CN102719818A - Phosphorus-free chromium-free conversion film treating agent for magnesium alloy workpiece and preparation method - Google Patents
Phosphorus-free chromium-free conversion film treating agent for magnesium alloy workpiece and preparation method Download PDFInfo
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- CN102719818A CN102719818A CN2012102071892A CN201210207189A CN102719818A CN 102719818 A CN102719818 A CN 102719818A CN 2012102071892 A CN2012102071892 A CN 2012102071892A CN 201210207189 A CN201210207189 A CN 201210207189A CN 102719818 A CN102719818 A CN 102719818A
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Abstract
The invention discloses a phosphorus-free chromium-free conversion film treating agent for a magnesium alloy workpiece, which can form a uniform and compact conversion film on surface of the magnesium alloy workpiece, and is stable in process, good in controllability, simple in operation and beneficial for environmental protection, and a preparation method. The treating agent comprises an agent A and an agent B, wherein the agent A is prepared from the following raw materials in percentage by weight: 1-8% of fluoro-zirconic acid, 0.1-1.5% of nitric acid, 1-6% of tannic acid, 1-8% of phytic acid, 1-6% of hydrofluoric acid, 0.1-2.5% of ammonium bicarbonate and the balance of purified water; and the agent B is prepared from the following raw materials in percentage by weight: 1-6% of polyethylene glycol, 1-5% of triethanolamine, 1-2% of defoaming agent and the balance of purified water.
Description
Technical field
The present invention relates to use the conversion film treatment agent before a kind of magnesium alloy workpiece spray-coating; Especially a kind of process stabilizing, controllability be good, simple to operate, be beneficial to environmental protection, and the magnesium alloy workpiece that changes into the conversion film even compact at magnesium alloy work-piece surface is with without phosphorus Chrome-free conversion film treatment agent and preparation method.
Background technology
Magnesiumalloy is that the minimum a kind of alloy of density and it have excellent strength-weight ratio in the alloy used of modern industry.At present, component, motor body, automobile component, daily-use electrical appliance, precision electronic device and the notebook computer casing etc. on aircraft takeoffs and landings wheel hub, guided missile guidance system, aerospace equipment, the satellite need the workpiece of weight reduction all to use the magnesiumalloy manufacturing.
Because magnesium is active chemical element, in the overwhelming majority's mineral acid and organic acid and neutral medium, all be not anti-corrosion, and corrosion also relatively seriously.Therefore; For the solidity to corrosion that improves magnesium alloy workpiece and ornamental, must carry out various finishes to its surface and cover with paint, lacquer, colour wash, etc. and handle, this just need carry out oxidation, passivation, phosphatization or anodic oxidation etc. to the cast magnesium alloys surface; Make it generate various conversion films, as the bottom of spray-coating organic coating.At present; Using more is that adopting conventional is the technology that adopts the chromaking Passivation Treatment after the phosphatization conversion processing of main body again with the manganous phosphate, and its technical process is: UW preparatory degreasing → UW degreasing → water rinse → water rinse → acid-wash activation → water rinse → neutralizing treatment → water rinse → ultrasonic surface adjustment → UW phosphatization → water rinse → UW commentaries on classics spray-coating of the pure washing → hot blast drying of passivation → water rinse → water rinse → UW → down of heating of heating of heating of heating.This process application contain the process materials that the phosphorous grade of chromium has severe toxicity, be unfavorable for environmental protection, can not detect through SGS, foreign exchange earning is restricted.
Summary of the invention
The present invention is in order to solve the above-mentioned technical problem of existing in prior technology; Provide a kind of process stabilizing, controllability good, simple to operate, be beneficial to environmental protection, the magnesium alloy workpiece that changes into the conversion film even compact at magnesium alloy work-piece surface is with without phosphorus Chrome-free conversion film treatment agent and preparation method.
