CN105002485A - Formula of composite phosphate film solution which adapts to hot stamping of ultra-high-strength steel sheet material blank - Google Patents

Formula of composite phosphate film solution which adapts to hot stamping of ultra-high-strength steel sheet material blank Download PDF

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Publication number
CN105002485A
CN105002485A CN201510517726.7A CN201510517726A CN105002485A CN 105002485 A CN105002485 A CN 105002485A CN 201510517726 A CN201510517726 A CN 201510517726A CN 105002485 A CN105002485 A CN 105002485A
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ultra
phosphate
phosphoric acid
sheet material
lithium
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CN105002485B (en
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徐淑波
赵中魁
张元彬
翟同广
任国成
林晓娟
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Shandong Jianzhu University
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Shandong Jianzhu University
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Abstract

The invention relates to the field of phosphate solution formulas. The phosphate solution is quite suitable for the parkerizing process performed on the ultra-high-strength steel sheet material blank before hot stamping; a composite phosphate solution is used for performing surface treatment on the ultra-high-strength steel sheet material blank, so as to obtain a high-temperature resistant composite lithium iron phosphate-calcium sulphate film which is used for improving the service life of molds. A composite lithium iron phosphate-calcium sulphate surface treatment liquid which adapts to hot stamping of the ultra-high-strength steel sheet material blank is prepared according to the chemical composition ratio provided by the invention, and the preparation method is as follows: firstly, synthesizing lithium iron phosphate using iron oxide Fe2O3, lithium hydroxide LiOH.H2O, lithium hydroxide LiOH.H2O, ammonium dihydrogen phosphate (NH4)2HPO4 and a carbon source C; then, mixing calcium sulfate CaSO4 ultra-fine powder, lithium iron phosphate LiFePO4 ultra-fine powder, phosphoric acid H3PO4 and distilled water H2O according to a mass ratio of calcium sulfate CaSO4 ultra-fine powder, lithium iron phosphate LiFePO4 ultra-fine powder, phosphoric acid H3PO4 to distilled water H2O being (40-60):(10-30):(5-10):(808-912) to prepare a phosphating solution; placing the to-be-treated ultra-high-strength steel sheet material blank into the phosphating solution at 55-60 DEG C, so that the blank can be coated with a dark gray phosphating film; finally, carrying out heating dehydrogenation process on the blank, so as to reduce the harm caused by hydrogen embrittlement; carrying out the saponification process to further improve the lubrication between the hot stamped sheet material and the mold.

