CN113789507A - Zinc-calcium-manganese phosphating solution and preparation method thereof - Google Patents
Zinc-calcium-manganese phosphating solution and preparation method thereof Download PDFInfo
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- CN113789507A CN113789507A CN202111075499.9A CN202111075499A CN113789507A CN 113789507 A CN113789507 A CN 113789507A CN 202111075499 A CN202111075499 A CN 202111075499A CN 113789507 A CN113789507 A CN 113789507A
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- QCMLJYVKYRRZQH-UHFFFAOYSA-N [Mn].[Ca].[Zn] Chemical compound [Mn].[Ca].[Zn] QCMLJYVKYRRZQH-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 75
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 48
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000012452 mother liquor Substances 0.000 claims abstract description 33
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 25
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 25
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 24
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 24
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 24
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 24
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000011787 zinc oxide Substances 0.000 claims abstract description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 20
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 18
- LJRGBERXYNQPJI-UHFFFAOYSA-M sodium;3-nitrobenzenesulfonate Chemical compound [Na+].[O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 LJRGBERXYNQPJI-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000007865 diluting Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000010413 mother solution Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 15
- 235000011837 pasties Nutrition 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 239000013049 sediment Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000005406 washing Methods 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical class [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- ZOVPEJCNNVXBCF-UHFFFAOYSA-K calcium manganese(2+) phosphate Chemical compound [Mn+2].P(=O)([O-])([O-])[O-].[Ca+2] ZOVPEJCNNVXBCF-UHFFFAOYSA-K 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/50—Treatment of iron or alloys based thereon
Abstract
The invention discloses a zinc-calcium-manganese phosphating solution and a preparation method thereof, wherein the zinc-calcium-manganese phosphating solution is formed by diluting phosphating mother solution and water according to the mass percentage of 1: 10-15; the phosphating mother liquor is prepared from the following raw materials in percentage by mass: 3 to 6 percent of zinc oxide, 10 to 15 percent of phosphoric acid, 0.1 to 0.5 percent of manganese carbonate, 10 to 15 percent of calcium hydroxide, 10 to 15 percent of nitric acid, 1 to 2 percent of citric acid, 0.1 to 1 percent of EDTA, 0.3 to 3 percent of sodium m-nitrobenzenesulfonate and water, wherein the sum of the mass percentages of the components is 100 percent. The zinc-calcium-manganese phosphating solution disclosed by the invention is used for treating the metal surface, the film forming speed is high, a phosphating film is uniform and fine, the corrosion resistance is good, the adhesive force on the metal surface is strong, the phosphating sediments are less, the preparation method is simple, the use is convenient, and the environmental protection performance is strong.
Description
Technical Field
The invention relates to the technical field of surface treatment of materials such as metal, and particularly relates to a zinc-calcium-manganese phosphating solution and a preparation method thereof.
Background
Among the pretreatment techniques for metal workpieces, phosphating is a common treatment technique. The mechanism is a chemical treatment method in which a metal is brought into contact with a phosphate solution containing metal ions such as zinc, manganese, calcium, iron, etc., and a chemical reaction occurs to form a stable insoluble phosphate film on the surface of the metal. The film formed is called a phosphating film. The main effects of phosphating are as follows: improve corrosion resistance, improve adhesion between the substrate and the coating or other organic finishing layer, provide a clean surface, and improve cold working properties of the material such as wire drawing, tube drawing, extrusion, and the like. The phosphorization process can be divided into normal temperature, low temperature, medium temperature and high temperature phosphorization according to the operation temperature. The ordinary temperature range of normal temperature phosphorization is between 5 and 35 ℃, the ordinary temperature range of low temperature phosphorization is between 35 and 45 ℃, the ordinary temperature range of medium temperature phosphorization is between 50 and 70 ℃, and the ordinary temperature range of high temperature phosphorization is above 80 ℃. The medium-high temperature phosphating is mainly of zinc series, and in recent years, medium-high temperature zinc-calcium series phosphating appears, and the corrosion resistance of the latter is often improved compared with that of the former. Nevertheless, according to the national standard GB/T6807-1986, the corrosion resistance of the copper sulfate solution is less than 15min and rarely exceeds 20min in a spot experiment, and even the corrosion resistance of the high-temperature manganese phosphating solution is hardly more than 30 min. However, many metal workpieces have a very high requirement for corrosion resistance, and in this case, ordinary zinc-based phosphating or zinc-calcium-based phosphating hardly satisfies the requirement for corrosion resistance.
