂;1-10%的无机碱;0.1-0.5%的消泡剂;和余量的水。
应注意,这些现有技术引文中的许多具有使用硼化合物的共性。这被认为是不利的。硼化合物对人和动物有刺激性,特别是刺激人的鼻子、喉咙和眼睛。人类高度暴露于硼可引起胃、肾和脑的感染。此外,从工业径流释放到土壤中的硼化合物可以将土壤中天然硼的水平补充到毒性点,对于韧皮部不动植物是相当容易达到这一点的。土壤中的这种硼毒性难以减弱。
本领域中认为需要开发不含硼和硼化合物但在金属基材的冷加工中保持有效实用性的含水润滑组合物。
发明内容
根据本发明的第一方面,提供了一种含水润滑组合物,基于组合物的重量,其包含:
1-20wt%的a)至少一种水溶性无机盐,所述一种或多种无机盐处于溶解状态;
b)至少一种颗粒状固体润滑剂;
0.1-5wt%的c)至少一种流变控制剂;
0.1-5wt%的d)至少一种碱;和
0.1-5wt%的e)至少一种选自以下组的表面活性剂:阴离子表面活性剂、非离子表面活性剂、阳离子表面活性剂、两性表面活性剂和两性离子表面活性剂,
其中所述组合物不含硼和硼化合物,并且其特征还在于b)所述至少一种固体润滑剂与a)所述至少一种水溶性无机盐的重量比[(b):(a)]为0.1:1至1:1。
在本发明的一个重要实施方案中,基于组合物的重量,含水润滑组合物包含:
2-20wt%、优选5-20wt%的a)所述至少一种水溶性无机盐,所述一种或多种无机盐处于溶解状态;
b)所述至少一种颗粒状固体润滑剂;
0.1-2.5wt%、优选0.1-2wt%的c)所述至少一种流变控制剂;
0.1-2.5wt%、优选0.1-2wt%的d)所述至少一种碱;和
0.1-2.5wt%、优选0.1-2wt%的e)至少一种选自以下组的表面活性剂:阴离子表面活性剂、非离子表面活性剂、阳离子表面活性剂、两性表面活性剂和两性离子表面活性剂,
其中所述组合物不含硼和硼化合物,并且其特征还在于b)所述至少一种固体润滑剂与a)所述至少一种水溶性无机盐的重量比[(b):(a)]为0.1:1至1:1,优选0.2:1至1:1。
所述含水润滑组合物可任选地具有7至10、优选7至9的pH。
所述含水润滑组合物通常包含基于组合物的重量,60至90wt%、优选65至85wt%、更优选65至80wt%的水。作为水含量表征的替代或补充,所述含水润滑组合物的特征可在于使用Brookfield粘度计在25℃下测量的0.005-1Pa·s的粘度。
组合物中包括的流变控制剂c)的总量应为组分a)和b)按重量计总量的1至10wt%,优选2至8wt%。优选包括在组合物中的所述或每种流变控制剂是触变胶。
基于组合物的重量,根据本发明的示例性含水润滑组合物包含:
作为部分a)的5-20wt%的硫酸钠、三聚磷酸钾和三聚磷酸钠的混合物,其中该混合物的每种盐处于溶解状态;
固体润滑剂b),其包含或由以下物质组成:
至少一种选自以下组的磷酸盐:磷酸锌、磷酸锌钙和磷酸锰;和
至少一种选自以下组的蜡:聚乙烯蜡;氧化聚乙烯蜡;聚丙烯蜡;氧化聚丙烯蜡;和基于乙烯或丙烯作为主要单体的共聚蜡,
此外,其中所述至少一种蜡的特征在于400至30,000g/mol、优选1000至25,000g/mol的数均分子量(Mn);
作为部分c)的0.1-2wt%的至少一种触变胶,其选自以下组:纤维素衍生物;和多糖;
作为部分d)的0.1-2wt%的至少一种碱,其选自以下组:
双(2-(N,N’-二甲基氨基)乙基)醚;双(叔丁基氨基乙基)醚、1,2-双(叔丁基氨基乙氧基)乙烷;1,2-双(叔丁基氨基乙氧基乙氧基)乙烷;双[2-(异丙基氨基)丙基]醚;1,2-[2-异丙基氨基)-丙氧基]乙烷;和
作为部分e)的0.1-2wt%的至少一种选自以下组的表面活性剂:阴离子表面活性剂、非离子表面活性剂、阳离子表面活性剂、两性表面活性剂和两性离子表面活性剂,
其中所述组合物不含硼和硼化合物,并且其特征还在于b)所述至少一种固体润滑剂与a)所述水溶性无机盐的混合物的重量比[(b):(a)]为0.2:1至1:1,优选0.4:1至1:1。
根据本发明的第二方面,提供如上文和所附权利要求中所限定的含水水基润滑组合物或由其获得的干膜在金属基材的塑性冷加工中的用途。
本发明进一步提供了一种用于固体金属基材的塑性冷加工的方法,该方法通过以机械方式迫使所述固体金属基材穿过由至少一个金属加工工具的至少一个固体表面界定的孔,所述方法包含以下步骤:
i)将如本文以上和所附权利要求中所限定的含水润滑组合物施用到所述金属基材的至少一个固体表面上,一个或多个表面如果未被涂覆将在所述方法期间直接接触固体金属加工工具表面;
ii)干燥所施用的含水润滑组合物以在所述金属基材的所述至少一个固体表面上形成膜;和
(iii)以机械方式迫使在步骤ii)中形成的金属基材通过由至少一个金属加工工具表面限定的所述孔,使得金属基材被冷加工。
定义
如本文使用,除非另外表明,单数形式的冠词“一种”、“一个”和“所述”包括复数指代物。
本文所用的术语“包含(comprising/comprises/comprised of)”与“包括(including/includes)”、“含有(containing/contains”)”同义,并且是包括性的或开放式的,并且不排除另外的未列举的成员、要素或方法步骤。如果有使用,则短语“由…组成”是封闭的,并且排除所有另外的要素。此外,短语“基本上由…组成”不包括另外的材料元素,但允许包括基本上不改变本发明的性质的非材料元素。
