CN102041517B - Water-soluble non-phosphorus degreasing agent for permanent magnet material - Google Patents
Water-soluble non-phosphorus degreasing agent for permanent magnet material Download PDFInfo
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- CN102041517B CN102041517B CN200910235746.XA CN200910235746A CN102041517B CN 102041517 B CN102041517 B CN 102041517B CN 200910235746 A CN200910235746 A CN 200910235746A CN 102041517 B CN102041517 B CN 102041517B
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Abstract
The invention provides a novel water-soluble non-phosphorus degreasing agent for a permanent magnet material, comprising alkali, a cleaning auxiliary agent and a surface active agent, wherein the alkali is a mixture of two or more of sodium hydroxide, sodium carbonate and sodium gluconate; the cleaning auxiliary agent is a polyacrylic acid polymer; and the surface active agent is a low-foam non-ionic surface active agent. The novel water-soluble non-phosphorus degreasing agent for the permanent magnet material has the characteristics of neutrality, non-phosphorus property, environmental-protection performance and low temperature. According to the invention, the degreasing agent has good wettability, permeability, emulsibility and strong degreasing capability, and can prevent grease dirt from being adsorbed again; the degreasing solution is stable, has high grease dirt capacity and can be used in a long term; and meanwhile, by using the non-ionic surface active agent, the foam is little, the washing performance is superior, the water can be softened, and the corrosion of the permanent magnet material in degreasing powder can be avoided.
Description
Technical field
The present invention relates to the field of surface treatment of material, especially relate to the degreasing technique of permanent magnet material, specifically, the present invention relates to a kind of water-soluble non-phosphorus degreasing agent for permanent magnet material.
Background technology
The application and development of neodymium iron boron (NdFeB) permanent magnet material is very rapid in recent years, and the protection success or not of Nd-Fe-Bo permanent magnet material is related to one of gordian technique that can material apply.This material is to be mainly prepared from by powder metallurgical technique by elements such as rare earth metal neodymium (Nd), iron and boron.As the strongest current magneticsubstance, be widely used in all fields such as electroplating device, machinery, medical treatment, automobile, application prospect is very wide.
The porous material that Nd-Fe-Bo permanent magnet material is prepared from as a kind of powder metallurgical technique, because of rich neodymium phase wherein, neodymium iron boron principal phase and borderline phase are easy to form intergranular corrosion, very easily corrosion in damp and hot environment, because corrosion failure causes decline or the damage of magnetic property, have a strong impact on the work-ing life of Nd-Fe-B permanent magnet, reduced stability and the reliability of product.Therefore, must carry out rotproofing to Nd-Fe-Bo permanent magnet material.The anti-corrosion method of Nd-Fe-Bo permanent magnet material has much at present.Wherein there are the several different methods such as electronickelling (CN1928163, CN1928163), electro-galvanizing (CN1421547A, CN1056133A, CN1056133), shooting of multi-layer nickel electroplating, copper facing (CN1514889A), phosphatization, electrocoating paint.
Before all surface is processed, in order to make the combination that coating and matrix are good, it is the requisite step of a step that material matrix is carried out to degreasing degreasing.Oil removing only will be to the very large problem of the anticorrosion generation of Nd-Fe-Bo permanent magnet material.
Existing degreaser is studied preparation mainly for metal or alloy such as ferrous materials or zinc, copper, obtain the degreaser of better effects often can not obtain good effect for neodymium-iron-boron permanent magnetic material surface at these material surface energies.This be because: neodymium-iron-boron permanent magnetic material surface is loose porous, and greasy dirt in space is difficult for removing, its corrosion-resistant simultaneously, conventional strong basicity easily causes the corrosion of material matrix, affects its performance.