Disclosure of Invention
The invention aims to provide a zinc-calcium-manganese phosphating solution with strong corrosion resistance and a preparation method thereof aiming at the defect of insufficient corrosion resistance of medium-high temperature zinc-calcium phosphating and medium-high temperature manganese phosphating.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a zinc-calcium-manganese phosphating solution is formed by diluting phosphating mother liquor and water according to the mass ratio of 1 (10-15); wherein the phosphating mother liquor comprises the following raw materials in percentage by mass:
as a further improvement of the invention, the zinc-calcium-manganese phosphating solution is formed by diluting a phosphating mother solution and water according to the mass ratio of 1 (10-13); wherein the phosphating mother liquor comprises the following raw materials in percentage by mass:
as a further improvement of the invention, the zinc-calcium-manganese phosphating solution is formed by diluting phosphating mother liquor and water according to the mass ratio of 1: 10; wherein the phosphating mother liquor comprises the following raw materials in percentage by mass:
a preparation method of zinc-calcium-manganese phosphating solution comprises the following steps:
taking zinc oxide, phosphoric acid, manganese carbonate, calcium hydroxide, nitric acid, citric acid, EDTA, sodium m-nitrobenzenesulfonate and water in required amounts according to the mass percentage of the raw materials of the phosphating mother liquor;
mixing zinc oxide and calcium hydroxide, adding a proper amount of water, and stirring to obtain a pasty solution A;
adding nitric acid and phosphoric acid into the pasty solution A, and stirring until zinc oxide and calcium hydroxide are fully dissolved to obtain a solution B;
gradually adding manganese carbonate into the solution B, and stirring until all manganese carbonate is added and dissolved to obtain a solution C;
continuously adding citric acid, EDTA, sodium m-nitrobenzenesulfonate and water into the solution C, and stirring to obtain a phosphating mother solution;
and diluting the phosphating mother liquor and water according to the mass ratio to obtain the zinc-calcium-manganese phosphating liquor.
The whole process of obtaining the zinc-calcium-manganese phosphating solution is carried out under the conditions of normal temperature and normal pressure.
The concentration of the phosphoric acid is 85%.
The concentration of the nitric acid is 68%.
Compared with the prior art, the invention has the following advantages:
the zinc-calcium-manganese phosphating solution disclosed by the invention is used for treating the metal surface, the film forming speed is high, a phosphating film is uniform and fine, the corrosion resistance is good, the adhesive force on the metal surface is strong, the phosphating sediments are less, the preparation method is simple, the use is convenient, and the environmental protection performance is strong.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
Unless otherwise specified herein, "comprising," including, "" containing, "" having, "or the like, means" consisting of … … "and" consisting essentially of … …, "e.g.," a comprises a "means" a comprises a and the other, "and" a comprises a only.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
The invention provides a zinc-calcium-manganese phosphating solution which is formed by diluting a phosphating mother solution and water according to the mass percentage of 1 (10-15); wherein the phosphating mother liquor is prepared from the following raw materials in percentage by mass: 3 to 6 percent of zinc oxide, 10 to 15 percent of phosphoric acid, 0.1 to 0.5 percent of manganese carbonate, 10 to 15 percent of calcium hydroxide, 10 to 15 percent of nitric acid, 1 to 2 percent of citric acid, 0.1 to 1 percent of EDTA, 0.3 to 3 percent of sodium m-nitrobenzenesulfonate and the balance of water, wherein the sum of the content percentages of all the components in the formula is equal to 100 percent.
The function and principle of each part in the formula of the invention are as follows:
the manganese carbonate has the function of providing metal manganese ions required in the phosphating solution and enhancing the corrosion resistance and the wear resistance of the phosphating film.
Calcium hydroxide is used as a calcium agent in the phosphating solution, manganese calcium phosphate crystal nuclei are formed on the basis of the original manganese iron phosphate crystal nuclei after the calcium hydroxide is added, the crystals formed after the crystal nuclei grow up are compact and uniform, gaps among the crystals are small, and the corrosion resistance of a phosphating film is further enhanced.
