CN102121103A - Low-temperature slag-free zinc bonderite as well as preparation method and applications thereof - Google Patents
Low-temperature slag-free zinc bonderite as well as preparation method and applications thereof Download PDFInfo
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- CN102121103A CN102121103A CN2010103001900A CN201010300190A CN102121103A CN 102121103 A CN102121103 A CN 102121103A CN 2010103001900 A CN2010103001900 A CN 2010103001900A CN 201010300190 A CN201010300190 A CN 201010300190A CN 102121103 A CN102121103 A CN 102121103A
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- zinc
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Links
- 239000011701 zinc Substances 0.000 title claims abstract description 44
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 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 78
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 44
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 40
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 31
- 239000002893 slag Substances 0.000 claims abstract description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011787 zinc oxide Substances 0.000 claims abstract description 22
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 21
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 20
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 20
- 239000008139 complexing agent Substances 0.000 claims abstract description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 11
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 56
- 239000012530 fluid Substances 0.000 claims description 27
- 235000014692 zinc oxide Nutrition 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 235000017550 sodium carbonate Nutrition 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 7
- 235000011837 pasties Nutrition 0.000 claims description 6
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 claims description 4
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 229940095064 tartrate Drugs 0.000 claims description 4
- 239000002184 metal Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 229960001484 edetic acid Drugs 0.000 abstract 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000011975 tartaric acid Substances 0.000 abstract 1
- 235000002906 tartaric acid Nutrition 0.000 abstract 1
- 239000013049 sediment Substances 0.000 description 39
- 229910019142 PO4 Inorganic materials 0.000 description 28
- 239000010452 phosphate Substances 0.000 description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 25
- 238000012360 testing method Methods 0.000 description 21
- 239000012452 mother liquor Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001737 promoting effect Effects 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- -1 iron ion Chemical class 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 230000003203 everyday effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 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 description 4
- 229910000165 zinc phosphate Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 229940116007 ferrous phosphate Drugs 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910000398 iron phosphate Inorganic materials 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical group [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- 229910000155 iron(II) phosphate Chemical group 0.000 description 3
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical group [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000000254 damaging effect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
The invention belongs to the field of metal surface processing, and discloses a low-temperature slag-free zinc bonderite comprising the following components in parts by weight: 280-285 parts of bonderite, 100-105 parts of phosphoric acid, 93-96 parts of zinc oxide, 15-16 parts of sodium carbonate, 2.0-2.2 parts of citric acid, 1.0-1.2 parts of sodium fluoride, 1.0 part of sodium nitrite, 48-50 parts of complexing agent, and the balance of water, wherein, the total components by weight are 1000 parts, the complexing agent is an aqueous solution composed of ethylene diamine tetraacetic acid (EDTA), citric acid, tartaric acid and sodium tungstate. By utilizing the bonderite provided by the invention, the prejudice that a large amount of dregs must exist in the zinc bonderite considered by the traditional view is overcome, and nearly no slag exists in phosphating, the phosphating time is short, and the temperature is low. The preparation method is simple, and is easily operated and controlled.
Description
Technical field
The invention belongs to technical field of surface, being specifically related to a kind of low temperature does not have the agent of slag Zinc phosphating.
Background technology
Phosphatization is as the anticorrosion and ornamental processing that the metallic surface is carried out, and in industrialization degree more and more higher today, its application also more and more widely.Such as in all trades and professions such as furniture, household electrical appliances, automobile, boats and ships, machinery, weapons and space flight and aviation, irreplaceable effect is arranged.
Progress, the industrial expansion of society have been accelerated the pollution of environment, make our green home suffer unprecedented pressure.Phosphatization also has been subjected to great challenge as a kind of traditional requisite pretreatment technology.Because phosphorization agent in the process of process metal surfaces, can successively produce a large amount of sediments.Phosphorization agent is aging easily simultaneously, can produce waste liquid in the process of changing tank liquor, thereby causes the eutrophication pollution of environment in discharging process easily, produces such as phenomenons such as red tide, green China.