Technical solution of the present invention is: a kind of magnesium alloy workpiece is characterized in that comprising A agent and B agent with without phosphorus Chrome-free conversion film treatment agent, and said A agent is following with raw material and mass percent:
Fluorine zirconic acid 1～8%
Nitric acid 0.1～1.5%
Tannic acid 1～6%
Phytic acid 1～8%
Hydrofluoric acid 1～6%
Bicarbonate of ammonia 0.1～2.5%
The pure water surplus
Said B agent is following with raw material and mass percent:
Polyoxyethylene glycol 1～6%
Trolamine 1～5%
Skimmer 1～2%
The pure water surplus.
A kind of above-mentioned magnesium alloy workpiece is with the preparation method of without phosphorus Chrome-free conversion film treatment agent; It is characterized in that said A agent carries out as follows: the pure water that will calculate weighing earlier joins in the reaction kettle; Agitator; The control rotating speed is 80 rev/mins, and fluorine zirconic acid, nitric acid, tannic acid, phytic acid, hydrofluoric acid, the bicarbonate of ammonia that will calculate weighing more successively join in the reaction kettle slowly, whenever add a kind of raw material and all will stir 10～20 minutes; When all reinforced continued stirrings that finishes, be the lightpink transparent liquid until solution; Said B agent is carried out as follows: the pure water that will calculate weighing earlier joins in the reaction kettle; Agitator; The control rotating speed is 60 rev/mins; Polyoxyethylene glycol, trolamine, the skimmer that will calculate weighing more successively join in the reaction kettle slowly, stir while feeding in raw material, and are the light beige transparent liquid until solution.
The present invention is to be host with the rare-earth salts, is auxiliary agent with oxygen anion salt, and introducing phytic acid and tannic acid simultaneously is additive.Because of phytic acid is very rare multiple tooth sequestrant for magnesiumalloy, it can not only make magnesiumalloy anticorrosive, more can improve the cohesiveness of magnesiumalloy and organic coating; Tannic acid is the complex compound of multi-phenol, and it is acid that the solution after hydrolysis is, and ability oligodynamical magnesium metal can generate the conversion rete then.The present invention is phosphorus-containing acid ion, 6 valency chromium ion and heavy metallic salts not, and Chrome-free is without phosphorus, and is trickle at the formed conversion film film of magnesium alloy work-piece surface crystalline substance, rete is fine and close, continuous whole, and is strong with the bonding force of magnesiumalloy metallic surface; Rete has porousness, adsorptivity, with organic sprayed coating strong adhesion; Magnesiumalloy metals ion and the nonmetallic ion poor mobility in rete, the crystal structure of rete is stable.The coating of spray-coating is done tack, wet tack and the detection of boiling water tack and is all reached 0 grade standard; Simultaneously also through shock-resistance, anti-cupping property, resistance to bending, wear resistance and salt fog resistance detection index item by item, have process stabilizing, controllability good, simple to operate, be beneficial to advantage such as environmental protection.
Embodiment
Embodiment 1:
The embodiment of the invention 1 comprises A agent and B agent, and said A agent is following with raw material and mass percent:
Fluorine zirconic acid 1%
Nitric acid 1.5%
Tannic acid 6%
Phytic acid 1%
Hydrofluoric acid 1%
Bicarbonate of ammonia 0.1%
The pure water surplus
Said B agent is following with raw material and mass percent:
Polyoxyethylene glycol 1%
Trolamine 5%
Skimmer 1%
The pure water surplus.
The preparation method is: said A agent is carried out as follows: the pure water that will calculate weighing earlier joins in the reaction kettle; Agitator; The control rotating speed is 80 rev/mins, and fluorine zirconic acid, nitric acid, tannic acid, phytic acid, hydrofluoric acid, the bicarbonate of ammonia that will calculate weighing more successively join in the reaction kettle slowly, whenever add a kind of raw material and all will stir 10～20 minutes; When whole reinforced continued stir abouts 1 hour of finishing, solution is the lightpink transparent liquid; Said B agent is carried out as follows: the pure water that will calculate weighing earlier joins in the reaction kettle; Agitator; The control rotating speed is 60 rev/mins; Polyoxyethylene glycol, trolamine, the skimmer that will calculate weighing more successively join in the reaction kettle slowly, stir about 1 hour while feeding in raw material, and solution is the light beige transparent liquid.