The zinc oxide mainly provides zinc ions in the phosphating solution and is a main component for forming a phosphating film.
EDTA and citric acid are complexing agents in the phosphating solution, and can reduce the sediment amount of the phosphating reaction.
The sodium m-nitrobenzenesulfonate is an accelerant, and can improve the phosphating reaction speed, shorten the phosphating time, ensure the moderate thickness of a phosphating film formed on the metal surface and ensure the uniform and compact crystal grains of the phosphating film, thereby enhancing the adhesive force of the phosphating film.
The preparation method of the phosphating solution comprises the following steps:
weighing zinc oxide, phosphoric acid, manganese carbonate, calcium hydroxide, nitric acid, citric acid, EDTA, sodium m-nitrobenzenesulfonate and water which are required by the corresponding amount according to the mass percentage of the phosphating mother liquor;
putting zinc oxide and calcium hydroxide into a beaker, adding a proper amount of water, quickly stirring into paste, and then continuously stirring for 20-40 min to obtain a paste solution A;
step three, slowly adding nitric acid and phosphoric acid into the pasty solution A while stirring, and continuously stirring for 30min after zinc oxide and calcium hydroxide are fully dissolved to obtain a solution B;
step four, while stirring, gradually adding manganese carbonate into the solution B until all manganese carbonate is added and dissolved to obtain a solution C;
step five, stopping stirring, continuously adding citric acid, EDTA, sodium m-nitrobenzenesulfonate and water into the solution C, and continuously stirring for 60-120 min to obtain phosphating mother liquor;
and step six, diluting the phosphating mother liquor obtained in the step five with water according to the mass percentage of 1: 10-15 to obtain the phosphating liquor required to be prepared.
Specifically, the steps one to six are carried out under normal temperature conditions. The steps one to six are carried out under normal pressure.
Preferably, the concentration of the phosphoric acid is 85% and the concentration of the nitric acid is 68%.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The following examples use instrumentation conventional in the art. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
Example 1
The phosphating solution of the embodiment 1 is formed by diluting phosphating mother liquor and water according to the mass percent of 1: 10; wherein the phosphating mother liquor is prepared from the following raw materials in percentage by mass: 3% of zinc oxide, 10% of phosphoric acid, 0.1% of manganese carbonate, 10% of calcium hydroxide, 10% of nitric acid, 1% of citric acid, 0.1% of EDTA, 0.3% of sodium m-nitrobenzenesulfonate and water, wherein the sum of the mass percentages of the components is 100%.
The zinc calcium manganese phosphating solution of the example 1 is realized by the following steps:
weighing zinc oxide, phosphoric acid, manganese carbonate, calcium hydroxide, nitric acid, citric acid, EDTA, sodium m-nitrobenzenesulfonate and water which are required by the mass percentage of the phosphating mother liquor in the embodiment 1;
putting zinc oxide and calcium hydroxide into a beaker, adding a proper amount of water, quickly stirring into paste, and then continuously stirring for 20-25 min to obtain a paste solution A;
step three, slowly adding nitric acid and phosphoric acid into the pasty solution A while stirring, and continuously stirring for 30min after zinc oxide and calcium hydroxide are fully dissolved to obtain a solution B;
step four, while stirring, gradually adding manganese carbonate into the solution B until all manganese carbonate is added and dissolved to obtain a solution C;
step five, stopping stirring, continuously adding citric acid, EDTA, sodium m-nitrobenzenesulfonate and water into the solution C, and continuously stirring for 60-70 min to obtain a phosphating mother liquor;
and step six, diluting the phosphating mother liquor obtained in the step five with water according to the mass percentage of 1:10 to obtain the phosphating liquor required to be prepared.
Example 2
The phosphating solution of the embodiment 2 is formed by diluting phosphating mother liquor and water according to the mass percent of 1: 13; wherein the phosphating mother liquor is prepared from the following raw materials in percentage by mass: 5 percent of zinc oxide, 12.5 percent of phosphoric acid, 0.3 percent of manganese carbonate, 12.5 percent of calcium hydroxide, 12.5 percent of nitric acid, 1.5 percent of citric acid, 0.5 percent of EDTA, 1.5 percent of sodium m-nitrobenzenesulfonate and water, wherein the sum of the mass percentages of the components is 100 percent.