How fundamentally to solve the generation of sediment and the problem of aging of tank liquor? no matter be external or domestic, simple high temperature phosphorization from 19 end of the centurys, or the complicated normal temperature phosphating at the beginning of the 21 century, just on energy consumption, reduce to some extent, all the time can't change its contaminative, and the user is in the expensive cost that disposes waste liquid, paid during waste residue to environment.No matter be the phosphorization treatment technology outstanding figure " Henkel Corp. " of Germany or domestic leading " Chengdu is happy and auspicious ", there's no one who doesn't or isn't this defective carried out unremitting research, but can only reduce the generation of sediment slightly eventually, and can't stop.Study carefully the principle that it produces sediment: when producing phosphatize phosphate coat, phosphate radical and zine ion, ferrous ion and iron ion produce water-fast throw outs such as zinc phosphate, tertiary iron phosphate and ferrous phosphate respectively when phosphorization agent and metal reaction.This mixed type throw out, in use just show as the sediment of white, this sediment is adsorbed on the surface of metal product easily, to the following process of metal product or the consequence of ornamental damaging property of meeting, simultaneously operator's labour intensity has also been strengthened, because must salvage sediment every day 3 to 4 times, otherwise just can't carry out ordinary production.Every according to statistics processing 10000m
2The metallic surface, can produce 50 to 100kg sediment, wherein the content of zinc just reaches 10 to 17kg, zinc is as deficient non-ferrous metal, price is climbed and is risen several times in recent years, and the generation of this sediment causes global zinc not know will be wasted how much!
Notification number is the Chinese invention patent of CN100443632C, a kind of low-temperature zinc-based phosphatization liquid is provided, its raw material by following concentration is formed: zinc oxide 100g/L, 80% phosphoric acid 230g/L, 30% nitric acid 280g/L, single nickel salt 2.67g/L, manganous carbonate 0.2g/L, ethylenediamine tetraacetic acid (EDTA) 0.66g/L, citric acid 5.0g/L, Sodium peroxoborate 1.0g/L and yellow soda ash 2.3g/L, the Zinc phosphating agent phosphatization temperature that it provides is 30-38 ℃, in addition, do not solve the problem that there is sediment in the Zinc phosphating agent.Publication number is China's invention of CN101429658A, a kind of Zinc phosphating agent is provided, formulated by weight by following compositions: primary zinc phosphate: tricresyl phosphate sodium polyphosphate: catalyzer: polyoxyethylene glycol=40-80: 10-50: 5-15: 2-8, there is the problem of sediment in the also also unresolved phosphorization agent of the Zinc phosphating agent of this invention, and its phosphatization temperature is indeterminate.
Summary of the invention
At existing Zinc phosphating agent have sediment, the shortcoming and defect of aspects such as energy consumption is big, labor intensity is big, the wasting of resources, the contriver at first provides a kind of low temperature does not have the agent of slag Zinc phosphating, phosphorization agent is possessed need not to heat and can use, no sediment produces, and does not need characteristics such as replacing; Another goal of the invention provides the preparation method that described low temperature does not have the agent of slag Zinc phosphating.
The objective of the invention is to be implemented by the following technical programs:
The contriver at first provides a kind of low temperature not have the agent of slag Zinc phosphating, its composition comprises the composition of following weight part: nitric acid 280-285 part, phosphatase 11 00-105 part, zinc oxide 93-96 part, soda ash 15-16 part, citric acid 2.0-2.2 part, Sodium Fluoride 1.0-1.2 part, 1.0 parts of Sodium Nitrites and complexing agent 48-50 part add water to 1000 parts.
As preferred version, there is not the agent of slag Zinc phosphating according to low temperature of the present invention, wherein, described complexing agent is grouped into by the one-tenth of following weight part: EDTA4.5-5 part, citric acid 0.8-1.5 part, tartrate 3-3.5 part, sodium wolframate 0.5-0.7 part add water to 48-50 part.
Above-mentioned low temperature does not have the effect of each composition in the slag Zinc phosphating agent prescription:
Nitric acid is accelerated phosphating reaction speed, reduces phosphatization temperature;
Phosphoric acid provides PO
4 3+With free acidity, be reacted into main salt with ZnO;
Zinc oxide provides Zn
2+
Soda ash provides Na
+
Citric acid refinement phosphatize phosphate coat;
Sodium Fluoride provides F
-Fining agent, the soda acid buffering;
Sodium Nitrite promotes phosphating reaction to comment;
The complexing agent complexing action makes phosphorization agent can't produce sediment.
