CN106893953B - 一种钴基非晶合金粉末及生产方法 - Google Patents
一种钴基非晶合金粉末及生产方法 Download PDFInfo
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- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 33
- 239000000843 powder Substances 0.000 title claims abstract description 26
- 239000010941 cobalt Substances 0.000 title claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 239000000956 alloy Substances 0.000 claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005275 alloying Methods 0.000 claims abstract description 7
- 238000009713 electroplating Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000008139 complexing agent Substances 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 238000012216 screening Methods 0.000 claims abstract description 4
- 238000005238 degreasing Methods 0.000 claims abstract description 3
- 238000007747 plating Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 230000033001 locomotion Effects 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical group C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 3
- 229940081974 saccharin Drugs 0.000 claims description 3
- 235000019204 saccharin Nutrition 0.000 claims description 3
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- 238000004448 titration Methods 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000004615 ingredient Substances 0.000 abstract description 3
- 238000005096 rolling process Methods 0.000 abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 abstract description 2
- 229910052702 rhenium Inorganic materials 0.000 abstract description 2
- 238000007790 scraping Methods 0.000 abstract description 2
- 238000005480 shot peening Methods 0.000 abstract description 2
- 238000004070 electrodeposition Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910018104 Ni-P Inorganic materials 0.000 description 2
- 229910018536 Ni—P Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000001154 acute effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 239000006247 magnetic powder Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
-
- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/04—Electroplating with moving electrodes
- C25D5/06—Brush or pad plating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