The zinc calcium manganese phosphating solution of the example 2 is realized by the following steps:
weighing zinc oxide, phosphoric acid, manganese carbonate, calcium hydroxide, nitric acid, citric acid, EDTA, sodium m-nitrobenzenesulfonate and water which are required by the mass percentage of the phosphating mother liquor in the embodiment 2;
putting zinc oxide and calcium hydroxide into a beaker, adding a proper amount of water, quickly stirring into paste, and then continuously stirring for 25-30 min to obtain a paste solution A;
step three, slowly adding nitric acid and phosphoric acid into the pasty solution A while stirring, and continuously stirring for 30min after zinc oxide and calcium hydroxide are fully dissolved to obtain a solution B;
step four, while stirring, gradually adding manganese carbonate into the solution B until all manganese carbonate is added and dissolved to obtain a solution C;
step five, stopping stirring, continuously adding citric acid, EDTA, sodium m-nitrobenzenesulfonate and water into the solution C, and continuously stirring for 80-100 min to obtain phosphating mother liquor;
and step six, diluting the phosphating mother liquor obtained in the step five with water according to the mass percentage of 1:13 to obtain the phosphating liquor required to be prepared.
Example 3
The phosphating solution of the embodiment 3 is formed by diluting phosphating mother liquor and water according to the mass percent of 1: 15; wherein the phosphating mother liquor is prepared from the following raw materials in percentage by mass: 6% of zinc oxide, 15% of phosphoric acid, 0.5% of manganese carbonate, 15% of calcium hydroxide, 15% of nitric acid, 2% of citric acid, 1% of EDTA, 3% of sodium m-nitrobenzenesulfonate and water, wherein the sum of the mass percentages of the components is 100%.
The zinc-calcium-manganese phosphating solution of the embodiment 3 is realized by the following steps:
weighing zinc oxide, phosphoric acid, manganese carbonate, calcium hydroxide, nitric acid, citric acid, EDTA, sodium m-nitrobenzenesulfonate and water which are required by the mass percentage of the phosphating mother liquor in the embodiment 3;
putting zinc oxide and calcium hydroxide into a beaker, adding a proper amount of water, quickly stirring into paste, and then continuously stirring for 35-40 min to obtain a paste solution A;
step three, slowly adding nitric acid and phosphoric acid into the pasty solution A while stirring, and continuously stirring for 30min after zinc oxide and calcium hydroxide are fully dissolved to obtain a solution B;
step four, while stirring, gradually adding manganese carbonate into the solution B until all manganese carbonate is added and dissolved to obtain a solution C;
step five, stopping stirring, continuously adding citric acid, EDTA, sodium m-nitrobenzenesulfonate and water into the solution C, and continuously stirring for 100-120 min to obtain phosphating mother liquor;
and step six, diluting the phosphating mother liquor obtained in the step five with water according to the mass percentage of 1:15 to obtain the phosphating liquor required to be prepared.
The phosphating solutions prepared in examples 1 to 3 were subjected to a phosphating process to verify their effectiveness. The specific process is as follows:
the phosphating processes used in examples 1 to 3 were: oil removal (cold-rolled low-carbon steel test piece) → water washing → rust removal → water washing → surface conditioning → phosphating → water washing → drying (natural drying).
After the cold-rolled low-carbon steel test piece is subjected to oil removal, water washing, rust removal, water washing and surface conditioning, the phosphating solution prepared in the embodiment 1 to the embodiment 3 is used for phosphating, the total acidity is controlled to be 20-25 points, the free acidity is controlled to be 2-3 points, the phosphating temperature is controlled to be 50-70 ℃, and the phosphating time is 10-15 min.
And washing the phosphorized test piece with water, and naturally drying.
The surface of the dried test piece forms a complete light blue gray phosphating film with fine and smooth surface.
The phosphating film is subjected to a copper sulfate spot experiment according to GB/T6807-1986 technical conditions for phosphating treatment before painting of steel workpieces, and is subjected to a 3% sodium chloride aqueous solution immersion experiment test and a neutral salt spray experiment test to test the corrosion resistance of the film according to GB/T6807-2001 technical conditions for phosphating treatment before painting of steel workpieces.