当量、浓度、尺寸和其他参数以范围、优选的范围、上限值、下限值或优选的上限值和下限值的形式表示时,应当理解,通过将任何上限或优选值与任何下限或优选值组合可获得的任何范围也被具体公开,而不管所获得的范围是否在上下文中明确提及。
这里经常使用单词“优选(preferable/preferred/preferably)”、“特别地”和“期望地”及其同义词来指代在某些情况下可以提供特定益处的本公开的实施方案。然而,一个或多个优选的或优选地、特别的和理想的实施方案的叙述并不暗示其他实施方案不是有用的并且不旨在将那些其他实施方案排除在本公开的范围之外。
如贯穿本申请所使用的,词语“可”以允许的意义使用,这意味着具有潜力,而不是以强制的意义使用。
如本文所用,室温为23℃加或减2℃。
如本文所用,数均分子量(Mn)和重均分子量(Mw)通过凝胶渗透色谱法(GPC)用四氢呋喃(THF)作为洗脱剂根据DIN 55672-1:2007-08测定。术语多分散性(PD)得自Mw和Mn并计算为(Mw/Mn)。
如本文所用,“d50粒度”是指粒度分布使得按重量计至少50%的颗粒具有小于指定值的粒度直径。除非另有说明,否则该粒度通过激光衍射测定。
本文所用术语“含水润滑组合物”是指实际接触金属基材的组合物。如本领域中已知的,这种接触可以在所谓的“浴”中发生,浴的形状、大小和布置使得至少部分基材浸入其中。此外,该浴的尺寸应允许含水润滑组合物在负载的基材周围和遍布负载的基材移动,该移动可通过再循环和/或超声进一步增强。浴内组合物的pH、浴的温度和基材的接触时间是结果有效变量,只要可能,应手动或自动监测。
如本文所用,术语“合金”是指由两种或多种金属或金属和非金属组成的物质,它们通常通过熔融在一起并在融化时彼此溶解而紧密结合。因此,术语“X合金”表示其中金属X为主要构成组分的合金,并且其中基于金属计,X通常占合金的至少40wt%,更通常至少50wt%或至少60wt%。
如本文所用,“C1-Cn烷基”是指含有1至n个碳原子的单价基团,其为烷烃的残基并且包括直链和支化有机基团。因此,“C1-C18烷基”是指含有1至18个碳原子的单价基团,其为烷烃的残基并且包括直链和支化有机基团。烷基的实例包括但不限于:甲基;乙基;丙基;异丙基;正丁基;异丁基;仲丁基;叔丁基;正戊基;正己基;正庚基;和2-乙基己基。在本发明中,这样的烷基可以是未取代的或可以被一个或多个卤素取代。当适用于给定的部分(R)时,对于烷基内的一个或多个非卤素取代基的耐受性将在说明书中指出。
本文所用的术语“C1-Cn羟基烷基”是指具有1至n个碳原子的HO-(烷基)基团,其中取代基的连接点是通过氧原子,并且烷基如上所定义。
“烷氧基”是指由-OA表示的单价基团,其中A是烷基:其非限制性实例是甲氧基、乙氧基和异丙氧基。本文所用的术语“C1-C12烷氧基烷基”是指具有如上所定义的烷氧基取代基的烷基,其中部分(烷基-O-烷基)总共包含1至12个碳原子:这些基团包括甲氧基甲基(-CH2OCH3)、2-甲氧基乙基(-CH2CH2OCH3)和2-乙氧基乙基。
本文所用的术语“亚烷基”定义为饱和的二价烃基。一般而言,在本公开中,这样的亚烷基可以是未取代的或可以被一个或多个卤素取代。
术语“C3–C30环烷基”应理解为是指具有3至30个碳原子的饱和单环或多环烃基。在本发明中,这样的环烷基可以是未取代的或可以被一个或多个卤素取代。当适用于给定的部分(R)时,对于环烷基内的一个或多个非卤素取代基的耐受性将在说明书中指出。环烷基的实例包括:环丙基;环丁基;环戊基;环己基;环庚基;环辛基;金刚烷;和降冰片烷。
如本文所用,“亚环烷基”是指通过从环烷基的一个或多个环去除两个氢原子而形成的二价基团。
如本文所用,单独使用或作为较大部分的一部分(如在“芳烷基”中)使用的“C6-C18芳基”是指单环、双环和三环环系,其中单环环系是芳族的或双环或三环环系中的至少一个环是芳族的。双环和三环环系包括苯并稠合的2-3元碳环。在本发明中,这样的芳基可以是未取代的或可以被一个或多个卤素取代。当适用于给定的部分(R)时,对于芳基内的一个或多个非卤素取代基的耐受性将在说明书中指出。示例性芳基包括:苯基;(C1-C4)烷基苯基,例如甲苯基和乙基苯基;茚基;萘基,四氢萘基,四氢茚基;四氢蒽基;和蒽基。并且可以注意到优选苯基。
“亚芳基”(当独立使用或相对于诸如亚烷芳基的组合部分使用时)是指通过从如上定义的芳基的一个或多个环除去两个氢原子形成的二价基团,其中氢原子可以从相同或不同的环除去。列举的实例包括亚苯基和亚萘基。
如本文所用,“C2-C20烯基”是指具有2至20个碳原子和至少一个烯属不饱和单元的烃基。烯基可以是直链、支化或环状的,并且可以任选地被一个或多个卤素取代。在适用于给定部分(R)的情况下,对于烯基基团内的一个或多个非卤素取代基的耐受性将在说明书中指出。如本领域普通技术人员所理解的,术语“烯基”还涵盖具有“顺式”和“反式”构型或可替代地“E”和“Z”构型的基团。所述C2-C20烯基的实例包括但不限于:-CH=CH2;-CH=CHCH3;-CH2CH=CH2;-C(=CH2)(CH3);-CH=CHCH2CH3;-CH2CH=CHCH3;-CH2CH2CH=CH2;-CH=C(CH3)2;-CH2C(=CH2)(CH3);-C(=CH2)CH2CH3;-C(CH3)=CHCH3;-C(CH3)CH=CH2;-CH=CHCH2CH2CH3;-CH2CH=CHCH2CH3;-CH2CH2CH=CHCH3;-CH2CH2CH2CH=CH2;-C(=CH2)CH2CH2CH3;-C(CH3)=CHCH2CH3;-CH(CH3)CH=CHCH;-CH(CH3)CH2CH=CH2;-CH2CH=C(CH3)2;1-环戊-1-烯基;1-环戊-2-烯基;1-环戊-3-烯基;1-环己-1-烯基;1-环己-2-烯基;和1-环己基-3-烯基。