Description

A kind of composite phosphate coating solution formula adapting to the hot stamping of ultrahigh-strength steel plate
Technical field
The present invention relates to a kind of phosphate solution formulation art, the phosphating process that this solution carries out before being particularly adapted to the hot stamping of ultrahigh-strength steel plate blank, needing to carry out surface treatment by compound phosphoric acid salts solution to ultrahigh-strength steel plate blank, obtaining the resistant to elevated temperatures compound phosphoric acid ferrous lithium-calcium sulfate salt film of one deck energy for improving die life.
Background technology
At present, the application processed metallic surface by Phosphating Solution widely, the twentieth century initial stage is due to the invention of tool steel and metal surface phosphating technology, achieve the extruding of ferrous metal, first the extruding of ferrous metal is applied to military project, most typical product is cartridge case, and the nineteen fifties extruding of ferrous metal starts to be applied to civilian, manufactures field be at present widely used at automobile component.The technique forming phosphate film at workpiece surface obtains good application as the gordian technique of the extruding realizing ferrous metal.Wherein phosphatization being carried out for extruding being in great demand of industry to metallic surface, along with the development of hot stamping technology, phosphatization being carried out to ferrous metal plate blank, then carry out hot press-formedly can improving die life and workpiece surface quality.
For the Phosphating Solution being adapted to ferrous metal hot stamping, require by Phosphating Solution phosphatization, form phosphate film at workpiece surface, film thickness is generally 10-15 μm, and frictional coefficient is about 0.05.The phosphate film formed, is made up of tiny plate crystal tissue.Require that this rete is quite soft, heat-resisting, in vesicular, have very strong adsorption to lubricant, and have certain plasticity, can with workpiece viscous deformation.Therefore, the effect of phosphate coating is the isolation bed course between mould and workpiece, decreases surface friction, improves die life.But due to the phosphate coating prepared by traditional Phosphating Solution be usually applicable to cold extrusion when working temperature higher than phosphate coating during 200 ° of C usually start decompose.In recent years, the hot press-formed technology occurred, the quenching heat treatment to plate can be realized while being shaped, improving the forming property of material, greatly extend the range of application of high strength ultrahigh-strength steel at auto parts, for superstrength hot stamping, general temperature is slightly lower than superstrength recrystallization temperature, and at 900 ° of more than C as the hot stamping of steel, at this moment phosphate coating is destroyed, satisfied lubrication can not be obtained in punching course, greatly reduce the life-span of mould.
Therefore, based on above-mentioned purpose, a kind of ultrahigh-strength steel provided by the invention carries out hot stamping, need to carry out surface treatment by compound phosphoric acid ferrous lithium-calcium sulfate salt solution to ultrahigh-strength steel plate blank, obtain the resistant to elevated temperatures compound phosphoric acid ferrous lithium-calcium sulfate salt film of one deck energy, compound phosphoric acid ferrous lithium-calcium sulfate salt the film adopting the method to be formed can be high temperature resistant, in plate blank process, compound phosphoric acid ferrous lithium-calcium sulfate salt film attachment workpiece ability is strong, greatly can improve die life, there is very important industrial application value.
Summary of the invention
The object of patent of the present invention is: the technical deficiency of decomposing for hot stamping phosphate coating, there is provided that surface recombination LiFePO 4-calcium sulfate salt film adhesive ability is strong, high temperature resistant not to be decomposed, low production cost, non-pollution discharge, a kind of surface treatment method being adapted to superstrength steel hot can produced in conventional hot stamping condition undertissue, more traditional phosphoric acid zinc salt film can the feature of high temperature resistant, good stability.
The technical scheme of patent of the present invention is: the present invention is a kind of compound phosphoric acid ferrous lithium-calcium sulfate salt surface treatment method being adapted to superstrength steel hot, as follows:
The present invention be adapted to the compound phosphoric acid ferrous lithium-calcium sulfate salt solution of superstrength steel hot, first by ferric oxide Fe 2o 3, lithium hydroxide LiOHH 2o, lithium hydroxide LiOHH 2o, primary ammonium phosphate (NH 4) 2hPO 4, carbon source C synthesizing lithium ferrous phosphate, its quality proportioning is: (159.68): (65.88): (115.03): (254.11): (12), reacts as follows:
LiOHH 2o=(heats 50-150 DEG C) LiOH+H 2o
(NH 4) 2hPO 4=(heating 50-210 DEG C) 2 (NH) 3+ H 3pO 4
LiOH+H 3pO 4=(heating 50-210 DEG C) LiH 2pO 4+ H 2o
2LiH 2pO 4+ Fe 2o 3+ C=(heating 480-900 DEG C) 2LiFePO 4+ 2H 2o+CO
Comprise calcium sulfate CaSO 4ultrafine powder, LiFePO 4 ultrafine powder LiFePO 4, phosphoric acid H 3pO 4with distilled water H 2o, its quality proportioning is: (40-60): (10-30): (5-10): (808-912).
Compound phosphoric acid ferrous lithium-calcium sulfate salt that the present invention produces is LiFePO 4and CaSO 4one deck salt film, superstrength steel hot can be adapted to.
Compound phosphoric acid ferrous lithium for the hot stamping of ultrahigh-strength steel plate blank of the present invention-calcium sulfate salt surface-treated method:
The first step: the plate blank after blanking is carried out Spheroidizing Annealing process, Heating temperature should be incubated 3-4 hour lower than this material re-crystallizes temperature 50 ° of below C;
Second step: plate blank is carried out shot peening 15Min by shotblasting machine, removes the burr that plate blank surface is tiny, strengthening surface quality;
3rd step: carry out pickling, adopts the sulphuric acid soln of 2% to carry out pickling;
4th step: the compound phosphoric acid ferrous lithium-calcium sulfate salt solution pending plate blank being put into 55 ° of-60 ° of C processes 5-10Min;
5th step: carry out heating dehydrogenation process, reduces the harm of hydrogen embrittlement.
6th step: carry out saponification process, strengthens further between plate blank blank and mould and lubricates.
Compared with prior art, tool of the present invention has the following advantages:
(1) superstrength steel hot is applicable to: the phosphate coating composition of acquisition is compound phosphoric acid ferrous lithium-calcium sulfate salt, generally just decomposes at 1200 ° of more than C, can high temperature resistantly not decompose, meet the requirement of superstrength steel hot.
(2) with low cost: the starting material of employing are basic chemical industry product, cheap, meet large-scale industrial application service requirements.
(3) easy and simple to handle: the present invention is not carrying out under large change condition, traditional phosphating soap metallization processes equipment can be used, reliably easy and simple to handle.
(4) phosphating time is short, effective: after blank adopts calcium salt overlay film, and rete is soft, heat-resisting, in vesicular, have very strong adsorption to lubricant, and has certain plasticity, and phosphating time is short, effective.
Embodiment
Provide most preferred embodiment of the present invention below:
Plate blank after blanking is carried out Spheroidizing Annealing process, and Heating temperature should be incubated 3-4 hour lower than this material re-crystallizes temperature 50 ° of below C; By shotblasting machine, plate blank is carried out shot peening 15Min, remove the burr that plate blank surface is tiny, strengthening surface quality; Carry out pickling, adopt the sulphuric acid soln of 2% to carry out pickling; Provide chemical composition ratio according to invention, configure a kind of compound phosphoric acid ferrous lithium-calcium sulfate salt surface treatment liquid being adapted to superstrength steel hot: first by ferric oxide Fe 2o 3, lithium hydroxide LiOHH 2o, lithium hydroxide LiOHH 2o, primary ammonium phosphate (NH 4) 2hPO 4, carbon source C synthesizing lithium ferrous phosphate, secondly will comprise calcium sulfate CaSO 4ultrafine powder, LiFePO 4 ultrafine powder LiFePO 4, phosphoric acid H 3pO 4, and distilled water H 2o, its quality proportioning is: (40-60): (10-30): (5-10): (808-912).In the present embodiment, its quality proportioning can select following any one: 40:10:5:808; 60:30:10:912; 45:15:8:830; 50:20:9:880.Compound phosphoric acid ferrous lithium-calcium sulfate salt solution that pending hot stamping plate blank puts into 55 ° of-60 ° of C is processed 5-10Min; Carry out heating dehydrogenation process, reduce the harm of hydrogen embrittlement.Carry out saponification process, strengthen further between plate blank blank and mould and lubricate.