The raw materials used commercially available prod that is.
Embodiment 2:
The embodiment of the invention 2 comprises A agent and B agent, and said A agent is following with raw material and mass percent:
Fluorine zirconic acid 8%
Nitric acid 0.1%
Tannic acid 1%
Phytic acid 8%
Hydrofluoric acid 6%
Bicarbonate of ammonia 2.5%
The pure water surplus
Said B agent is following with raw material and mass percent:
Polyoxyethylene glycol 6%
Trolamine 1%
Skimmer 2%
The pure water surplus.
The preparation method is with embodiment 1, the raw materials used commercially available prod that is.
Embodiment 3:
The embodiment of the invention 2 comprises A agent and B agent, and said A agent is following with raw material and mass percent:
Fluorine zirconic acid 5%
Nitric acid 1%
Tannic acid 3%
Phytic acid 5%
Hydrofluoric acid 3%
Bicarbonate of ammonia 1.5%
The pure water surplus
Said B agent is following with raw material and mass percent:
Polyoxyethylene glycol 3%
Trolamine 3%
Skimmer 1.5%
The pure water surplus.
The preparation method is with embodiment 1, the raw materials used commercially available prod that is.
During use, get A agent and B agent, adopt pure water preparation working fluid, the concentration of A agent is 6%, and the concentration of B agent is 1%, and pH value is controlled at 3.5～3.8Pt.Technical process is following: the preparatory degreasing of UW normal temperature → UW normal temperature degreasing → water rinse → water rinse → acid-wash activation → water rinse → neutralizing treatment → water rinse → water rinse → UW normal temperature change into conversion processing → water rinse → water rinse → water rinse → water purification wash → water purification washes → hot blast drying → change spray-coating down, the present invention is UW normal temperature and changes into transformation treating agent.
The embodiment of the invention 1,2,3; Change into the conversion film even compact at magnesium alloy work-piece surface; Do tack, wet tack and the detection of boiling water tack for the coating of spray-coating and all reach 0 grade standard, simultaneously also through shock-resistance, anti-cupping property, resistance to bending, wear resistance and salt fog resistance detection index item by item.
The present invention changes into the mechanism that changes into film at magnesiumalloy: under the combined action of rare earth metal salt, oxygen anion salt, phytic acid, tannic acid; At first on magnesium alloy work-piece surface, form stable particle crystallization nuclei; Be nucleogenesis, promote crystal growth with continued.Because nucleation and crystal growth are not in work of treatment liquid; And the influence that just on magnesium alloy work-piece surface, takes place and receive the diffusion of work of treatment liquid concentration difference; Brought out the heterogeneous nucleation effect that the magnesium alloy work-piece surface crystallization takes place, changed into the carrying out that changes into the film reaction process and be of value to.
Claims (2)
1. a magnesium alloy workpiece is characterized in that comprising A agent and B agent with without phosphorus Chrome-free conversion film treatment agent, and said A agent is following with raw material and mass percent:
Fluorine zirconic acid 1～8%
Nitric acid 0.1～1.5%
Tannic acid 1～6%
Phytic acid 1～8%
Hydrofluoric acid 1～6%
Bicarbonate of ammonia 0.1～2.5%
The pure water surplus
Said B agent is following with raw material and mass percent:
Polyoxyethylene glycol 1～6%
Trolamine 1～5%
Skimmer 1～2%
The pure water surplus.
