CN101362201B - Method for preparing Cu/Sn coated iron powder - Google Patents
Method for preparing Cu/Sn coated iron powder Download PDFInfo
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- CN101362201B CN101362201B CN2008102328142A CN200810232814A CN101362201B CN 101362201 B CN101362201 B CN 101362201B CN 2008102328142 A CN2008102328142 A CN 2008102328142A CN 200810232814 A CN200810232814 A CN 200810232814A CN 101362201 B CN101362201 B CN 101362201B
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Abstract
The invention relates to a method for preparing Cu/Sn-coated iron powder, which consists of following steps: (1) acid cleaning is carried out to iron powder in hydrochloric acid to get rid of grease and impurity on the surface of the iron powder; (2) plating is exerted to the pretreated iron powder in a copper sulphate solution containing composite addictive to obtain Cu/Fe-coated iron powder; and (3) the plating is exerted to the Cu/Fe-coated iron powder in a stannous chloride solution containing addictive to obtain the Cu/Sn-coated iron powder. The method for preparing Cu/Sn-coated iron powder has the advantages that by controlling the viscosity of main salt, adding proper composite addictive, and changing the temperature and the pH value of a plating solution, the relative content of Cu, Sn and Fe in the composite powder is regulated, thus realizing a compact plating layer with the quantitative coating of 18 plus or minus 2 percent of Cu and 2 plus or minus 0.3 percent of Sn on the iron powder to meet requirements for producing sintered metal product.
Description
Technical field
The present invention relates to a kind of preparation method of Cu/Sn coated iron powder, be specifically related to select compound additive, regulate bath pH value and temperature, be implemented in the method that the iron powder surface quantitatively coats 18 ± 2%Cu and 2 ± 0.3%Sn successively by the control main salt concentration.
Background technology
Cladding powder is a kind of novel heterogeneous compound powder alloy material, and numerous, the unique properties of its kind has been widely used for fields such as national defense industry, machine-building, chemical industry.Cladding powder has heterogeneity on microcosmic, coat complete, can be by the characteristics of outstanding each component of different demands; On macroscopic view, have homogeneity, can make the product structure even, significantly reduce or eliminate and mix that the inhomogeneous product composition tissue that causes differs, the disadvantage of unstable properties.In addition, cladding powder can also change the surface characteristic of powder, thereby improves the processing performance of powder, powdered metallurgical material that processability is more excellent and goods.
Traditional oiliness bearing raw material adopts and mixes iron powder and bronze powder, produce composition and metallographic structure segregation inevitably, cause hard to reach the inhomogeneities of performance mutually, cause bearing operation noise to raise and the shortening in service life, therefore be raw material with the iron powder, research and development prepare the technology of Cu-Sn/Fe composite powder, can fundamentally overcome the shortcoming of traditional mechanical mixture powder, solve the chemical composition and the microstructure segregation problem of oiliness bearing product effectively.
At present, the method for industrial normal employing copper, tin codeposition prepares the Cu-Sn/Fe composite powder.Co-electrodeposition method has been simplified process, and its major defect is that to mantoquita especially the utilization rate of tin salt is lower, and coating compactness is relatively poor.The inventive method coats copper layer and tin layer successively on iron powder surface, the utilization rate of mantoquita and tin salt is reached more than 90%, provides cost savings greatly, and can obtain densification, continuous, complete coating, and this kind method yet there are no report.
Summary of the invention
The method that the purpose of this invention is to provide a kind of Cu/Sn coated iron powder, this method is selected compound additive by the control main salt concentration, regulates bath pH value and temperature, quantitatively coat 18 ± 2%Cu and 2 ± 0.3%Sn successively on the iron powder surface, the advantage that preparation technology is simple, cost is low is arranged.
Technical scheme of the present invention is: will mix with the copper sulfate bath that contains compound additive sodium acetate, propenyl thiocarbamide, polyethylene glycol through the iron powder of overpickling earlier, the mass ratio of sodium acetate, propenyl thiocarbamide, polyethylene glycol is 30:1:10.Under stirring condition, react under the room temperature, make the Cu/Fe cladding powder.Then the Cu/Fe cladding powder that makes is mixed with the stannous chloride plating bath that contains additive, it is 1.2～1.5 with the pH value that the temperature of regulating plating bath is 80～90 ℃, reacts under stirring condition, finally obtains the Cu/Sn coated iron powder.