Claims (1)

1. adapt to a composite phosphate coating solution formula for ultrahigh-strength steel plate hot stamping, it is characterized in that first by ferric oxide Fe 2o 3, lithium hydroxide LiOHH 2o, lithium hydroxide LiOHH 2o, primary ammonium phosphate (NH 4) 2hPO 4, carbon source C synthesizing lithium ferrous phosphate, then will comprise calcium sulfate CaSO 4ultrafine powder, LiFePO 4 ultrafine powder LiFePO 4, phosphoric acid H 3pO 4with distilled water H 2it is LiFePO that O synthesizes compound phosphoric acid ferrous lithium-calcium sulfate salt 4and CaSO 4one deck salt film:
A () LiFePO 4 is by ferric oxide Fe 2o 3, lithium hydroxide LiOHH 2o, lithium hydroxide LiOHH 2o, primary ammonium phosphate (NH 4) 2hPO 4, carbon source C synthesizes;
Compound phosphoric acid ferrous lithium-each the composition proportion of calcium phosphate salt solution of (b) superstrength degree steel hot: calcium sulfate CaSO 4ultrafine powder, LiFePO 4 ultrafine powder LiFePO 4, phosphoric acid H 3pO 4with distilled water H 2o, its quality proportioning is: 40-60): (10-30): (5-10): (808-912);
One deck salt film of what c the composite phosphate coating solution formula of () described adaptation superstrength degree steel plate material hot stamping was produced is a kind of compound phosphoric acid ferrous lithium-calcium sulfate salt, the high temperature of this composition ability 1200 ° of C, can be adapted to the hot stamping of superstrength degree steel plate material.
CN201510517726.7A 2015-08-22 2015-08-22 A kind of composite phosphate coating solution formula for adapting to unimach plate drop stamping Expired - Fee Related CN105002485B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101956191A (en) * 2010-11-08 2011-01-26 大连三达奥克化学股份有限公司 Car cast aluminum alloy cylinder body and manganese black phosphating agent for piston and preparation method thereof
CN103643230A (en) * 2013-12-07 2014-03-19 山东建筑大学 Surface treatment method for composite sulfuric acid-phosphomycin calcium applicable to warm extrusion
CN104250742A (en) * 2013-06-28 2014-12-31 无锡洛社科技创业有限公司 Phosphatization liquid for steel pipe cold rolling processing pretreatment

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101956191A (en) * 2010-11-08 2011-01-26 大连三达奥克化学股份有限公司 Car cast aluminum alloy cylinder body and manganese black phosphating agent for piston and preparation method thereof
CN104250742A (en) * 2013-06-28 2014-12-31 无锡洛社科技创业有限公司 Phosphatization liquid for steel pipe cold rolling processing pretreatment
CN103643230A (en) * 2013-12-07 2014-03-19 山东建筑大学 Surface treatment method for composite sulfuric acid-phosphomycin calcium applicable to warm extrusion

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