术语“亚烯基”是指通过从如上定义的烯基除去两个氢原子形成的二价基团。
如本文所用,“烷基芳基”是指烷基取代的芳基,两个基团如上定义。此外,本文所用的“芳烷基”是指被如上定义的芳基取代的烷基。
本文所用的术语“杂”是指含有一个或多个诸如N、O、Si和S的杂原子的基团或部分。因此,例如“杂环”是指具有例如N、O、Si或S作为环结构的一部分的环状基团。“杂烷基”、“杂环烷基”和“杂芳基”部分分别是如上文所定义的烷基、环烷基和芳基,其含有N、O、Si或S作为其结构的一部分。
本文所用的术语“碱”是指以下物质:其能够在极性或非极性溶剂中提取质子;或者,其能够提供氢氧根阴离子(OH-)。
术语“胺”根据其在本领域中的普通含义使用并且广泛地指含有具有孤对电子的氮原子的化合物。
本文所用的“C1-C9杂芳基胺”是指芳环(其可存在于单环或多环体系中)的至少一个碳原子被氮原子取代的化合物。优选地,C1-C9杂芳基胺具有1至3个被氮原子取代的芳环碳原子。杂芳基胺可以是未取代的或在杂芳基环的任何位置被一个或多个C1-C4烷基取代。除了烃环的至少一个碳原子被氮原子取代之外,杂芳基胺的一个或多个碳原子还可以被其他杂原子取代。杂芳基胺的实例包括但不限于吡啶、吡咯、嘧啶、咪唑、喹唑啉、嘌呤、吡唑和三唑。
如本文所用,术语“C1-C9杂环胺”是指可为单环或多环的脂族化合物,其中给定烃环的至少一个碳原子且优选1或2个碳原子被氮原子取代。环碳原子数总计为1至9。杂环胺可以是未取代的或在杂环的任何位置,包括一个或多个氮原子,被一个或多个如上定义的C1-C4烷基取代。除了烃环的至少一个碳原子被氮原子取代之外,杂环胺的一个或多个碳原子还可以被其他杂原子取代。杂环胺的实例包括但不限于哌嗪、吡咯烷和吗啉。
“氨基酸”是具有一个或多于一个诸如氨基、胍基、亚氨基或肼基团的碱性基团的有机酸,碱性基团连接在除羧基之外的任何碳原子上。如本文所用,术语“碱性氨基酸”是指具有可接受质子的额外碱性基团的氨基酸。碱性氨基酸的实例包括但不限于精氨酸和赖氨酸,包括各自的L-和D-形式。
如本文所用,术语“氨基糖”是指具有一个或多个羟基被-NR2基团取代的单糖单元,其中每个R独立地选自H或C1-C4烷基。氨基糖的实例包括但不限于葡糖胺和N-甲基葡糖胺。
组合物的粘度可以使用RVT型Brookfield粘度计在20℃和50%相对湿度(RH)的标准条件下测定。使用已知粘度的硅油校准粘度计,硅油的粘度为5000cps至50000cps。连接到粘度计的一组RV转子用于校准。含水润滑组合物的测量使用6号转子以20转/分钟的速度进行1分钟,直到粘度计平衡。然后使用校准计算对应于平衡读数的粘度。
本发明组合物在本文中定义为“基本上不含”某些化合物、元素、离子或其他类似组分。术语“基本上不含”是指化合物、元素、离子或其他类似组分不是有意添加到组合物中,并且至多仅以对涂层的期望性质没有(不利)影响的痕量存在。示例性的痕量按组合物的重量计小于1000ppm。术语“基本上不含”涵盖术语“不含”,后一术语指示其中指定化合物、元素、离子或其他类似组分完全不存在于组合物中或不以可通过本领域中通常使用的技术测量的任何量存在的那些实施方案。
具体实施方式
a)水溶性无机盐
基于组合物的重量,本公开的含水润滑组合物包含1至20wt%的a)至少一种水溶性无机盐。含水润滑组合物应优选包含2至20wt%、例如5至20wt%的a)所述至少一种水溶性无机盐。所述或每种包括的水溶性无机盐在含水润滑组合物中处于溶解状态。
除了诸如硼酸盐的含有硼的无机盐被排除在外的事实之外,盐的化学性质并不重要。水溶性无机盐应在待冷加工的金属基材上形成涂层。
可在本公开中单独或组合使用的合适的水溶性无机盐的非限制性实例包括:磷酸盐,诸如磷酸钙;多磷酸盐,包括碱金属多磷酸盐;碱金属硅酸盐,特别是硅酸钠和硅酸钾;碱金属钨酸盐,特别是钨酸钠;钼酸盐,包括钼酸铵和钼酸碱金属盐,特别是钼酸钠;硫酸盐,包括碱金属硫酸盐,特别是硫酸钠和硫酸钾;和碳酸盐,包括碱金属碳酸盐,特别是碳酸钠或碳酸钾。
为完整起见,术语“多磷酸盐”是指包含经由共享氧原子连接在一起的至少2个、例如2至6个四面体磷酸盐(PO4)单元的基团:多磷酸盐可以是直链或环状的。在本公开中具有实用性的示例性碱金属多磷酸盐包括但不限于:焦磷酸四钠;焦磷酸四钾;三聚磷酸钠;三聚磷酸钾;偏磷酸钠;偏磷酸钾;六偏磷酸钠;六偏磷酸钾;六偏磷酸锂;及其混合物。
当组分a)包含硫酸钠、三聚磷酸钾和三聚磷酸钠的混合物时在本公开中已经获得了良好的结果。
b)固体润滑剂
含水润滑组合物包含b)至少一种颗粒状固体润滑剂。润滑剂颗粒通常分散在组合物中:当将该组合物施加到待加工基材的表面上并随后在其上干燥时,颗粒被沉积在该表面上。取决于固体润滑剂的性质,在干燥时可能发生沉积颗粒的一些聚结,导致在基材表面上形成润滑膜。