As 40～80% sodium hydroxide for oil removing in the publication number patent that is CN1056133, alkalescence has very strong corrodibility for the heterogeneous system of Nd-Fe-B permanent magnet too by force.But, as use the degreaser that alkalescence is too little, and can cause again grease to remove unclean, affect the combination of coating and matrix.In addition, in the degreasing technique having, contain water glass in above-mentioned patent, water glass can effectively improve deoiling effect.But at acid cleaning process thing water glass, can stick in the hole of neodymium iron boron, can affect the surface treatment effect of Nd-Fe-B permanent magnet.With respect to the corrosion-prone feature of neodymium iron boron heterogeneous system, chemical degreasing oil removing has become a Main Means and the necessary method of Nd-Fe-B permanent magnet pre-treatment.The effect of evaluating oil removing, mainly contains following three kinds of methods at present:
1, moisture film test method(s)
Product after degreasing, with after dilute sulphuric acid dipping, is sprayed to uniform water smoke, if there is greasy dirt, water will be separated, if do not had, can form a continuous moisture film.
2, fluorescence dye method
Oil-soluble fluorescence dye is added among greasy dirt, sample is immersed among greasy dirt, then sample is carried out to degreasing degreasing, washing, dry, under infrared rays, irradiate.If sample exists the bright spot of flash of light, prove that greasy dirt not yet moves back to the greatest extent, if nothing proves that greasy dirt eliminates completely.
3, contact angle method of testing
By the good sample of degreasing degreasing, drip the upper globule or smeared with cotton swab.If contact angle is little, illustrate that deoiling effect is better.
Washing assistant is as one of topmost additive in degreasing fluid, and it must have following several major function: 1. sequestering power: the Ca2+ in chelating water, Mg2+, and softening of water, to guarantee anion surfactant performance cleaning function; 2. dispersive ability: can promote dirt dispersion of particles, avoid occurring redeposition; 3. alkali surge capability: make the pH of dirt solution keep certain stability and be conducive to decontamination.Before the nineties, tripoly phosphate sodium STPP (STPP) is the washing assistant of commonly using the most, but due to the discharge of phosphorous scrub raffinate, has caused the eutrophication of rivers and lakes water systems, has caused the serious environmental pollution such as red tide.Therefore,, after the seventies, American-European countries just starts to find without phosphorus substitute.In China, in today of emphasizing Sustainable development and pay attention to day by day environmental protection, limit phosphorus and even taboo phosphorus are inexorable trends, without phosphatization, have become a big hot topic topic.
Summary of the invention
The object of the invention is, in order to overcome the defect of prior art, provides a kind of environmental protection degreaser of permanent magnet material, and a kind of new water-soluble non-phosphorus degreasing agent for Nd-Fe-Bo permanent magnet material is mainly provided.
According to the one side of invention, the invention provides a kind of water-soluble non-phosphorus degreasing agent for permanent magnet material, described degreaser contains alkali, cleaning additive and tensio-active agent, described alkali is two or more mixture in sodium hydroxide, sodium carbonate, Sunmorl N 60S, described cleaning additive can be acrylic acid polymer, for example, polyacrylic acid (PAA) macromolecule detergency promoter and derivative thereof, described tensio-active agent is low bubble nonionogenic tenside.Wherein, described cleaning additive is water-soluble polyelectrolyte macromolecular compound.
Wherein, described acrylic acid polymer is selected from least one in polyacrylic acid (PAA), vinylformic acid and acrylamide copolymer (DEA).
Wherein, described tensio-active agent is that Triton is Triton X-100 or alkylpolyoxyethylene-9 (AEO), and Triton chemical structural formula is:
Wherein, described alkali content is 20～50 grams per liters.
Wherein, described cleaning additive content is 5～15 grams per liters.
Wherein, described tensio-active agent addition is 3～5 grams per liters.
Wherein, the PH of described degreaser is 7.5～8.5.
Wherein, described degreaser is a kind of low temperature degreaser, and use temperature can be 10～80 ℃, and the best is 30～60 ℃.
Wherein, described permanent magnet material is sintered Nd-Fe-B permanent magnetic material or binding Nd-Fe-B permanent magnetic material.
