CN1044774A - 用于拉丝的水溶盐予涂层 - Google Patents

用于拉丝的水溶盐予涂层 Download PDF

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Publication number
CN1044774A
CN1044774A CN90101159A CN90101159A CN1044774A CN 1044774 A CN1044774 A CN 1044774A CN 90101159 A CN90101159 A CN 90101159A CN 90101159 A CN90101159 A CN 90101159A CN 1044774 A CN1044774 A CN 1044774A
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Prior art keywords
component
composition
total amount
water
gram
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CN90101159A
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托马斯·W·突尔
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Henkel Corp
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Henkel Corp
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Abstract

用于涂覆钢丝使之易于冷拉制的组合物，包括：
A、大约50-99.9Wt％的K2SO4；
B、大约0-49.99Wt％的K2B4O7和/或KBO2；和
C、大约0.01-5Wt％的铵皂和/或钾皂；组合物内钾离子加铵离子总量的至多50Wt％可用钠离子替代。这些组合物形成的涂层具有优良的晶态结构，可拉制性和低吸湿性。

Description

本申请是待批的1989年2月7日入档，流水号为307643共同申请之续申请。
本发明涉及用于冷拉制钢丝的改性水溶盐予涂层。
钢丝拉制前，通常将水溶盐涂层以水溶液形式进行涂覆。将溶液涂覆过的钢丝干燥，再将所得有盐涂层的钢丝通过使用干皂润滑剂的缩径拉模常规工艺进行拉制，该工艺是本领域公知的。水溶盐涂层起润滑剂载体的作用，将干皂盒的润滑剂拉入模内以便润滑。这些干燥固定的水溶盐涂层由于改进了将润滑剂带入模内的能力，证实比其他常规涂层如石灰或硼砂涂层优越。用于钢丝（一般是不锈钢丝）的典型可溶盐组合物含有硫酸钠和硼砂。这种可溶盐组合物使涂层具有极好的晶体结构，当有涂层的钢丝通过皂盒时能很好地粘结皂润滑剂，因而使钢丝具备良好的可拉制性。但是这种盐涂层暴露在环境气氛。特别是暴露在高湿度气氛时易于吸收过多水份。这种吸湿会严重防碍或者甚至不能拉制有涂层的钢丝。另方面，吸收少量水份的可溶盐涂层得到的几乎不是或完全不是结晶结构（也就是非晶态或珐琅质涂层），其粘结润滑剂和可拉制性方面都相当差。这种毫无选择余地的问题还未曾解决。
除在实施例中或其他指明的地方外，这里表示的各种成份的量或反应条件的数字可理解为所有情况下皆可加上“大约”二字。
现已发现，用于涂覆钢丝的组合物能够提供良好的晶体结构、皂的粘结性和可拉制性;同时，即使在潮湿天气也仅能吸收少量水份，亦即低吸湿性的均匀涂层。
本发明的组合物在用水稀释使用之前是干燥的混合物，含有下述成分：
A.50-99.99%（重量比，以下记作wt）的K2SO4，较佳为70-89.9wt%;
B.0-49.99wt%的K2B4O7和/或KBO2，较佳为10-29.9wt%;和
C.0.01-5wt%的铵或钾皂，较佳为0.1-1.0wt%;