一种钴基非晶合金粉末成分为:钴40‑95 wt%,合金元素为可以与钴一起电沉积的元素,如P、Ni、Fe、Cr、Mo、W、Re等中的一种或多种元素的组合。粉末的生产方法,包括以下步骤:(1)金属基板被镀表面的除锈、脱脂预处理;(2)电镀液组成:硫酸钴1‑4.5mol/L(优选2‑3.5mol/L)、酸0.3‑1mol/L、络合剂0.5‑5g/L、合金元素添加剂0.2‑2mol/L、添加剂0‑2g/L,余量水;(3)采用电刷镀方法制备非晶合金镀层;(4)采用机械或物理的方法,如轧制压延、喷丸、刮擦等方法使非晶合金镀层剥落;(5)非晶合金颗粒的球磨;(6)非晶合金粉末的筛分。
Description
技术领域
本发明涉及一种非晶合金粉末,尤其是涉及一种钴基非晶合金粉末及生产方法。
背景技术
随着电子电力、通信工业的发展,电子元器件向小型化、高频化和大电流方向发
展,而且对电子设备的电磁兼容性能的要求也越来越高,传统的非晶带材铁芯、软磁铁氧体
及金属磁粉芯等不能满足需求,应用受到限制。主要表现在:(1) 非晶带材铁芯在高频工作
时感应涡流导致损耗很大,限制其在高频领域的应用;(2) 软磁铁氧体高频损耗低,但是饱和磁感应强度和磁导率低,不能满足小型化和大电流的发展需求;(3) 金属磁粉芯存在着高频损耗高、直流叠加特性差或者价格昂贵等问题,限制了其应用范围。非晶磁性粉末由于其优异的软磁性能,可以满足各种电子元器件稳定化、小型化、高频化、大电流、高功率的需求,能极大促进汽车、电子、航空航天领域等高新技术行业的发展。
非晶结构具有长程无序、短程有序的结构,使粉末具有很多独特的性能。钴基非晶合金粉末除具有优异的磁性能,还具有耐高温、耐燃气腐蚀、耐磨、耐蚀等性能,在电子、涂层和硬质合金中得到广泛应用。而一些特殊场合对粉末性能提出更高的要求。
到目前为止,非晶合金粉末的制备工艺主要有水雾法、气雾法以及使用非晶薄带破碎制粉的工艺。水雾法具有大的冷却速率,可满足制备非晶态粉末的要求。然而,在水雾化过程中,所获得的粉末易形成氧化物,氧含量高,再者当熔融金属凝固时,产生的水蒸气会覆盖在熔融金属的表面,该水蒸气膜的存在将导致熔融的核心金属冷却强度降低,从而使粉末中心部分不能获得非晶态结构的问题,影响器件性能。气雾法由于冷却强度受限,只能制备非晶形成能力强的非晶合金粉末,且生产成本高。直接破碎法的优点在于对物料的选择性不强,材料利用率高,但需对非晶薄带进行脆化退火,很容易由于退火不均造成薄带内部晶化转变的不均匀,而且在破碎后容易产生带有锐角的粉末颗粒,为粉末的后续加工带来困难。
而与液态急冷法、溅射法制备非晶合金材料相比,电镀法更为经济,应用范围也更为广阔。电刷镀镀层的形成从本质上讲和电镀相同,都是溶液中的金属离子在负极(工件)上放电结晶的过程。但是和电镀相比,电刷镀中镀笔和工件有相对运动,因而被镀表面不是整体同时发生金属离子还原结晶,而是被镀表面各点在镀笔与其接触时发生瞬间放电结晶。因此,电刷镀技术在工艺方面有其独特之处,其特点可归纳如下:
1、设备简单,不需要镀槽,便于携带,适用于野外及现场修复。尤其对于大型、精密设备的现场不解体修复更具有实用价值;
2、工艺简单,操作灵活,不需要镀的部位不要用很多的材料保护;
3、操作过程中,阴极与阳极有相对运动,故允许使用较高的电流密度,它比槽镀使用的电流密度大几倍到几十倍;
4、镀液中金属离子含量高,所以镀积速度快(比槽镀快5倍~10倍);
5、有不同型号的镀笔,并配有形状不同、大小不一的不溶阳极,对各种不同几何形状及结构复杂的零部件都可修复;
6、费用低,经济效益大。
发明内容
针对上述问题,本发明基于电刷镀原理,提供了一种非晶合金材料组元的构成及比例选择范围更广的钴基非晶合金粉末及生产方法。
本发明的钴基非晶合金粉末成分为钴 40-95 wt %,合金元素为可以与钴一起电沉积的元素,如P、Fe、Cr、Ni、Mo、W、Re等中一种或多种元素的组合。
本发明钴基非晶合金粉末的生产方法,包括以下步骤:
(1)金属基板被镀表面的预处理:金属基板被镀表面可采用机械或化学方法除锈、脱脂;
(2)电镀液组成:氯化钴、硫酸钴或两者的混合物1-4.5mol/L(优选2-3.5mol/L)、酸0.3-1mol/L、络合剂0.5-5g/L、合金元素添加剂0.2-2mol/L、添加剂0-2g/L,余量水;
上所述合金元素添加剂中,铁以硫酸亚铁或氯化亚铁(需配有还原剂)、铬以铬酐、钼以钼酸钠、镍以硫酸镍或氯化镍、钨以钨酸钠、磷以亚磷酸或可溶性次磷酸盐、Re以Re可溶盐的形式添加;
上述酸包括硼酸、磷酸、羧酸等;
上述络合剂包括酒石酸、十二烷基苯磺酸钠、十二烷基硫酸钠、柠檬酸盐等;
上述添加剂为糖精、对甲苯磺酸胺等;
(3)非晶合金镀层的制备:采用电刷镀方法制备非晶合金镀层,阳极采用石墨,电极的电流密度为0.3-1.5A/mm2(优选0.8-1.2 A/mm2),电极相对运动速度为5-20m/min(优选10-15m/min),滴定强酸溶液使镀液Ph值小于1,施镀温度为30-60℃,;
(4)采用机械或物理的方法,如轧制压延、喷丸、刮擦等方法使非晶合金镀层剥落;
(5)非晶合金颗粒的球磨,将剥落的非晶颗粒在真空或惰性气体保护条件下进行球磨,球磨可采用球磨机、行星式球磨机等,球磨时间为2-24h,球料比为3-10:1;
(6)非晶合金粉末的筛分成不同粗细的钴基非晶合金粉末。
与现有技术相比,本发明具有以下优点:
1.与气雾法和直接破碎法相比,本工艺具有设备投资少、工艺简单,对非晶合金形成能力要求不高等特点;
2.与水雾法相比,粉末不会产生氧化和部分非晶化的问题;