所述至少一种颗粒状固体润滑剂与a)所述至少一种水溶性无机盐的重量比[(b):(a)]在水基润滑剂中应在0.1:1至1:1的范围内。优选地,所述重量比[(b):(a)]在0.2:1至1:1、特别是0.4:1至1:1或0.4:1至0.8:1的范围内。该比的特定值尤其应基于待进行塑性加工的金属坯料的特定形状、加工条件和加工装置来选择。当该重量比具有低于0.1:1的值时,所得涂层将具有降低的润滑性能,并且因此可能发生金属工件的磨损和咬合。超过1:1的重量比可导致涂层硬度降低和基材与涂层之间的粘附力降低:当在这些情况下将金属引入工具的嘴部时,在表面上形成的干燥涂层非常容易剥离,这导致受损的润滑性能。
不意图限制本公开,颗粒状固体润滑剂将常规地选自:i)层状固体,包括滑石、云母、石墨、硫化锌(ZnS)、硫化镉(CdS)、二硫化钼(MoS2)、硒化钼(MoSe2);二硫化钨(WS2)、二硫化硒(SeS2)、氟化钙(CaF2)和钠-铝氟化物,诸如美国专利3,377,279中公开的冰晶石和改性冰晶石;ii)金属皂,包括脂肪酸的金属盐,所述脂肪酸诸如月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、羟基硬脂酸和山萮酸;iii)润滑氧化物,包括氧化钛、氧化镉、氧化钴、氧化锌和二氧化硅(SiO2);iv)非层状润滑的金属化合物,诸如氟化铈(CeF3)、氢氧化钙、碳酸钙、磷酸锌、磷酸锌钙和磷酸锰;v)软单质金属,包括金、银、铅、锡、铟和钡;vi)固体聚合物润滑剂,包括聚四氟乙烯(PTFE)、氟化乙丙烯(FEP)、聚缩醛、聚酰亚胺、聚醚醚酮(PEEK)和超高分子量聚乙烯(UHWPE);和vii)蜡。这种颗粒状润滑剂可以单独使用或组合使用。
为了完整起见,上述术语“云母”涵盖合成云母和天然云母,诸如绢云母和白云母。此外,金属皂通常包括钙、铝、镁、钡、锌、铅、锂或钾作为组成金属;优选使用硬脂酸钙作为金属皂。
不意图限制本发明,在含水润滑组合物中具有实用性的示例性蜡包括:石蜡[CASNo.8002-74-2];聚乙烯蜡[CAS No.9002-88-4];聚乙烯-聚丙烯蜡;共聚聚乙烯蜡,例如乙烯与至少一种选自(甲基)丙烯酸、马来酸酐、乙酸乙烯酯和乙烯醇的单体的共聚物,该共聚物可在例如CAS No.38531-18-9、104912-80-3和219843-86-4下获得;聚丁烯蜡;Fischer-Tropsch蜡;氧化蜡,例如氧化聚乙烯蜡[CAS No.68441-17-8];极性改性聚丙烯蜡;微晶蜡,例如微晶石蜡[CAS No.63231-60-7];褐煤蜡和褐煤蜡萃余液;褐煤酸及其盐和酯;脂肪酸酰胺,诸如芥酸酰胺[CAS No.112-84-5]、油酰胺[CAS No.301-02-0]和1,2-亚乙基双(硬脂酰胺)[CAS No.110-30-5];和巴西棕榈蜡。
优选地,本发明组合物中包括的任何蜡满足以下条件中的至少一个:i)小于200mgKOH/g、优选小于100mg KOH/g的酸值;ii)40至200℃、优选60至180℃的熔点;和iii)至少200g/mol、优选至少400g/mol的数均分子量(Mn)。出于完整性考虑,这些条件并不相互排斥:蜡可以满足这些条件中的一个、两个或理想地三个。
注意到特别优选使用选自聚乙烯蜡、氧化聚乙烯蜡、聚丙烯蜡、氧化聚丙烯蜡和基于乙烯或丙烯作为主要单体的共聚蜡的至少一种蜡。例如,在示例性实施方案中,固体润滑剂包含以下或由以下组成:至少一种选自以下组的磷酸盐:磷酸锌、磷酸锌钙和磷酸锰;和选自聚乙烯蜡、氧化聚乙烯蜡、聚丙烯蜡、氧化聚丙烯蜡和基于乙烯或丙烯作为主要单体的共聚蜡的至少一种蜡。在这些实施方案中,组合物中包括的所述或每种蜡的特征还应当在于400至30,000g/mol、优选1000至25,000g/mol的数均分子量(Mn)。
为了促进它们包括在本发明的含水组合物中,可以首先提供所述或每种固体颗粒状润滑剂:i)以细碎粉末形式,特别是微粉化形式,其特征在于通过激光衍射测量的d50粒度小于5微米;和/或ii)作为水分散体,该分散体的颗粒可以理想地特征在于通过动态光散射测量的小于5微米的d50粒度。在示例性实施方案中,包括在含水组合物中的所述或每种固体颗粒状润滑剂可以具有通过激光衍射测量的小于2微米、优选小于1微米的d50粒度。
c)流变控制剂
基于组合物重量,本公开的含水润滑组合物包含0.1至5wt%的c)至少一种流变控制剂。含水组合物可优选包含0.1至2.5wt%、例如0.1至2wt%的c)所述至少一种流变控制剂。
在某些实施方案中,组合物中包括的一种或多种流变控制剂c)的总量应为组分a)和b)的总重量的1至10wt%,例如2至8wt%。
本文所用术语“流变控制剂”是指能够吸收液体(例如但不限于水)、物理溶胀并由此改变液体粘度和流动性的化合物。流变控制剂还可以充当增稠剂并且用于将组合物(特别是固体润滑剂)的组分保持为分散形式,通常通过产生连续相基质。该试剂还可用于改变组合物的干燥特性。
特别提及的是,包括在组合物中的所述或每种流变控制剂应该是触变胶。根据其标准定义,触变胶是这样的物质,其本身或当分散在溶剂(在本文中为水)中时表现出当施加应力(诸如当搅拌时)时降低的粘度。
不意图限制本发明,所述至少一种流变剂应选自以下组:粘土,诸如蒙皂石粘土、合成锂蒙脱石粘土、胶态蒙脱石、硅铝酸盐粘土和衍生自天然蒙皂石粘土的胶态硅酸镁铝;气相二氧化硅(热解二氧化硅);羧基乙烯基聚合物;聚乙烯吡咯烷酮(PVP)聚合物和共聚物,诸如PVP/乙酸乙烯酯共聚物;聚丙烯酸酯;纤维素衍生物,诸如羧甲基纤维素(CMC)、羧羟甲基纤维素、乙氧基甲基纤维素、羟乙基纤维素和羟丙基纤维素;天然增稠剂,诸如藻酸盐、瓜尔胶、淀粉、黄蓍胶和刺槐豆胶;多糖,诸如黄原胶;和蛋白质,诸如酪蛋白、胶原蛋白和白蛋白。