2. the said magnesium alloy workpiece of claim 1 is with the preparation method of without phosphorus Chrome-free conversion film treatment agent; It is characterized in that said A agent carries out as follows: the pure water that will calculate weighing earlier joins in the reaction kettle; Agitator; The control rotating speed is 80 rev/mins, and fluorine zirconic acid, nitric acid, tannic acid, phytic acid, hydrofluoric acid, the bicarbonate of ammonia that will calculate weighing more successively join in the reaction kettle slowly, whenever add a kind of raw material and all will stir 10～20 minutes; When all reinforced continued stirrings that finishes, be the lightpink transparent liquid until solution; Said B agent is carried out as follows: the pure water that will calculate weighing earlier joins in the reaction kettle; Agitator; The control rotating speed is 60 rev/mins; Polyoxyethylene glycol, trolamine, the skimmer that will calculate weighing more successively join in the reaction kettle slowly, stir while feeding in raw material, and are the light beige transparent liquid until solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2012102071892A CN102719818A (en) | 2012-06-21 | 2012-06-21 | Phosphorus-free chromium-free conversion film treating agent for magnesium alloy workpiece and preparation method |
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| CN2012102071892A CN102719818A (en) | 2012-06-21 | 2012-06-21 | Phosphorus-free chromium-free conversion film treating agent for magnesium alloy workpiece and preparation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103103517A (en) * | 2012-11-13 | 2013-05-15 | 三达奥克化学股份有限公司 | Silver grey membrane treating agent for non-chromium and non-phosphorus iron and steel components and preparation method thereof |
| CN103103516A (en) * | 2012-11-13 | 2013-05-15 | 三达奥克化学股份有限公司 | Pure blue membrane treating agent for non-chromium and non-phosphorus iron and steel components and preparation method thereof |
| CN103668144A (en) * | 2013-12-24 | 2014-03-26 | 淮南天力生物工程开发有限公司 | Environmentally friendly organic metal treating fluid and preparation method thereof |
| CN106245017A (en) * | 2016-08-31 | 2016-12-21 | 立邦涂料（重庆）化工有限公司 | A kind of chemical conversion agent and preparation method |
| CN107034455A (en) * | 2017-05-04 | 2017-08-11 | 广州洋源化工有限公司 | One kind chemical conversion agent and its preparation method and application |
| CN107460473A (en) * | 2017-08-13 | 2017-12-12 | 上海釜强智能科技有限公司 | A kind of passivation of metal surfaces handling process |
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| CN102392238A (en) * | 2011-11-07 | 2012-03-28 | 大连三达奥克化学股份有限公司 | Normal temperature skin film forming agent of aluminum profile for building, which can replace chromizing agent |
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| CN101665934A (en) * | 2009-09-27 | 2010-03-10 | 大连三达奥克化学股份有限公司 | Film treating agent for treatment before electro-coating of die-cast aluminum alloy workpiece and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103103517A (en) * | 2012-11-13 | 2013-05-15 | 三达奥克化学股份有限公司 | Silver grey membrane treating agent for non-chromium and non-phosphorus iron and steel components and preparation method thereof |
| CN103103516A (en) * | 2012-11-13 | 2013-05-15 | 三达奥克化学股份有限公司 | Pure blue membrane treating agent for non-chromium and non-phosphorus iron and steel components and preparation method thereof |
| CN103668144A (en) * | 2013-12-24 | 2014-03-26 | 淮南天力生物工程开发有限公司 | Environmentally friendly organic metal treating fluid and preparation method thereof |
| CN103668144B (en) * | 2013-12-24 | 2016-01-20 | 淮南天力生物工程开发有限公司 | A kind of environment-friendly type organo-metallic treatment solution and preparation method thereof |
| CN106245017A (en) * | 2016-08-31 | 2016-12-21 | 立邦涂料（重庆）化工有限公司 | A kind of chemical conversion agent and preparation method |
| CN107034455A (en) * | 2017-05-04 | 2017-08-11 | 广州洋源化工有限公司 | One kind chemical conversion agent and its preparation method and application |
| CN107034455B (en) * | 2017-05-04 | 2019-01-01 | 广州洋源化工有限公司 | A kind of chemical conversion agent and its preparation method and application |
| CN107460473A (en) * | 2017-08-13 | 2017-12-12 | 上海釜强智能科技有限公司 | A kind of passivation of metal surfaces handling process |
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Application publication date: 20121010 |