其中，在A、B和C内钾和铵离子总量的至多为50wt%，较佳为不超过10wt%可用钠离子更替，因为钠离子越多，吸水性越大。有钠离子时，钠离子可存在于组分A.，B.和C.的一种或多种之中，如存在于组分C.中，可部分是或全部是钠皂。也可存于组分A.和/或B.中，可为一种钠盐或钾盐，也可为二者混合物，但钠离子总量要有限制。
上述组合物在钢丝上提供良好结晶性完全出乎予料，因为不含组分C.的上述组合物在钢丝上得非均匀涂层而毫无用处，这种涂层的皂粘结性和可拉制性都不能令人满意。水溶液中的组合物涂到钢丝上随后干燥或令其干燥时，皂的存在，以某种不知道的方式，提供一种至少部分结晶化的均匀涂层。
用作组分A.的K2SO4可是化学纯或工业级品位物质，出于成本考虑，后者较佳。
用作组分B.的K2B4O7也可是化学纯或工业纯，通常可用且在此使用的是四水合物（K2B4O7.4H2O）。同样，KBO2可单独用作组分B.或以任何比例与K2B4O7混合，可为化学纯也可为工业纯。
铵或钾皂是C12-C22脂肪酸的一种或多种铵和/或钾盐，或者两种以上的C12-C22脂肪酸混和酸的一种或多种铵和/或钾盐。脂肪酸一般为饱和非支链的，带有铵或钾的硬脂酸盐在此使用较佳;也可使用一或二烯属C12-C22不饱和脂肪酸，可单独使用其一也可使用二者的混合物和/或与饱和脂肪酸的混合物。例如，由动物脂油或可可豆油或其混和物皂化制得脂肪酸混合物，再由此得到铵或钾皂用作组分C更为有益。此外，支链的或含脂肪环烃的C12-C22脂肪酸铵或钾盐亦可在此使用，可单独使用其一也可使用其与直链脂肪酸盐的混合物。树脂酸，如松香酸的铵或钾盐也可用作组分C。
用本发明组合物涂覆的丝一般是钢丝，通常是不锈钢丝。然而，其他基体的丝也可使用本发明的涂层组合物来涂覆，例如低碳钢，钛、钒、钨、铝、铜、镍、锆等等及其合金。
进行涂覆的方式是将本发明    组合物的水溶液与钢丝接触，然后令湿涂层干燥固定，可使用或不使用热源。水溶液一般在水中含组合物为75-400g/l，较佳为150-250g/l。
可用任何常规技术将丝与溶液进行接触，既可整束接触也可连续进线接触;在打卷贮存、运输和使用之前，要让制得的湿涂层钢丝在空气中干燥。有涂层的丝随后通过常规缩径装置时要使用皂盒（例如常规的干皂润滑剂）。丝上的涂层起载体作用，将干皂润滑剂带入模具。
根据本发明，丝的处理包括下列步骤：
1.清洗丝-清洗用组合物为本领域公知技术，不属本发明范围。
2.用水冲洗。
3.酸洗-酸洗用组合物也是熟知的，酸洗用组合物的选择不属本发明范围。
4.水冲洗。
5.如前述用本发明组合物进行涂覆。
6.如前述将涂覆过的丝进行干燥制得本发明有涂层的丝。
仍如前述，随后将有涂层的丝进行拉制。
用于制备本发明水溶液的水最好是蒸馏水或去离子水，但也可使用自来水，只要它不太硬且含溶解的钠盐少就行。
下列实施例仅用来解释并非限制本发明。
实施例1
将下列组合物水溶液涂覆不锈钢片，测其结构和吸水性。将不锈钢片浸在各种组合物水溶液中，然后取出钢片令其在新鲜（空气）中干燥，以此方式使不锈钢片上涂层。
（a）每升去离子水含187.2g的75wt%Na2SO4和25wt%Na2B4O7·10H2O之混合物。
使用温度190°F。
（b）每升去离子水含187.2g75wt%K2SO4和25wt%K2B4O7·4H2O的混合物。
使用温度190°F。
（c）于如（a）制备的水溶液中加入5g/l的硬脂酸钠。
使用温度190°F。
（d）在如（b）制备的水溶液中加入5g/l的硬脂酸铵。
使用温度190°F。
将上述组合物涂覆的不锈钢片部分进行测试其吸水性和结构。试验结果列于表Ⅰ中。表Ⅰ内的RH＝相对湿度。
表Ⅰ
吸水性＊
涂覆液    90-95%RH/环境气氛
组合物    90分    /24小时    结构
（a）    16.5%    107.0%    结晶态
（b）    5.1%    2.7%    非晶珐琅质（釉）
（c）    16.1%    -    结晶/部分珐琅质
（d）    7.5%    3.4%    结晶/部分珐琅质
＊在涂层中水份的平均百分数。通过测试未涂覆和已涂覆的钢片在空气中暴露前后之重量差别而测定水份吸收量。
从表Ⅰ可见，本发明组合物，组合物（d），制备的涂层具有良好结晶性和低吸水性。