当组合物中包括颗粒状流变控制剂时,这些应优选最初以微粉化形式提供,其特征在于通过激光衍射测量的d50粒度小于5微米,特别是小于2微米。例如,气相二氧化硅、天然粘土和合成粘土(如用于包含在组合物中所提供的)的特征在于通过激光衍射测量的5-100nm、例如5-40nm的d50粒度。
除上述之外,可以注意到优选使用纤维素衍生物和/或多糖作为流变控制剂。例如,当在含水润滑组合物包含羧甲基纤维素(CMC)和黄原胶中的至少一种,优选两者的情况下,已经获得了关于含水润滑组合物的稳定性和保质期的良好结果。
d)碱
为了提供生物稳定性和抗锈蚀性,本公开的含水润滑组合物包含基于组合物的重量计0.1至5wt%的d)至少一种碱。含水润滑组合物可优选包含0.1至2.5wt%、例如0.1至2wt%的d)所述至少一种碱。
在某些实施方案中,其并不旨在与以上给出的优选重量范围相互排斥,碱的添加量应使得含水润滑组合物具有7至10、例如7至9的pH。
通常,包括在组合物中的所述或每种碱选自以下组:
碱金属醇盐;
氨;
具有通式(NRa 4)+(OH)-的季铵氢氧化物化合物,其中每个Ra独立地选自C1-C4烷基;
具有通式N(Rb)(Rc)(Rd)的脂族、芳族或混合脂族-芳族单胺,其中:Rb是C1-C12烷基、C1-C12羟烷基、C2-C12烷氧基烷基、C3-C18环烷基、C2-C12烯基、C6-C10芳基、C7-C18芳烷基或C7-C18烷基芳基;并且Rc和Rd独立地选自氢、C1-C12烷基、C1-C12羟烷基、C2-C12烷氧基烷基、C3-C18环烷基、C2-C12烯基、C6-C10芳基、C7-C18芳烷基或C7-C18烷基芳基;
脂族、芳族或混合脂族-芳族多胺,其中两个或更多个氨基-N(Rc)(Rd)通过亚烷基、羟基亚烷基,烷氧基亚烷基、亚环烷基、亚烯基、亚芳基、亚芳烷基或烷基亚芳基连接,氨基可以相同或不同并且其中Rc和Rd如上所定义;
C1-C9杂环胺;
C1-C9杂芳基胺;
碱性氨基酸,诸如精氨酸和赖氨酸;和
氨基糖。
合适的碱金属醇盐通常选自锂、钠或钾的脂族、芳族或芳脂族醇盐。其非限制性实例为锂、钠或钾的以下醇盐:甲醇盐、乙醇盐、正丙醇盐、异丙醇盐、正丁醇盐、仲丁醇盐、叔丁醇盐、正戊醇盐、异戊醇盐、己醇盐、戊基醇盐、3,7-二甲基-3-辛醇盐、苯酚盐、2,4-二叔丁基苯酚盐、2,6-二叔丁基苯酚盐、3,5-二叔丁基苯酚盐和2,4-二叔丁基-4-甲基苯酚盐。优选使用钠、钾或锂的脂族(C1-C4)醇盐,特别是甲醇盐、乙醇盐、正丙醇盐、异丙醇盐、正丁醇盐、仲丁醇盐和叔丁醇盐。
如上所述,组合物可以任选地包含氨(NH3)作为碱,其独立地或与其他所列碱组合。为了完整性,包括在组合物中的氨的组分重量是基于NH3计算的。氨将作为氨溶液NH3(aq)存在于本发明的含水组合物中,所述氨溶液涵盖氨在水中的弱碱性溶液,在本领域中可称为氢氧化铵、氨水、氨液、液氨、含水氨,或简称为氨。虽然术语“氢氧化铵”表示具有组成[NH4 +][OH-]的碱,但实际上不可能分离NH4OH样品,因为这些离子不包含氨溶液中氨总量的显著部分,除非在极稀氨溶液的情况下。
不意图限制本公开,合适的碱性胺(其可单独或组合包括在含水润滑组合物中)包括:甲胺;二甲胺;三甲胺;乙胺;二乙胺;三乙胺;环己胺;二甲基环己胺;乙醇胺;2-(二乙基氨基)乙醇;N,N-二甲基乙醇胺、2,2’-二羟基二乙胺(二乙醇胺);N-甲基哌啶;吡啶;2,6-二甲基吡啶;2,4,6-三甲基吡啶;喹啉;哌嗪;吡咯烷酮;1-(2-羟基乙基)吡咯烷;吗啉;N-甲基吗啉;4-(2-羟基乙基)吗啉;双(2-(N,N’-二甲基氨基)乙基)醚;双(叔丁基氨基乙基)醚、1,2-双(叔丁基氨基乙氧基)乙烷;1,2-双(叔丁基氨基乙氧基乙氧基)乙烷;双[2-(异丙基氨基)丙基]醚;1,2-[2-异丙基氨基)-丙氧基]乙烷;苯胺;N-甲基苯胺;4-甲基苯胺;4-羟基苯胺;吡咯;嘧啶;咪唑;喹唑啉;嘌呤;吡唑;和三唑。
当组合物包含至少一种选自以下组的碱时:双(2-(N,N’-二甲基氨基)乙基)醚;双(叔丁基氨基乙基)醚、1,2-双(叔丁基氨基乙氧基)乙烷;1,2-双(叔丁基氨基乙氧基乙氧基)乙烷;双[2-(异丙基氨基)丙基]醚;1,2-[2-异丙基氨基)-丙氧基]乙烷,获得了良好的结果。特别优选使用双(2-(N,N’-二甲基氨基)乙基)醚。
e)表面活性剂
该含水润滑组合物包含基于组合物的重量为0.1至5wt%的e)至少一种选自以下组的表面活性剂:阴离子表面活性剂、非离子表面活性剂、阳离子表面活性剂、两性表面活性剂和两性离子表面活性剂。基于组合物的重量,组合物可以包含0.1至2.5wt%、例如0.1至2wt%的e)所述至少一种表面活性剂。
在本公开中具有实用性的合适的非离子表面活性剂包括:C5至C25脂族醇与每摩尔所述醇1至25摩尔环氧乙烷的缩合产物,其中脂族醇的亚烷基链可以是直链或支化的,伯或仲的;烷基聚糖苷;烷基甘油醚;失水山梨糖醇酯;和脂肪酸酰胺表面活性剂。示例性的市售非离子表面活性剂包括:NeodolTM91-5、NeodolTM91-8和NeodolTM23-5,购自ShellInternational Research Maatschappij BV;Lutensol A7N、Lutensol XP 50、LutensolXL150、LutensolTMXL70、LutensolTMT07和LutensolTMON50,购自BASF;Novel 1412-7、IsalchemTM、LialTM和MarlipalTMO13/70,购自Sasol。