The principle that the Zinc phosphating agent produces sediment is: when producing phosphatize phosphate coat, phosphate radical and zine ion, ferrous ion and iron ion produce water-fast throw outs such as zinc phosphate, tertiary iron phosphate and ferrous phosphate respectively when phosphorization agent and metal reaction.This mixed type throw out, in use just show as the sediment of white, this sediment is adsorbed on the surface of metal product easily, and to the following process of metal product or the consequence of ornamental damaging property of meeting, simultaneously operator's labour intensity has also been strengthened, because must salvage sediment every day 3 to 4 times, otherwise just can't produce normally.Reaction mechanism and its physics-chem characteristic that the contriver produces according to sediment, research through the several years, experiment through thousands of times, final by adopting mixed type complexing agent and in conjunction with the strong oxidizing property of nitric acid, phosphate radical, ferrous ion, iron ion, zine ion are all existed in solution with water-soluble complexing ion state, the present invention mainly is the effect by complexing agent, and sediment is converted into water-soluble material, has fundamentally stopped the generation of sediment.And this sediment is actually the effective constituent of phosphatize phosphate coat, forms with the crystalline state because the composition of phosphatize phosphate coat is exactly zinc phosphate, tertiary iron phosphate and ferrous phosphate.Thereby stoped the generation of sediment, in fact also stoped the waste of resource.
The present invention also provides above-mentioned low temperature not have the preparation method of slag Zinc phosphating agent, comprise: at first with zinc oxide, soda ash, citric acid, Sodium Fluoride, Sodium Nitrite difference water furnishing mashed prod, drop into nitric acid, phosphoric acid, zinc oxide pasty state thing, soda ash mashed prod, citric acid mashed prod, Sodium Fluoride mashed prod, Sodium Nitrite mashed prod and complexing agent then in reaction vessel successively, reaction adds water to 1000 parts after finishing.
As preferably, there is not the preparation method of slag Zinc phosphating agent according to low temperature of the present invention, the time of reaction was at least 2 hours.At normal temperatures and pressures, react completely and generally reach 2 hours and all can finish.Described normal temperature, normal pressure are the general implications of this area indication.Normal temperature also is room temperature, is commonly defined as 25 degrees centigrade.Be similar to and think that normal pressure is exactly standard atmospheric pressure, i.e. a 100KPa.Normal temperature and pressure refers to the temperature and pressure that the people feels more, probably is: ± 20%, normal atmosphere ± 20% of 25 degree.
The above-mentioned low-temperature zinc-based phosphatization agent of the present invention is as mother liquor, and during bonderizing, the working fluid that is made into suitable concentration according to this area current techique can use, and the main technical details of described mother liquor and working fluid is the table 1 of face as follows:
Table 1
| Sequence number | Project | Index |
| 1 | The mother liquor outward appearance | Light green liquid |
| 2 | Mother liquor total acidity (point) | 200～220 |
| 3 | Proportion (g/cm) | 1.20～1.26 |
| 4 | Proportioning (%) | 3～5 |
| 5 | Working fluid total acidity (point) | 12～20 |
| 6 | Working fluid free acidity (point) | 0.8～1.5 |
| 7 | Promotion is counted | 0.5～2.0 |
| 8 | PH value | 2～4 |
| 9 | Treatment temp (℃) | 5～40 |
| 10 | Treatment time (min) | 8～15 |
Described working fluid is prepared as follows and is got final product (in preparation 1000kg working fluid):
Get the raw materials ready: low temperature does not have slag Zinc phosphating agent (being mother liquor) 30-50kg, promotor (20% sodium nitrite solution) 2-3kg, and surplus is a water.
Preparation process: get 2/3 water, adding low temperature does not have slag Zinc phosphating agent (being mother liquor), stirs; Add water to 1000kg then; Then add promotor (20% sodium nitrite solution), stir, promptly can be used for bonderizing.