实施例2
本实施例说明钠和钾离子的相对比例对水溶盐涂层吸水性的作用。在本实施例中，不锈钢片按实施例1的方式用下列表Ⅱ所示组合物进行涂覆，表Ⅱ同时也给出试验结果。在表Ⅱ中，M＝体积克分子浓度或叫作克分子/升溶液，RH＝相对湿度。
实施例3
本实施例说明石灰涂层与已知的钠基盐组合物涂层以及本发明的低钠盐组合物涂层相对比的相对吸水性。用实施例1中的不锈钢丝试样按实施例1的工艺用下列组合物水溶液制备涂层：
（j）每升去离子水中含187.2g75wt%Na2SO4和25wt%Na2B4O7·10H2O的混合物。
使用温度190°F。
（k）每升去离子水含187.2g79wt%K2SO4，20wt%Na2B4O7·10H2O和1摩尔%硬脂酸铵。
使用温度190°F。
（l）去离子水中含3wt%石灰。
使用温度190°F。
（m）去离子水中含6wt%石灰。
使用温度190°F。
结果列于下表Ⅲ。
表Ⅲ
涂覆液    吸收水份%，80-90%RH，24小时
组合物
（j）    28.3%
（k）    3.0%
（l）    17.6%
（m）    18.4%
如表Ⅲ所示，本发明组合物（k）与石灰（l）和（k）涂层相比，明显降低吸水性。实施例4
评价十种不同涂覆液组合物对水份吸收、结构、涂层均匀性及每英寸不锈钢片上结晶情况等性能。
不锈钢片用表Ⅳ列出的涂覆组合物和涂覆液按实施例1的工艺进行涂覆，所不同的是湿涂层片在250°F下烘10分钟使它干燥。水份的吸收在一小室中测定，令该小室的温度和湿度分别恒定在80°F和92%。用（Surtronic    3    Surface    Prophylometer）测定每寸涂层上结晶体的数目。肉眼观察涂层特征和外观。
表Ⅳ
涂层液成分 涂层组合物（g/l) (g/l)硬脂酸盐
钠 钾   硫酸盐 四硼酸盐
A-硫酸钠B-硫酸钠和四硼酸钠C-硫酸钠和硬脂酸钠皂（10.0g/l)D-硫酸钾E-硫酸钾和硬脂酸钠皂（10.0g/l)F-硫酸钾和硬脂酸钠皂（0.1g/l)G-硫酸钾和硬脂酸铵皂（0.1g/l)H-硫酸钾和四硼酸钾I-硫酸钾和四硼酸钠J-硫酸钾四硼酸钠和硬脂酸钠 54.351.955.0-0.7痕量--5.75.7 ---75.275.275.275.272.363.963.9 113.296.3113.292.392.392.392.378.678.678.6 -19.3-----16.719.619.6 --9.3-0.090.090.09--0.09
表Ⅳ（续）
涂层液成分 水分吸收120分钟RM = 92%80F 晶体每英寸 涂层特征 涂层外观
A-硫酸钠B-硫酸钠和四硼酸钠C-硫酸钠和硬脂酸钠皂（10.0g/l)D-硫酸钾E-硫酸钾和硬脂酸钠皂（10.0g/l)F-硫酸钾和硬脂酸钠皂（0.1g/l)G-硫酸钾和硬脂酸铵皂（0.1g/l)H-硫酸钾和四硼酸钾I-硫酸钾和四硼酸钠J-硫酸钾四硼酸钠和硬脂酸钠 120％98％103％0％1％1％1％4％7％5％ 87126167435080779386153 混合釉／晶体结晶态结晶态混和，主要是釉混和，主要是釉混和釉／晶体混和釉／晶体混和釉／晶体混和釉／晶体结晶态 不均匀均匀不均匀不均匀不均匀均匀不均匀不均匀不均匀均匀
表Ⅳ中，涂覆组合物F、G和J是本发明的组合物，而A、B、C、D、E、H和I是对比组合物。表Ⅳ可见组合物F、G和J可形成均匀涂层，同时仅吸收少量水份。能形成均匀涂层的对比组合物只有组合物B，但呈现高度吸湿而令人不能接受。事实上组合物A、B和C都显出令人无法接受的高吸湿性，因为在潮湿条件下丝的可拉制性较差。涂覆组合物E是含硫酸钾和硬脂酸钠皂的本发明组合物，但硬脂酸钠皂含量过高，得到不均匀的、主要是釉的涂层，丝的可拉制性不可取。涂覆组合物D、H和I是含钾盐的本发明组合物，但不含皂，得到的都是不可接受的非均匀涂层，因之丝的可拉制性亦不能接受。本发明的涂覆组合物F、G和J进行比较时，组合物J含碱金属四硼酸盐，生成基本为晶态的涂层。然而在本发明的涂覆组合物中，四硼酸盐的存在，也可不存在，依然是高度可取的。