Compared with prior art, a kind of water-soluble non-phosphorus degreasing agent for permanent magnet material provided by the invention, is neutrality, and use temperature is low; This degreaser has good wettability, perviousness and emulsifying property, and the ability of deoiling is strong, can prevent that greasy dirt from adsorbing again; Solution-stabilized, the greasy dirt charge capacity of skim soln is large, energy life-time service; Owing to using, nonionogenic tenside foam is few, and washing performance is superior, can softening water, can prevent that the permanent magnet material being easily corroded is corroded in degreasing powder.Therefore, the invention provides a kind of environmental protection, the without phosphorus degreaser for permanent magnet material is newly filled a prescription.
Embodiment
Below with reference to embodiment, the present invention will be further described, and embodiments of the invention are only for technical scheme of the present invention is described, and non-limiting the present invention.
Embodiment 1
Weighing sodium hydroxide is 5 grams respectively, 15 grams, sodium carbonate, and 5 grams of DEA, 5 grams of Triton, are dissolved in 1 premium on currency, and PH is 7.5,80 ℃ of temperature.Sintered Nd-Fe-B permanent magnetic material sample is divided into three parts and puts into wherein oil removing 1 minute, 5 minutes, 24 hours.
Embodiment 2
Weighing sodium hydroxide is 5 grams respectively, 15 grams, sodium carbonate, and 20 grams of Sunmorl N 60Ss, PAA15 gram, 3 grams of Triton, are dissolved in 1 premium on currency, and PH is 8.0, temperature 60 C.Binding Nd-Fe-B permanent magnetic material sample is divided into three parts and puts into wherein oil removing 1 minute, 5 minutes, 24 hours.
Embodiment 3
Weighing sodium hydroxide is 10 grams respectively, 15 grams, sodium carbonate, and 5 grams of Sunmorl N 60Ss, PAA10 gram, 4 grams of Triton, are dissolved in 1 premium on currency, and PH is 8.0, temperature 60 C.Sintered Nd-Fe-B permanent magnetic material sample is divided into three parts and puts into wherein oil removing 1 minute, 5 minutes, 24 hours.
Embodiment 4
Weighing sodium hydroxide is 5 grams respectively, 20 grams of Sunmorl N 60Ss, and 15 grams, sodium carbonate, DEA10 gram, 4 grams of AEO, are dissolved in 1 premium on currency, and PH is 8.5,30 ℃ of temperature.Binding Nd-Fe-B permanent magnetic material sample is divided into three parts and puts into wherein oil removing 1 minute, 5 minutes, 24 hours.
Embodiment 5
Weighing sodium hydroxide is 15 grams respectively, 20 grams of Sunmorl N 60Ss, and 15 grams, sodium carbonate, PAA10 gram, 5 grams of DEA, 4 grams of AEO, are dissolved in 1 premium on currency, and PH is 8.5,10 ℃ of temperature.Sintered Nd-Fe-B permanent magnetic material sample is divided into two portions and puts into wherein oil removing 1 minute, 5 minutes, 24 hours.
Embodiment 6
Weighing sodium hydroxide is 5 grams respectively, 10 grams of Sunmorl N 60Ss, and 10 grams, sodium carbonate, DEA5 gram, 4 grams of Triton, are dissolved in 1 premium on currency, and PH is 8.0,40 ℃ of temperature.Sintered Nd-Fe-B permanent magnetic material sample is divided into three parts and puts into wherein oil removing 1 minute, 5 minutes, 24 hours.
Embodiment 7
Weighing sodium hydroxide is 15 grams respectively, 10 grams of Sunmorl N 60Ss, and 15 grams, sodium carbonate, DEA5 gram, 10 grams of PAA, 4 grams of Triton, are dissolved in 1 premium on currency, and PH is 8.3, temperature 60 C.Sintered Nd-Fe-B permanent magnetic material sample is divided into three parts and puts into wherein oil removing 1 minute, 5 minutes, 24 hours.