With the above-mentioned working fluid check and analysis that prepare, its total acidity is the 12-20 point, and free acidity is the 0.8-1.5 point, and promoting counts is that 0.5-2.0, pH value are 2-4, can satisfy the bonderizing requirement fully.Workpiece with required processing is immersed in the working fluid then, can obtain required phosphatize phosphate coat at phosphatization temperature 5-40 ℃ of following bonderizing 8-15 minute.
To gained phosphatize phosphate coat service check, the result is as follows:
Test piece specification: cold-reduced sheet: 120mm*80mm*1mm.
Phosphatize phosphate coat outward appearance: press GB2828-88 and carry out, meet the requirements.
Phosphorization film quality: press GB6807-91 and measure, be 1.5-3.0g/m
2, reach the phosphatization requirement fully.
Phosphatize phosphate coat solidity to corrosion: press GB6807-91 appendix D and measure spot corrosion 1 minute.
Shock-resistance: spray polyurethane paint on the steel plate that will handle with this phosphatization liquid.Press GB1732 and measure shock-resistance 500Ncm.
Snappiness: press GB1731 and measure snappiness by φ=1mm.
Adhesion test: press GB1720 and measure 1 grade of sticking power, and not during phosphatization sticking power be the 2-3 level, illustrate that this phosphatize phosphate coat and paint film have good matching capacity.
Phosphorization agent prescription of the present invention is by the stable performance of a large amount of test inventions and good technical recipe, meets the more and more higher service requirements of steel plate as outer covering piece.Phosphorization agent of the present invention is the low-temperature zinc-based phosphatization agent, belongs to pseudo-conversion film, be applicable to steel coating before, the cold-extruded pre-treatment.
The present invention is a kind of energy-saving phosphatization agent of excellent property, and working temperature low (temperature: 5-40 ℃), time short (8-15 minute), energy consumption is little, can generate a kind of excellent dense phosphatization crystalline film at steel surface.
The present invention has compared great advantage with traditional Zinc phosphating agent, and is specific as follows:
1: no sediment.Reducing discharging, the particularly discharging of solid waste is zero.
2: save man-hour, reduce labour intensity, the workman need not salvage sediment.
3: workpiece surface is clean, and the workpiece surface when having overcome conventional phosphatizing easily is stained with and is stained with sediment, thereby causes directly influencing the outward appearance of workpiece and the shortcoming of plastic-blasting quality.
4: cold operation (5-40 ℃), need not heat, reduce energy consumption.
5: phosphatize phosphate coat exquisiteness, smooth, reduced the usage quantity of molding powder.
6: under equal price, this product can be saved 5～10% phosphorization agent cost than traditional phosphorization agent.Because the effective ingredient of the sediment that is produced during conventional phosphatizing phosphatize phosphate coat in fact all the time.And this product makes phosphorization agent can't produce sediment by complexing action, allows effective ingredient all be converted into phosphatize phosphate coat, thereby has reduced unit cost.
Embodiment
Below in conjunction with embodiment, be described more specifically content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, all will fall into protection domain of the present invention any pro forma accommodation and/or the change that the present invention made.
In the present invention, if not refer in particular to, all part, per-cents are weight unit, and all equipment and raw material etc. all can be buied from market or the industry is commonly used.
Embodiment 1
Get the raw materials ready:
There is not the agent of slag Zinc phosphating by preparation 1000kg low temperature, nitric acid 285kg, phosphatase 11 05kg, zinc oxide 96kg, soda ash 16kg, citric acid 2.2kg, Sodium Fluoride 1.2kg, Sodium Nitrite 1.0kg and complexing agent 50kg, surplus is a water.
Contain EDTA5kg, citric acid 1.5kg, tartrate 3kg, sodium wolframate 0.5kg in the 50kg complexing agent, surplus is a water.