3.与直接破碎法相比,由于采用PH值较小条件下沉积,致使镀层内产生了较大的内应力和较多孔隙,镀层无需脆化退火破碎,且也不会产生带有锐角的粉末颗粒;
4.与电镀法+破碎法制备非晶合金粉末法相比,由于电刷镀两电极间有相对运动,电镀液也是流动状态,因此,没有电镀产生的浓差极化问题,可以使用相对更大的电流密度,提高粉末的生产效率;
5.与常规电刷镀而言,因为对镀层应力和表面质量没有要求,因此可采用更大的电流密度,既提高了非晶合金镀层的制备速度,也有利于获得更疏松和具有更大内应力的非晶合金镀层,从而更易对非晶合金镀层进行机械剥离;
6.本方法无需考虑对材料的非晶形成能力,可通过调整电镀液各主要成分的浓度配比,可获得不同组元构成和比例的非晶合金粉末,因此,本方法的适用性更为广泛,可操作性更强,可满足不同场合的性能要求。
具体实施方式
以下结合实施例对本发明作进一步说明。
实施例1 Co-P非晶合金粉末的制备
本实施例非晶合金粉末Co含量的92.4wt%,P含量为复合镀层的7.6wt%。
其制备工艺,包括以下步骤:
(1)金属基板表面的预处理:金属基板选用45号钢板,被镀基板表面经机械加工,然后在20wt%氢氧化钠溶液清洗10min去除油脂;
(2)电镀液组成:氯化钴0.6mol/L,硫酸钴2mol/L,硼酸0.65mol/L,次磷酸钠0.55mol/L,十二烷基苯磺酸钠1.5g/L,糖精0.1g/L,水余量;
(4)非晶合金镀层的制备:预处理后的镀件接入电镀槽阴极,阳极采用石墨,搅拌电镀液,电极的电流密度为0.5A/mm2,施镀温度为60℃,滴定盐酸使电镀液Ph值为0.6;
(5)采用轧制压延法剥离非晶合金镀层;
(6)非晶合金颗粒的球磨,采用行星球磨机球磨,非晶合金粉末充氩气保护,球磨5h,球料比为5:1;
(7)非晶合金粉末的筛分,采用200目和400目筛子分筛,其中大于200目粉末所占比例为24%,200-400目粉末所占比例为59%,小于400目粉末所占比例为17%。
实施例2 Co-Ni-P非晶合金粉末的制备
本实施例Co-Ni-P非晶合金粉末成分为,Co含量80.3wt%,Ni含量为10.8wt%,P含量为8.9wt%。
其制备工艺,包括以下步骤:
(1)金属基板表面的预处理:金属基板选用45号钢板,被镀基板表面经机械加工,然后在20wt%氢氧化钠溶液清洗10min去除油脂;
(2)电镀液的组成:氯化钴0.4mol/L,硫酸钴2.8mol/L,硫酸镍0.9mol/L,磷酸0.8mol/L,亚磷酸0.45mol/L,对甲苯磺酸胺0.2g/L,酒石酸1g/L、十二烷基苯磺酸钠0.8g/L;
(4)非晶合金镀层的制备:预处理后的金属基板接入电镀槽阴极,阳极采用石墨,机械搅拌电镀液,电极的电流密度为0.8A/mm2,施镀温度为50℃,滴定盐酸使电镀液Ph值为0.8;
(5)非晶合金镀层的剥离:采用刮擦法剥离镀层;
(6)非晶合金颗粒的球磨,采用行星式球磨机球磨,非晶合金粉末充氩气保护球磨7h,球料比为3:1;
(7)非晶合金粉末的筛分,采用200目和400目筛子分筛,其中大于200目粉末所占比例为26%,200-400目粉末所占比例为56%,小于400目粉末所占比例为18%。
Claims (1)
1.一种钴基非晶合金粉末的生产方法,其特征在于,包括以下步骤:
(1)金属基板被镀表面的除锈、脱脂预处理;
(2)电镀液组成:硫酸钴2-3.5mol/L、酸0.3-1mol/L、络合剂0.5-5g/L、合金元素添加剂0.2-2mol/L、添加剂0-2g/L,水适量;
上述合金元素添加剂中,铁以硫酸亚铁或氯化亚铁、铬以铬酐、钼以钼酸钠、镍以硫酸镍或氯化镍、磷以亚磷酸或可溶性次磷酸盐、Re以Re可溶盐的形式添加,铁元素需配有还原剂;
上述酸包括硼酸、磷酸、羧酸;
上述络合剂包括酒石酸、十二烷基苯磺酸钠、十二烷基硫酸钠、柠檬酸盐;
上述添加剂为糖精、对甲苯磺酸胺;
(3)非晶合金镀层的制备:采用电刷镀方法制备非晶合金镀层,阳极采用石墨,电极的电流密度为0.8-1.2A/mm2,电极相对运动速度为10-15m/min,滴定强酸溶液使镀液pH值小于1,施镀温度为30-60℃;
(4)采用物理的方法使非晶合金镀层剥落;
(5)非晶合金颗粒的球磨;
(6)非晶合金粉末的筛分。
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CN108149158A (zh) * | 2017-12-27 | 2018-06-12 | 刘志红 | 一种Co-Ni-P非晶粉末制备工艺 |
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CN108179366A (zh) * | 2017-12-28 | 2018-06-19 | 刘志红 | 一种Ni合金非晶态粉末的生产方法 |
CN108179365A (zh) * | 2017-12-28 | 2018-06-19 | 刘志红 | 一种电刷镀法Ni-Co-P非晶态粉末的生产工艺 |
CN108145148A (zh) * | 2017-12-28 | 2018-06-12 | 刘志红 | 一种基于电刷镀镍合金非晶态粉末的生产工艺 |
CN107937945A (zh) * | 2017-12-29 | 2018-04-20 | 刘志红 | 一种电镀法制备Ni‑Fe‑P非晶态粉末工艺 |
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