Embodiment 8
Weighing sodium hydroxide is 15 grams respectively, 10 grams of Sunmorl N 60Ss, and 15 grams, sodium carbonate, PAA5 gram, DEA5 gram, 4 grams of Triton, are dissolved in 1 premium on currency, and PH is 8.2,55 ℃ of temperature.Binding Nd-Fe-B permanent magnetic material sample is divided into three parts and puts into wherein oil removing 1 minute, 5 minutes, 24 hours.
Comparative example 1
Take respectively conventional in the market degreaser (U.S. hard chemical industry 888 degreasing powders), be dissolved in 1 premium on currency, PH is 11.0,55 ℃ of temperature.Sintered Nd-Fe-B permanent magnetic material sample is divided into three parts and puts into wherein oil removing 1 minute, 5 minutes, 24 hours.
Deoiling effect of the present invention is evaluated:
In order to compare the deoiling effect of degreaser in the embodiment of the present invention 1～8 and comparative example 1, use moisture film test to evaluate, result is as shown in the table, and specific operation process is as follows:
Embodiment 1～8 and comparative example's 1 degreasing degreasing effect
| No. embodiment | 1 minute | 5 minutes | 24 hours |
| Embodiment 1 | Moisture film continuous bright, liquid is bright | Moisture film continuous bright, liquid is bright | Moisture film continuous bright, liquid is bright |
| Embodiment 2 | Moisture film continuous bright, liquid is bright | Moisture film continuous bright, liquid is bright | Moisture film continuous bright, liquid is bright |
| Embodiment 3 | Moisture film continuous bright, liquid is bright | Moisture film continuous bright, liquid is bright | Moisture film continuous bright, liquid is bright |
| Embodiment 4 | Moisture film continuous bright, liquid is bright | Moisture film continuous bright, liquid is bright | Moisture film continuous bright, liquid is bright |
| Embodiment 5 | Moisture film continuous bright, liquid is bright | Moisture film continuous bright, liquid is bright | Moisture film continuous bright, liquid is bright |
| Embodiment 6 | Moisture film continuous bright, liquid is bright | Moisture film continuous bright, liquid is bright | Moisture film continuous bright, liquid is bright |
| Embodiment 7 | Moisture film continuous bright, liquid is bright | Moisture film continuous bright, liquid is bright | Moisture film continuous bright, liquid is bright |
| Embodiment 8 | Moisture film continuous bright, liquid is bright | Moisture film continuous bright, liquid is bright | Moisture film continuous bright, liquid is bright |
| Comparative example 1 | Moisture film is discontinuous, and liquid is bright | Moisture film continuous bright, liquid is bright | Liquid is muddy, occurs yellow floss, |
From upper table, adopt the comparative example 1 of commercially available degreaser in prior art can find out with adopting the comparing result of the embodiment 1～8 of degreaser of the present invention, in moisture film test, degreaser processing efficiency of the present invention is high, required time is short, and greasy dirt charge capacity is large, can life-time service.Degreaser processing sample of the present invention surface can reach the effect of thoroughly deoiling in 1 minute, now sample surfaces moisture film test shows as moisture film continuous bright, liquid is bright, through 5 minutes even after 24 hours moisture film still show as continuous bright, liquid is also still bright, and commercially available degreaser processing sample surface treatment sample surfaces can not reach the effect of thoroughly deoiling for 1 minute, it is discontinuous that now sample surfaces moisture film test shows as moisture film, liquid is bright, and after 24 hours, liquid will become muddy, occurs yellow floss.This explanation, not only environmental protection is without phosphorus for non-phosphorus degreasing agent of the present invention, oil removing ability is strong, and greasy dirt charge capacity is large, energy life-time service, and can prevent that permanent magnet material is corroded in degreaser, it is neutral that PH is, more phosphorous than what commonly use, the degreaser that PH is 11 has obvious advantage.