Preparation process is as follows:
At first with zinc oxide, soda ash, citric acid, Sodium Fluoride, Sodium Nitrite difference water furnishing mashed prod, successively nitric acid, phosphoric acid, zinc oxide pasty state thing, soda ash mashed prod, citric acid mashed prod, Sodium Fluoride mashed prod, Sodium Nitrite mashed prod and complexing agent are dropped in the reactor then, reaction is carried out finishing after 2 hours, add water to 1000 parts again, both having got low temperature does not have the agent of slag Zinc phosphating.
After testing, it is mother liquor that the low temperature of present embodiment preparation does not have the agent of slag Zinc phosphating, and its outward appearance is a light green liquid, and the mother liquor total acidity is 205 points, proportion 1.05g/cm.
Embodiment 2
Get the raw materials ready:
There is not the agent of slag Zinc phosphating by preparation 1000kg low temperature, nitric acid 280kg, phosphatase 11 00kg, zinc oxide 93 kg, soda ash 15kg, citric acid 2.0kg, Sodium Fluoride 1.0kg, Sodium Nitrite 1.0kg and complexing agent 48kg, surplus is a water.
Contain EDTA4.5kg, citric acid 0.8kg, tartrate 3.5kg, sodium wolframate 0.7kg in the 48kg complexing agent, surplus is a water.
Preparation process is as follows:
At first with zinc oxide, soda ash, citric acid, Sodium Fluoride, Sodium Nitrite difference water furnishing mashed prod, successively nitric acid, phosphoric acid, zinc oxide pasty state thing, soda ash mashed prod, citric acid mashed prod, Sodium Fluoride mashed prod, Sodium Nitrite mashed prod and complexing agent are dropped in the reactor then, reaction is carried out finishing after 2 hours, add water to 1000 parts again, both having got low temperature does not have the agent of slag Zinc phosphating.
After testing, it is mother liquor that the low temperature of present embodiment preparation does not have the agent of slag Zinc phosphating, and its outward appearance is a light green liquid, and mother liquor complete cross section degree is 220 points, proportion 1.22g/cm.
Comparative example 1
Get the raw materials ready:
There is not the agent of slag Zinc phosphating by preparation 1000kg low temperature, nitric acid 160kg, phosphoric acid 295kg, zinc oxide 110kg, citric acid 1.8kg, Sodium Fluoride 1.5kg, surplus is a water.
Preparation process is as follows:
At first with zinc oxide, citric acid, Sodium Fluoride difference water furnishing mashed prod, successively nitric acid, phosphoric acid, zinc oxide pasty state thing, citric acid mashed prod and Sodium Fluoride mashed prod are dropped in the reactor then, reaction is carried out finishing after 2 hours, adds water to 1000 parts again, makes phosphorization agent.
Comparative example 2
Get the raw materials ready:
There is not the agent of slag Zinc phosphating by preparation 1000kg low temperature, nitric acid 63.5kg, phosphoric acid 210kg, zinc oxide 74.5kg, citric acid 2.5kg, Sodium Fluoride 2kg, surplus is a water.
Preparation process is as follows:
At first with zinc oxide, citric acid, Sodium Fluoride difference water furnishing mashed prod, successively nitric acid, phosphoric acid, zinc oxide pasty state thing, citric acid mashed prod and Sodium Fluoride mashed prod are dropped in the reactor then, reaction is carried out finishing after 2 hours, adds water to 1000 parts again, makes phosphorization agent.
Application examples 1
Preparation 1000kg working fluid: put into 667kg water in the phosphatization groove, add the phosphorization agent mother liquor 40kg of embodiment 1 preparation then, add water to 1000kg after stirring, add promotor 20% sodium nitrite solution 3kg again, stir.After testing, the working fluid worker acidity of preparation is 12 points, and free acidity is 0.9 point, and promoting to count is 1.0, and the pH value is 2.5.
Bonderizing: above-mentioned working fluid is put in test piece, handled 10 minutes down at 25 ℃.Obviously as can be seen, there is not sediment to produce in the bonderizing.And phosphatize phosphate coat detection to making.
Service check:
Test piece specification: cold-reduced sheet: 120mm*80mm*1mm
Phosphatize phosphate coat outward appearance: press GB2828-88 and carry out, meet the requirements
Phosphorization film quality: press GB6807-91 and measure, be 1.88-2.05g/m
2, reach the phosphatization requirement fully.