合适的两性表面活性剂和两性离子表面活性剂包括:通式(RmRnRoN-O)的氧化胺,其中Rm是C1-C18烷基并且Rn和Ro独立地选自C1-C4烷基、C1-C4羟烷基和C1-C6烷氧基烷基;和甜菜碱,诸如烷基甜菜碱、碳甜菜碱(carbobetaine)、烷基酰胺甜菜碱、咪唑啉鎓甜菜碱、磺基甜菜碱和磷基甜菜碱。示例性甜菜碱包括:合适的甜菜碱的实例包括但不限于:山萮酰氨基丙基甜菜碱;低芥酸酰胺丙基甜菜碱(canolamidopropyl betaines);癸酰氨丙基甜菜碱;椰油酰胺乙基甜菜碱;椰油酰胺基丙基甜菜碱;椰油酰胺基丙基羟基磺基甜菜碱;油酰胺基丙基甜菜碱;异硬脂酰胺丙基甜菜碱;月桂酰氨基丙基甜菜碱;月桂基甜菜碱;月桂基羟基磺基甜菜碱;月桂基磺基甜菜碱;肉豆蔻酰胺丙基甜菜碱;肉豆蔻基甜菜碱;油酰胺基丙基甜菜碱;油酰氨基丙基羟基磺基甜菜碱;油烯基甜菜碱;油酸酰胺丙基甜菜碱;棕榈油酰胺丙基甜菜碱;棕榈酰氨基丙基甜菜碱;蓖麻醇酸酰氨基丙基甜菜碱;硬脂酰胺丙基甜菜碱;和硬脂基甜菜碱。
合适的阴离子表面活性剂是硫酸盐、磺基琥珀酸盐、磺基乙酸盐和/或磺酸盐。示例性磺酸盐表面活性剂包括:C6-C18烷基磺酸盐(石蜡磺酸盐);C6-C18烷基苯磺酸盐;C6-C18烷基甘油基磺酸盐;甲基酯磺酸酯(MES);和α-烯烃磺酸酯(AOS)。然而,作为阴离子表面活性剂,对于C6-C18烷基硫酸盐、C6-C18羟烷基硫酸盐和乙氧基化度为1至5的烷基乙氧基硫酸盐的水溶性盐,可优选单独或组合使用。
合适的阳离子表面活性剂通常是季铵表面活性剂,特别是选自单N-C6-C18烷基或N-C6-C18烯基铵表面活性剂的季铵表面活性剂,其中剩余的N位被C1-C3烷基或C1-C3羟烷基取代。还可以提及季铵醇的C6-C18烷基或C6-C18烯基酯。
辅料成分
本公开的含水润滑组合物可进一步包含可赋予这些组合物改进的性质的辅料和添加剂。辅料和添加剂可以例如赋予以下各项中的一种或多种:增强的边界润滑;缩短的干燥时间;减少的腐蚀作用;改进的稳定性;和更长的组合物保存期。这些辅料和添加剂可以以期望的组合和比例使用,条件是它们不会不利地影响组合物的性质和基本性能。尽管在一些情况下可能存在例外,但这些辅料和添加剂总计不应占含水润滑组合物总重量的5wt%以上。
此类辅料和添加剂包括:油类;耐磨添加剂;腐蚀抑制剂;抗氧化剂;游离脂肪酸,其可以产生用于边界润滑的反应层;荧光增白剂,特别是在可能需要在光照下确认固体润滑剂的沉积的情况下;和增粘剂。
油的添加可用于在含水组合物干燥之后在基材表面上形成油性表面,并且可补偿以固体润滑剂的不均匀膜沉积为特征的工件的那些区域中的降低的润滑性能。此外,在其中含水润滑组合物在升高的温度下施用的组合物的那些实施方案中,这通常通过用蒸汽管加热润滑剂来实现:向含水润滑组合物中添加油可抑制固体颗粒状润滑剂粘附到加热管上。
油可以单独或组合使用,并且可以选自矿物油、动物油、动物脂肪、植物油和合成油。然而,所述或每种添加的油的特征通常应当在于以下各项中的至少一项并且优选全部:在150至300℃范围内的闪点;-20至20℃的熔点;和在40℃下测定的5至100厘斯的粘度。
超过20℃的熔点可导致水基润滑剂中油的乳化性和再乳化性降低,并因此导致处理浴稳定性降低的趋势。熔点低于-20℃的油性组分通常具有降低的闪点。同样,低于5厘斯的粘度通常与低闪点有关,其导致大量气体的后加工产生并因此导致点燃风险。同样地,当添加的油的粘度低于5厘斯时,固体润滑剂颗粒之间的滑移减小并且润滑性能趋于下降。相反,超过100厘斯的粘度通常导致水基润滑剂中油性组分的乳化性和再乳化性降低。
增粘剂用于改善润滑剂的传递速率并确保所施用和干燥的润滑组合物保持在适当位置以提供所需的润滑。组合物中包括的所述或每种增粘树脂优选地特征在于:70至150℃的软化点;并且,在150℃下小于2000Pa·s的粘度。
可单独或组合用于本发明的示例性增粘树脂包括:脂族和环脂族石油烃树脂;芳族石油烃树脂及其氢化衍生物;脂族/芳族石油衍生的烃树脂和氢化衍生物;聚环戊二烯树脂,氢化聚环戊二烯树脂和芳族改性的氢化聚环戊二烯树脂;萜烯、芳香族萜烯和氢化萜烯;聚萜烯、芳族改性的聚萜烯和萜烯酚醛树脂;α-甲基苯乙烯和其他乙烯基芳族单体的共聚物;和脂松香、脂松香酯、木松香、木松香酯、妥尔油松香、妥尔油松香酯和氢化松香酯。
含水组合物的制备
通过简单混合各种组分和任何辅助成分来配制含水润滑组合物。虽然组分的混合顺序不受限制,但可以谨慎地首先形成一种或多种流变控制剂(c)的水分散体,然后在搅拌下向分散体中加入无机盐(a)、固体润滑剂(b)和其他组分。固体润滑剂(b)应理想地在流变控制剂(c)和无机盐两者之后添加以确保形成稳定、均匀的分散体。如前所述,可能有利的是将颗粒组分和聚合物组分预制备为水分散体(例如固体含量为45至60wt%)以促进它们与组合物的其他组分的混合。无机盐a)也可以作为预制备的溶液加入或可以以固体形式但在确保盐在最终含水润滑组合物中呈溶解形式的混合条件下加入。