It should be noted that, foregoing invention content and embodiment are intended to prove the practical application of technical scheme provided by the present invention, should not be construed as limiting the scope of the present invention.Those skilled in the art are in spirit of the present invention and principle, when doing various modifications, be equal to and replace or improve.Protection scope of the present invention is as the criterion with appended claims.
Claims (4)
1. for a water-soluble non-phosphorus degreasing agent for permanent magnet material, it is characterized in that, described degreaser is comprised of alkali, cleaning additive and tensio-active agent; Described alkali is the mixture of the mixture of sodium hydroxide and Sunmorl N 60S or the mixture of sodium carbonate and Sunmorl N 60S or sodium hydroxide, sodium carbonate and Sunmorl N 60S, and described alkali content is 20～50 grams per liters; Described cleaning additive is acrylic acid polymer, and described acrylic acid polymer is vinylformic acid and acrylamide copolymer or vinylformic acid and acrylamide copolymer and polyacrylic mixture, and described cleaning additive content is 5～15 grams per liters; Described tensio-active agent is low bubble nonionogenic tenside, and described low bubble nonionogenic tenside is Triton X-100 or alkylpolyoxyethylene-9, and described surfactant content is 3～5 grams per liters; The pH of described degreaser is 7.5～8.5.
2. water-soluble non-phosphorus degreasing agent according to claim 1, is characterized in that, the use temperature of described degreaser is 10～80 ℃.
3. water-soluble non-phosphorus degreasing agent according to claim 2, is characterized in that, the use temperature of described degreaser is 30～60 ℃.
4. water-soluble non-phosphorus degreasing agent according to claim 1, is characterized in that, described permanent magnet material is sintered Nd-Fe-B permanent magnetic material or binding Nd-Fe-B permanent magnetic material.
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| CN200910235746.XA CN102041517B (en) | 2009-10-13 | 2009-10-13 | Water-soluble non-phosphorus degreasing agent for permanent magnet material |
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| CN102492952B (en) * | 2011-11-18 | 2014-02-19 | 东莞市东辉贸易有限公司 | Phosphorus-free degreasing powder, production process and phosphorus-free degreasing process thereof |
| CN107604374A (en) * | 2017-08-11 | 2018-01-19 | 徐州华通浮动油封科技有限公司 | A kind of ironware high-temperature situation goes down fluid composition |
| CN109183051A (en) * | 2018-08-03 | 2019-01-11 | 南京派诺金属表面处理技术有限公司 | It is without phosphorus, without low bubble seconds degreasing agent of silicon one-component room temperature and preparation method thereof |
| CN111549361A (en) * | 2020-05-12 | 2020-08-18 | 江苏兰诺磁业有限公司 | Method for plating double-layer zinc on surface of neodymium iron boron permanent magnet material |
| CN114892178B (en) * | 2022-05-12 | 2023-11-03 | 武汉奥邦表面技术有限公司 | Silicon-free phosphorus-free environment-friendly water-based degreasing agent and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5902415A (en) * | 1996-04-02 | 1999-05-11 | Church & Dwight Co., Inc. | Aqueous sodium salt metal cleaner and method of using same |
| CN101029389A (en) * | 2007-04-12 | 2007-09-05 | 北京中科三环高技术股份有限公司 | Surface protection of neodymium iron boron permanent-magnet material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1297646C (en) * | 2003-06-25 | 2007-01-31 | 蓝星清洗工程有限公司 | Neutral deoiling derusting cleaning agent |
| CN101351538A (en) * | 2005-11-01 | 2009-01-21 | 纳幕尔杜邦公司 | Solvent compositions comprising unsaturated fluorinated hydrocarbons |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5902415A (en) * | 1996-04-02 | 1999-05-11 | Church & Dwight Co., Inc. | Aqueous sodium salt metal cleaner and method of using same |
| CN101029389A (en) * | 2007-04-12 | 2007-09-05 | 北京中科三环高技术股份有限公司 | Surface protection of neodymium iron boron permanent-magnet material |
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