Phosphatize phosphate coat solidity to corrosion: press GB6807-91 appendix D and measure spot corrosion 1 minute.
Shock-resistance: spray polyurethane paint on the steel plate that will handle with this phosphatization liquid.Press GB1732 and measure shock-resistance 500Ncm.
Snappiness: press GB1731 and measure snappiness by φ=1mm.
Adhesion test: press GB1720 and measure 1 grade of sticking power, and not during phosphatization sticking power be the 2-3 level, illustrate that this phosphatize phosphate coat and paint film have good matching capacity.
Application examples 2
Preparation 1000kg working fluid: put into 667kg water in the phosphatization groove, add the phosphorization agent mother liquor 50kg of embodiment 2 preparations then, add water to 1000kg after stirring, add the sodium nitrite solution 2kg of promotor 20% again, stir.After testing, the working fluid total acidity of preparation is 20 points, and free acidity is 1.2 points, and promoting to count is 0.8, and the pH value is 3.0.
Bonderizing: above-mentioned working fluid is put in test piece, handled 20 minutes down at 25 ℃.Have only in the bonderizing to be close to a little sediment generation that does not have, continuous bonderizing is not had materially affect, need not carry out the salvaging of sediment.And phosphatize phosphate coat detection to making.
Service check:
Test piece specification: cold-reduced sheet: 120mm*80mm*1mm
Phosphatize phosphate coat outward appearance: press GB2828-88 and carry out, meet the requirements
Phosphorization film quality: press GB6807-91 and measure, be 1.90-2.15g/m
2, reach the phosphatization requirement fully.
Phosphatize phosphate coat solidity to corrosion: press GB6807-91 appendix D and measure spot corrosion 1 minute.
Shock-resistance: spray polyurethane paint on the steel plate that will handle with this phosphatization liquid.Press GB1732 and measure shock-resistance 500Ncm.
Snappiness: press GB1731 and measure snappiness by φ=1mm.
Adhesion test: press GB1720 and measure 1 grade of sticking power, and not during phosphatization sticking power be the 2-3 level, illustrate that this phosphatize phosphate coat and paint film have good matching capacity.
Application examples 3
Preparation 1000kg working fluid: put into 667kg water in the phosphatization groove, add the phosphorization agent mother liquor 30kg of embodiment 1 preparation then, add water to 1000kg after stirring, add promotor 20% sodium nitrite solution 3kg again, stir.After testing, the working fluid worker acidity of preparation is 14 points, and free acidity is 1.0 points, and promoting to count is 1.2, and the pH value is 4.0.
Bonderizing: above-mentioned working fluid is put in test piece, handled 8 minutes down at 25 ℃.Obviously as can be seen, there is not sediment to produce in the bonderizing.And phosphatize phosphate coat detection to making.
Service check:
Test piece specification: cold-reduced sheet: 120mm*80mm*1mm
Phosphatize phosphate coat outward appearance: press GB2828-88 and carry out, meet the requirements
Phosphorization film quality: press GB6807-91 and measure, be 1.90-2.05g/m
2, reach the phosphatization requirement fully.
Phosphatize phosphate coat solidity to corrosion: press GB6807-91 appendix D and measure spot corrosion 1 minute.
Shock-resistance: spray polyurethane paint on the steel plate that will handle with this phosphatization liquid.Press GB1732 and measure shock-resistance 500Ncm.
Snappiness: press GB1731 and measure snappiness by φ=1mm.
Adhesion test: press GB1720 and measure 1 grade of sticking power, and not during phosphatization sticking power be the 2-3 level, illustrate that this phosphatize phosphate coat and paint film have good matching capacity.
Use comparative example 1
Preparation 1000kg working fluid: put into 667kg water in the phosphatization groove, add the phosphorization agent mother liquor 50kg of comparative example 1 preparation then, add water to 1000kg after stirring, add the sodium nitrite solution 3kg of promotor 20% again, stir.After testing, the working fluid total acidity of preparation is 18 points, and free acidity is 1.2 points, and promoting to count is 1.0, and the pH value is 2.6.