如果需要,含水润滑组合物可以在其应用之前很好地制备。然而,在一个有趣的替代实施方案中,浓缩的组合物可以首先通过将各组分仅与所施用的组合物中存在的一部分水混合来获得:然后,浓缩组合物可以在施用前不久用剩余的水稀释。据认为,这种浓缩组合物可以制备和储存为单包装浓缩物(其可仅用水稀释转化)或多部分浓缩物,其中两个或多个部分必须组合和稀释以形成根据本发明的完整加工组合物。任何稀释可以简单地通过在混合下加入水,特别是去离子水和/或软化水来实现。含水润滑组合物同样可以在漂洗料流中制备,由此将一种或多种浓缩物料流注入连续的水流中。
不特别意图限制含水润滑组合物中包括的水的量,基于组合物的重量,优选所述组合物包含60至90wt%、优选65至85wt%和更优选65至80wt%的水。在替代但非相互排斥的表征中,含水润滑组合物可通过使用Brookfield粘度计在25℃下测量的0.005至1Pa·s(50cps至1000cps)的粘度来定义。
方法和应用
在将组合物施加到金属基材之前,通常建议对相关表面进行预处理以除去其中的外来物质:如果适用,该步骤可促进组合物随后粘附到其上。这样的处理是本领域已知的,并且可以以例如通过使用以下中的一种或多种构成的单级或多级方式进行:用适合于基材的酸和任选存在的氧化剂进行蚀刻处理;声波处理;等离子体处理,包括化学等离子体处理、电晕处理、大气压等离子体处理和火焰等离子体处理;浸入水基碱性脱脂浴中;用水基清洁乳液处理;用清洁溶剂处理,诸如丙酮、四氯化碳或三氯乙烯;和用水漂洗,优选用去离子的或软化水。在使用水基碱性脱脂浴的那些情况下,任何残留在表面上的脱脂剂应理想地通过用去离子水或软化水冲洗基材表面而除去。
在所述清洁和/或脱脂之后,将含水润滑组合物施加到基材上。组合物可以在环境温度下施用,或者含水组合物的温度可以在施用之前升高至例如30℃至90℃、例如30℃至70℃的温度。
为了生产双面镀覆片材,商业上常规的是制备如上所述的操作浴,并通过但不限于浸渍和浸涂将含水润滑组合物施加到基材上。含水润滑组合物的接触时间不是关键的,但应当足以使基材的温度与操作浴中组合物的温度平衡。示例性接触时间为1分钟至15分钟,例如2至10分钟。
可用于将含水润滑组合物施加到基材的单个表面或多个表面的替代技术包括但不限于:涂漆;刷涂;流涂;辊涂;擦拭;空气雾化喷涂;空气辅助喷涂;无空气喷涂;大容量低压喷涂;和空气辅助的无空气喷涂。
在施用步骤结束时,使用例如环境空气干燥、循环热空气、强制空气干燥或红外加热来干燥制品。在干燥期间控制基材的表面温度:峰值金属温度(PMT)不需要超过150℃,更具体地,应当在100至125℃的范围内,例如100至120℃。
上述处理应当在金属基材上产生保护膜,所述膜优选具有1至50g/m2、优选1至40g/m2或5至40g/m2的膜重量。要进行的金属加工的类型,加工程度和基材表面粗糙度将决定干燥涂层的最佳厚度。然而,通常,当干燥的膜太薄时,在加工工具和基材本身之间会发生接触,然后容易发生咬合。当干燥的膜太厚时,一部分膜可能不会被拉入加工工具和基材之间的界面中:因此该部分将构成水基润滑剂的废物。
没有意图限制水基润滑组合物可以施加到的基础基材。因此,合适的基材金属基材可包括但不限于:铁;钛;镍;锌;铜;铝;锡;钴;及其合金。可特别提及包含钢或由钢组成的基材,其实例包括:符合ASTM编号A653要求的镀锌钢和合金化镀锌钢(galvannealsteel);购自Bethlehem Steel公司的55%Al/43.4%Zn/1.6%Si合金镀覆钢板;和/>购自Weirton Steel的5%Al/95%Zn合金涂覆的钢板。
含水润滑组合物施加到其上的基材的初始形式也不需要限制,除了说该形式必须适合于要使用的工具和在冷加工之后要获得的目标形状或形式。虽然当然不排除更复杂的形状,但可以提供金属和合金基材的传统坯料形式包括:片材;板材;长方体;球体;环形;实心圆柱体;管;和线。
如上所述,本公开还提供了水性水基润滑剂组合物或由其获得的干膜在金属基材的塑性冷加工中的用途。
本公开进一步提供了一种用于固体金属基材的塑性冷加工的方法,该方法通过以机械方式迫使所述固体金属基材穿过由至少一个金属加工工具的至少一个固体表面界定的孔,所述方法包含以下步骤:
i)将如本文以上中所限定的含水润滑组合物施用到所述金属基材的至少一个固体表面上,一个或多个表面如果未被涂覆将在所述方法期间直接接触固体金属加工工具表面;
ii)干燥所施用的含水润滑组合物以在所述金属基材的所述至少一个固体表面上形成膜;和
(iii)以机械方式迫使在步骤ii)中形成的金属基材通过由至少一个金属加工工具表面限定的所述孔,使得金属基材被冷加工。
公认的是,金属的塑性冷加工通常是反复的过程。因此,上述方法可包括以下另外的步骤:
iv)从步骤iii)中形成的冷加工的金属基材的所述至少一个固体表面上除去残余膜;
v)将步骤iv)中获得的所述金属基材退火;和
vi)重复步骤i)至iii)。
在一个实施方案中,步骤iv)包含用碱性脱脂剂处理残余膜。特别优选的是,步骤iv)不包含用酸性酸洗液处理残余膜。
在步骤iii)之后获得的残余润滑膜在退火之前未被除去的情况下,润滑膜的碳、硫、磷和其他组分可渗入金属基材中,从而损害该基材的耐腐蚀性和机械强度。此外,在上述步骤i)的第二次(和进一步)重复中,残余润滑膜将不呈现含水润滑组合物将粘附到的表面。
在以下实施例中描述了本公开的各种特征和实施方案,其旨在是代表性的而非限制性的。
实施例
在实施例1中使用以下市售产品,实施例1代表根据本发明的组合物:下文提及的其它成分可从Sigma Aldrich公司获得。
ChemipearlTMW900:低分子量聚乙烯(PE),购自Mitsui Chemicals。