Claims (18)

1、一种用来涂覆钢丝使之易于冷拉制的组合物，包括：
A.大约50-99.9wt%的组分选自Na2SO4，K2SO4及其混合物；
B.大约0-49.9wt%的组分选自Na2B4O7，NaBO2，K2B4O7，KBO2及其任意二种组分以上的混合物；和
C.大约0.01-5wt%的组分选自钾皂、钠皂和铵皂；
其中，重量百分比是基于组合物中组分A、B和C的总重量，且其中所含钠离子不得超过组合物中A、B和C组分中的钠、钾和铵离子总量的50wt%。
2、一种用于拉制钢丝的方法，其改进之处在于拉制前用一种组合物涂覆钢丝，该组合物包括：
（A）大约50-99.99wt%的组分选自K2SO4，Na2SO4及其混合物。
（B）大约0-49.99wt%的组分选自Na2B4O7，NaBO2，K2B4O7，KBO2及其中任二种组分以上的混合物，和
（C）大约0.01-5wt%的组分选自铵皂、钾皂、钠皂及其任二种以上组分的混合物;
其中，重量百分数是基于组合物中组分A，B和C的总重量，且其中所含钠离子不得多于组合物中钠离子加钾离子加铵离子总量的50wt%。
3、根据权利要求2的方法，其中含组分A大约70-89.9wt%，组分B大约10-29.9wt%，含组分C大约0.1-1.0wt%。
4、根据权利要求2的方法，其中组分C选自硬脂酸铵，硬脂酸钾和硬脂酸钠。
5、根据权利要求2的方法，其中钠离子含量不超过组合物中钠离子加钾离子加铵离子总量的10wt%。
6、根据权利要求5的方法，其中的组合物中基本不含钠离子。
7、根据权利要求2的方法，其中含组分A大约70-89.9wt%。
8、根据权利要求2的方法，其中含组分B大约10-29.9wt%。
9、根据权利要求2的方法，其中含组分C大约0.1-1.0wt%。
10、根据权利要求2的方法，其中组分B选自K2B4O7和Na2B4O7。
11、根据权利要求2的方法，其中组合物内含有溶解组分A、B、C使之形成水溶液的水。
12、根据权利要求11的方法，其中每升溶液内组合物含组分A、B和C的总量为大约70-400克。
13、根据权利要求12的方法，其中每升水溶液中含组分A、B和C的总量为大约150-250克。
14、根据权利要求5的方法，其中组合物内含有溶解组分A、B、C使之形成水溶液的水，每升水溶液中含组分A、B、C的总量为大约70-400克。
15、根据权利要求6的方法，其中组合物内含有溶解组分A、B、C使之形成水溶液的水，每升水溶液中含组分A、B、C的总量为大约70-400克。
16、根据权利要求3的方法，其中组合物内含有溶解组分A、B、C使之成为水溶液的水，每升水溶液中含有组分A、B、C的总量为大约70-400克。
17、根据权利要求4的方法，其中组合物内含有溶解组分A、B、C使之成为水溶液的水，每升水溶液中含组分A、B、C的总量为大约70-400克。
18、根据权利要求5的方法，其中组合物内含有溶解组分A、B、C使之成为水溶液的水，每升水溶液含组分A、B、C的总量为大约70-400克。
CN90101159A 1989-02-07 1990-02-07 用于拉丝的水溶盐予涂层 Pending CN1044774A (zh)

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CN102152069A (zh) * 2011-01-30 2011-08-17 烟台鑫杰特钢有限公司 一种气阀钢型材生产方法

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DE4440301A1 (de) * 1994-11-11 1996-05-15 Metallgesellschaft Ag Schmiermittelträgersalz für die Metallumformung
CN104593125B (zh) * 2015-01-29 2017-07-11 南京工程学院 一种抗结块拉丝润滑粉
IT202200006158A1 (it) 2022-03-29 2023-09-29 Condoroil Chemical S R L Processo per produrre un rivestimento per operazioni di deformazione a freddo esente da boro

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US2957825A (en) * 1956-10-15 1960-10-25 Devex Corp Powdered soap lubricant containing inorganic sulfur salts
GB2003923B (en) * 1977-09-07 1982-03-10 Foseco Int Metal working lubricants
CH670106A5 (zh) * 1984-07-23 1989-05-12 Lonza Ag

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102152069A (zh) * 2011-01-30 2011-08-17 烟台鑫杰特钢有限公司 一种气阀钢型材生产方法
CN102152069B (zh) * 2011-01-30 2013-06-05 烟台鑫杰特钢有限公司 一种气阀钢型材生产方法

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ATE92951T1 (de) 1993-08-15
ES2059847T3 (es) 1994-11-16
CA2009377A1 (en) 1990-08-07
AU621980B2 (en) 1992-03-26
EP0382155B1 (en) 1993-08-11
BR9000543A (pt) 1991-01-15
ZA90917B (en) 1990-11-28
DK0382155T3 (da) 1993-09-20
JPH02229893A (ja) 1990-09-12
EP0382155A1 (en) 1990-08-16
DE69002649D1 (de) 1993-09-16
AU4920990A (en) 1990-08-16
DE69002649T2 (de) 1993-12-16

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