Bonderizing: above-mentioned working fluid is put in test piece (specification such as Application Example 1), handled 10 minutes down at 25 ℃.Have many sediments to produce in the bonderizing, influential to continuous bonderizing, every day, the workman need carry out 3 times sediment salvaging, and needed more to renew the working fluid of preparation after the time, otherwise bonderizing can't carry out.
Use comparative example 2
Preparation 1000kg working fluid: put into 667kg water in the phosphatization groove, add the phosphorization agent mother liquor 50kg of comparative example 2 preparations then, add water to 1000kg after stirring, add the sodium nitrite solution 2kg of promotor 20% again, stir.After testing, the working fluid total acidity of preparation is 20 points, and free acidity is 1.5 points, and promoting to count is 1.0, and the pH value is 2.5.
Bonderizing: above-mentioned working fluid is put in test piece (specification such as Application Example 1), handled 20 minutes down at 25 ℃.Have a lot, a large amount of sediments to produce in the bonderizing, continuous bonderizing is had a strong impact on, every day, the workman need carry out 4 times sediment salvaging, and needed more to renew the working fluid of preparation after the time, otherwise bonderizing can't carry out at all.
Industrial applicibility
No slag Zinc phosphating provided by the invention agent has solved that traditional Zinc phosphating agent exists that sediment, contaminate environment, non-ferrous metal zinc are wasted in a large number, inherent difficult problems such as labour intensity is big in the bonderizing.Product of the present invention is a kind of environmental protection, energy-conservation completely new product, and it was overturned and has recognized Zinc phosphating in the world so that the notion of a large amount of sediments to be arranged surely, introduced so far the reaction of causing a sensation property in the field of business to the market from 2007.Through the client use in 3 years, verified that product of the present invention has that bonderizing does not have that sediment produces, phosphorization agent need not heat premium propertiess such as can using, need not change in the bonderizing process working fluid during bonderizing.Thereby pushing bigger market to for product of the present invention lays a solid foundation.
Although the contriver has done comparatively detailed elaboration to technical scheme of the present invention and has enumerated, be to be understood that, for the those skilled in the art in this area, the foregoing description is modified and/or flexible or to adopt the replacement scheme that is equal to be obvious, the essence that all can not break away from spirit of the present invention, the term that occurs among the present invention is used for can not being construed as limiting the invention the elaboration of technical solution of the present invention and understanding.
Claims (6)
1. a low temperature does not have the agent of slag Zinc phosphating, it is characterized in that: its composition comprises the composition of following weight part: nitric acid 280-285 part, phosphatase 11 00-105 part, zinc oxide 93-96 part, soda ash 15-16 part, citric acid 2.0-2.2 part, Sodium Fluoride 1.0-1.2 part, 1.0 parts of Sodium Nitrites, complexing agent 48-50 part add water to 1000 parts.
2. low temperature as claimed in claim 1 does not have the agent of slag Zinc phosphating, it is characterized in that: described complexing agent is grouped into by the one-tenth of following weight part: EDTA4.5-5 part, citric acid 0.8-1.5 part, tartrate 3-3.5 part, sodium wolframate 0.5-0.7 part add water to 48-50 part.
3. claim 1 or 2 described low temperature do not have the preparation method of slag Zinc phosphating agent, it is characterized in that described preparation method comprises:
At first with zinc oxide, soda ash, citric acid, Sodium Fluoride, Sodium Nitrite difference water furnishing mashed prod, drop into nitric acid, phosphoric acid, zinc oxide pasty state thing, soda ash mashed prod, citric acid mashed prod, Sodium Fluoride mashed prod, Sodium Nitrite mashed prod and complexing agent then in reaction vessel successively, reaction adds water to 1000 parts after finishing.
4. preparation method as claimed in claim 3 is characterized in that the time of described reaction was at least 2 hours.
5. claim 1 or 2 described low temperature do not have the application of slag Zinc phosphating agent in bonderizing, it is characterized in that, in the described bonderizing: phosphorization agent is made into the working fluid of concentration 3-5wt%.
6. application as claimed in claim 5 is characterized in that, in the described bonderizing: phosphatization temperature is 5-40 ℃, and phosphating time is 5-18 minute.