In the comparison example, BW-240 black manganese phosphating solution produced by Beijing Alssem science and technology Limited is selected, and the phosphating process comprises the following steps: (weak alkaline degreasing → water washing →) degreasing and rust removal → water washing → activation → water washing → phosphating → water washing → natural airing. The total acidity is 18-45 points, the free acidity is 2.5-5.0, the acid ratio is 7.0-9.0, the phosphating temperature is 85-95 ℃, and the phosphating time is 8-20 min.
The phosphating film is subjected to a copper sulfate spot experiment according to GB/T6807-1986 technical conditions for phosphating treatment before painting of steel workpieces, and is subjected to a 3% sodium chloride aqueous solution immersion experiment test and a neutral salt spray experiment test to test the corrosion resistance of the film according to GB/T6807-2001 technical conditions for phosphating treatment before painting of steel workpieces.
The test results are shown in table 1 below.
TABLE 1 test results
From the test results in Table 1, it is seen that the phosphating films of examples 1-3 are finer and more excellent in corrosion resistance than the medium-high temperature zinc-calcium based phosphating films and the high temperature manganese based phosphating films than the comparative examples. In addition, the phosphating solution disclosed by the invention is high in film forming speed, strong in adhesive force on the metal surface, simple in preparation method, convenient to use, less in phosphating sediments and strong in environmental protection performance.
The invention also provides other examples, the preparation method is the same as example 1, and the specific formulation is shown in Table 2.
TABLE 2
The sum of the percentage contents of all the components of the formula is equal to 100 percent.
The phosphating films of the embodiments 4 to 7 have the advantages of fine thickness, high film forming speed, strong adhesive force on the metal surface, simple preparation method, convenient use, less phosphating sediments and strong environmental protection performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (7)
1. The zinc-calcium-manganese phosphating solution is characterized by being formed by diluting a phosphating mother solution and water according to the mass ratio of 1 (10-15); wherein the phosphating mother liquor comprises the following raw materials in percentage by mass:
2. the zinc-calcium-manganese phosphating solution according to claim 1, which is formed by diluting a phosphating mother solution and water according to the mass ratio of 1 (10-13); wherein the phosphating mother liquor comprises the following raw materials in percentage by mass:
3. the zinc-calcium-manganese phosphating solution according to claim 1, which is formed by diluting phosphating mother liquor and water according to a mass ratio of 1: 10; wherein the phosphating mother liquor comprises the following raw materials in percentage by mass:
4. a method for preparing a zinc-calcium-manganese phosphating solution according to claim 1, 2 or 3, which is characterized in that: the method comprises the following steps:
taking zinc oxide, phosphoric acid, manganese carbonate, calcium hydroxide, nitric acid, citric acid, EDTA, sodium m-nitrobenzenesulfonate and water in required amounts according to the mass percentage of the raw materials of the phosphating mother liquor;
mixing zinc oxide and calcium hydroxide, adding a proper amount of water, and stirring to obtain a pasty solution A;
adding nitric acid and phosphoric acid into the pasty solution A, and stirring until zinc oxide and calcium hydroxide are fully dissolved to obtain a solution B;
gradually adding manganese carbonate into the solution B, and stirring until all manganese carbonate is added and dissolved to obtain a solution C;
continuously adding citric acid, EDTA, sodium m-nitrobenzenesulfonate and water into the solution C, and stirring to obtain a phosphating mother solution;
and diluting the phosphating mother liquor and water according to the mass ratio to obtain the zinc-calcium-manganese phosphating liquor.
5. The method of claim 4,
the whole process of obtaining the zinc-calcium-manganese phosphating solution is carried out under the conditions of normal temperature and normal pressure.
6. The method of claim 4, wherein the concentration of phosphoric acid is 85%.
7. The method of claim 4, wherein the nitric acid is at a concentration of 68%.
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| CN114892154A (en) * | 2022-05-17 | 2022-08-12 | 洛阳轴承研究所有限公司 | High-corrosion-resistance phosphating solution for wind power main shaft bearing and phosphating method |
| CN115537791A (en) * | 2022-09-30 | 2022-12-30 | 安徽舜邦精细化工有限公司 | Technological method for phosphating and coating oil tank |
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