Laponite RD:高度纯化的合成胶态粘土,购自BYK Chemie。
Triton DF16:封端的乙氧基化醇表面活性剂,购自Dow Chemical。
Plurafac LF1430:烷氧基化脂肪醇表面活性剂,购自BASF。
Surfynol 440:非离子表面活性剂,购自Evonik Industries。
通过混合下表1中给出的各成分制备含水润滑组合物。制备无机盐(a)在水中的溶液,向其中加入流变控制剂(c)、碱(d)和表面活性剂,随后加入固体润滑剂(b)。固体润滑剂(b)作为在水中的预制备的分散体加入。
鉴于上述描述和实例,对于本领域技术人员来说显而易见的是,在不脱离权利要求的范围的情况下,可以对其进行等同的修改。
表1
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Claims (15)
1.一种含水润滑组合物,基于所述组合物的重量,其包含:
1-20wt%的a)至少一种水溶性无机盐,所述一种或多种无机盐处于溶解状态;
b)至少一种颗粒状固体润滑剂;
0.1-5wt%的c)至少一种流变控制剂;
0.1-5wt%的d)至少一种碱;和
0.1-5wt%的e)至少一种选自以下组的表面活性剂:阴离子表面活性剂、非离子表面活性剂、阳离子表面活性剂、两性表面活性剂和两性离子表面活性剂,
其中所述组合物不含硼和硼化合物,并且其特征还在于b)所述至少一种固体润滑剂与a)所述至少一种水溶性无机盐的重量比[(b):(a)]为0.1:1至1:1。
2.根据权利要求1所述的含水润滑组合物,基于所述组合物的重量,其包含:
2-20wt%、优选5-20wt%的a)所述至少一种水溶性无机盐;
b)所述至少一种颗粒状固体润滑剂;
0.1-2.5wt%、优选0.1-2wt%的c)所述至少一种流变控制剂;
0.1-2.5wt%、优选0.1-2wt%的d)所述至少一种碱;和
0.1-2.5wt%、优选0.1-2wt%的e)所述至少一种选自以下组的表面活性剂:阴离子表面活性剂、非离子表面活性剂、阳离子表面活性剂、两性表面活性剂和两性离子表面活性剂,
其中所述组合物不含硼和硼化合物,并且其特征还在于b)所述至少一种固体润滑剂与a)所述至少一种水溶性无机盐的重量比[(b):(a)]为0.1:1至1:1,优选0.2:1至1:1。
3.根据权利要求1或2所述的含水润滑组合物,基于所述组合物的重量,其包含60-90wt%、优选65-85wt%、更优选65-80wt%的水。
4.根据权利要求1至3中任一项所述的含水润滑组合物,其中所述组合物的特征在于使用Brookfield粘度计在25℃下测量的0.005-1Pa·s的粘度。
5.根据权利要求1至4中任一项所述的含水润滑组合物,其中所述组合物中包括的流变控制剂c)的总量为组分a)和b)的按重量计总量的1-10wt%,优选2-8wt%。
6.根据权利要求1至5中任一项所述的含水润滑组合物,其具有7至10、优选7至9的pH。
7.根据权利要求1至6中任一项所述的含水润滑组合物,其中组分a)包含硫酸钠、三聚磷酸钾和三聚磷酸钠的混合物。
8.根据权利要求1至7中任一项所述的含水润滑组合物,其中所述组合物中包括的所述或每种固体颗粒状润滑剂的特征在于通过激光衍射测量的d50粒度小于5微米。
9.根据权利要求1至8中任一项所述的含水润滑组合物,其中所述组分b)包含:
至少一种选自以下组的磷酸盐:磷酸锌、磷酸锌钙和磷酸锰;和
至少一种选自以下组的蜡:聚乙烯蜡;氧化聚乙烯蜡;聚丙烯蜡;氧化聚丙烯蜡;和基于乙烯或丙烯作为主要单体的共聚蜡,
此外,其中所述至少一种蜡的特征在于400-30000g/mol、优选1000-25000g/mol的数均分子量(Mn)。
10.根据权利要求1至9中任一项所述的含水润滑组合物,其中c)所述至少一种流变控制剂选自以下组:纤维素衍生物;和多糖。
11.根据权利要求10所述的含水润滑组合物,其中组分c)包含羧甲基纤维素(CMC)和黄原胶。
12.根据权利要求1至11中任一项所述的含水润滑组合物,其中d)所述至少一种碱选自以下组:双(2-(N,N’-二甲基氨基)乙基)醚;双(叔丁基氨基乙基)醚、1,2-双(叔丁基氨基乙氧基)乙烷;1,2-双(叔丁基氨基乙氧基乙氧基)乙烷;双[2-(异丙基氨基)丙基]醚;1,2-[2-异丙基氨基)-丙氧基]乙烷。
13.根据权利要求12所述的含水润滑组合物,其中组分d)包含双(2-(N,N’-二甲基氨基)乙基)醚或由双(2-(N,N’-二甲基氨基)乙基)醚组成。
14.根据权利要求1至13中任一项所限定的含水水基润滑组合物或由其获得的干膜在金属基材的塑性冷加工中的用途。
15.一种用于固体金属基材的塑性冷加工的方法,所述方法通过以机械方式迫使所述固体金属基材穿过由至少一个金属加工工具的至少一个固体表面界定的孔,所述方法包含以下步骤:
i)将根据权利要求1至13中任一项所限定的含水润滑组合物施用到所述金属基材的至少一个固体表面上,所述一个或多个表面如果未涂覆则在所述方法期间直接接触固体金属加工工具表面;
ii)干燥所施用的含水润滑组合物以在所述金属基材的所述至少一个固体表面上形成膜;和
(iii)以机械方式迫使在步骤ii)中形成的所述金属基材通过由至少一个金属加工工具表面限定的所述孔,使得所述金属基材被冷加工。
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