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| CN2010103001900A CN102121103B (en) | 2010-01-11 | 2010-01-11 | Low-temperature slag-free zinc bonderite as well as preparation method and applications thereof |
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| CN2010103001900A CN102121103B (en) | 2010-01-11 | 2010-01-11 | Low-temperature slag-free zinc bonderite as well as preparation method and applications thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102424963A (en) * | 2011-12-23 | 2012-04-25 | 无锡鸿海龙船机有限公司 | Phosphating treatment process for deformation-free anti-scratch inner sleeve |
| CN102965662A (en) * | 2012-10-22 | 2013-03-13 | 大连碧城环保科技有限公司 | Environmentally-protective slag reducing agent of phosphating solution |
| CN106011814A (en) * | 2016-06-17 | 2016-10-12 | 霍山县龙鑫金属制品有限公司 | Surface phosphating treatment technique for steel |
| CN106868488A (en) * | 2017-03-13 | 2017-06-20 | 衢州忠邦涂料有限公司 | One kind is without slag type bonderite |
| CN111876765A (en) * | 2020-08-04 | 2020-11-03 | 重庆广久辉科技有限公司 | Steel surface micro-slag pretreatment agent and preparation method thereof |
| CN112391618A (en) * | 2019-08-12 | 2021-02-23 | 东莞市颖兴金属表面处理材料有限公司 | Environment-friendly phosphating solution containing graphene oxide and preparation method thereof |
| CN113718238A (en) * | 2021-07-29 | 2021-11-30 | 重庆嘉陵特种装备有限公司 | Anticorrosive environment-friendly phosphating agent and preparation method thereof |
| CN114606483A (en) * | 2022-03-10 | 2022-06-10 | 常州市春雷浩宇环保科技有限公司 | Non-slag wear-resistant phosphating solution suitable for drawing deformation and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1029632C (en) * | 1992-04-06 | 1995-08-30 | 天津大学 | Multifunctional low-temp metal phosphorizing liquid and its preparing process |
| CN100383281C (en) * | 2004-04-09 | 2008-04-23 | 余取民 | Rapid zinc series, zinc-calcium series or iron series clean phosphatizing liquid under room-temperature with multiple styles |
| DE102005004586B4 (en) * | 2005-02-01 | 2007-12-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Starch phosphates, process for their preparation and their use |
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2010
- 2010-01-11 CN CN2010103001900A patent/CN102121103B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424963A (en) * | 2011-12-23 | 2012-04-25 | 无锡鸿海龙船机有限公司 | Phosphating treatment process for deformation-free anti-scratch inner sleeve |
| CN102424963B (en) * | 2011-12-23 | 2013-09-18 | 无锡鸿海龙船机有限公司 | Phosphate treatment technology for deformation-free scuffing-resistant inner sleeve |
| CN102965662A (en) * | 2012-10-22 | 2013-03-13 | 大连碧城环保科技有限公司 | Environmentally-protective slag reducing agent of phosphating solution |
| CN106011814A (en) * | 2016-06-17 | 2016-10-12 | 霍山县龙鑫金属制品有限公司 | Surface phosphating treatment technique for steel |
| CN106868488A (en) * | 2017-03-13 | 2017-06-20 | 衢州忠邦涂料有限公司 | One kind is without slag type bonderite |
| CN112391618A (en) * | 2019-08-12 | 2021-02-23 | 东莞市颖兴金属表面处理材料有限公司 | Environment-friendly phosphating solution containing graphene oxide and preparation method thereof |
| CN111876765A (en) * | 2020-08-04 | 2020-11-03 | 重庆广久辉科技有限公司 | Steel surface micro-slag pretreatment agent and preparation method thereof |
| CN113718238A (en) * | 2021-07-29 | 2021-11-30 | 重庆嘉陵特种装备有限公司 | Anticorrosive environment-friendly phosphating agent and preparation method thereof |
| CN114606483A (en) * | 2022-03-10 | 2022-06-10 | 常州市春雷浩宇环保科技有限公司 | Non-slag wear-resistant phosphating solution suitable for drawing deformation and preparation method thereof |
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