Technique effect of the present invention:
1) the present invention is coated on the iron powder surface equably with copper and tin, provides possibility for preparation has the premium properties sintered metal product.
2) the present invention has worked out the suitable replacement copper plating and the compound additive of tin by selection, contrast experiment, can obtain fine and close coating uniformly.
3) the present invention is by changing the concentration of main salt, and the temperature and the pH value of regulating plating bath can realize that copper and tin quantitatively are coated on the iron powder surface, and technology are simple, Cu
2+And Sn
2+The utilization rate of ion all can reach more than 90%, has saved cost.
Carry out ESEM, energy spectrum analysis and analysis method by use of spectrum with the inventive method Cu/Sn coated iron powder and measure, the ESEM result shows that the interface of clad and internal layer is apparent in view, and compares continuous whole.Energy spectrum analysis and Spectrum Analysis result show that composite powder mainly contains iron, copper and tin simple substance, and internal layer is the iron particle, and clad is mainly copper and tin simple substance.
Description of drawings
Fig. 1 is the process chart of Cu/Sn coated iron powder preparation of the present invention;
Fig. 2 is the diffraction spectra of Cu/Sn coated iron powder of the present invention;
Fig. 3 is the section metallograph of Cu/Sn coated iron powder of the present invention;
Fig. 4 is a Cu/Sn coated iron powder profile scanning electromicroscopic photograph of the present invention;
The specific embodiment
The preparation of Cu/Sn coated iron powder is mainly following process, referring to Fig. 1:
1) pickling: with concentration be 36% hydrochloric acid to be diluted to concentration be 1% hydrochloric acid, add iron powder and also stirred 3 minutes, with oxide and the greasy dirt of removing the iron powder surface, cleaned standby seam.
2) preparation of Cu/Fe cladding powder: copper sulphate is dissolved in the water, and adds additive in solution: sodium acetate, propenyl thiocarbamide, polyethylene glycol, temperature remains on room temperature, about pH=2, obtains plating bath 1.Then plating bath 1 is mixed with pretreated iron powder, under stirring condition, reacted 2～5 minutes; Reaction finishes, and composite powder is separated with waste liquid, and water repeatedly cleans, and makes Cu/Fe core-shell type cladding powder.
3) preparation of Cu/Sn coated iron powder: earlier citric acid is dissolved in the suitable quantity of water, treats to dissolve fully the back and add SnCl
22H
2O stirs and makes it abundant dissolving (attention: can not be with SnCl
22H
2O is directly soluble in water, otherwise Sn
2+Ion meeting hydrolysis generates a large amount of white precipitates), and in solution, going into dispersant: polyethylene glycol.The pH value of regulating plating bath is 1.2～1.5, and temperature is 80～90 ℃, obtains plating bath 2.Then plating bath 2 is mixed with the Cu/Fe cladding powder that has made, under stirring condition, reacted 2～5 minutes.Question response separates composite powder after finishing with waste liquid, water repeatedly cleans, and carries out vacuum drying at 80～100 ℃ at last, promptly gets the Cu/Sn coated iron powder.
Weighing 15g copper sulphate is dissolved in the low amounts of water, forms copper-bath, adds compound additive in described solution: the 1.5g sodium acetate, 0.05g the propenyl thiocarbamide, the 0.5g polyethylene glycol is fully behind the mixing, the pH of regulator solution is about 2, and supplementing water obtains blue plating bath 1 to 100ml.Plating bath 1 is remained on room temperature, and mix, open agitator and under the condition of 400r/min, carry out displacement reaction: Fe+Cu with pretreated 20g iron powder
2+→ Cu+Fe
2+The blueness for the treatment of plating bath fades away, and when iron powder became brownish red by canescence, reaction finished, and cleaned, and promptly got Cu/Fe core-shell type cladding powder.
Weighing 3g citric acid is dissolved in the low amounts of water, forms citric acid solution; Weighing 0.5g stannous chloride is dissolved in the above-mentioned solution under the edged stirring condition of limit, and adds the 0.5g polyethylene glycol; Fully regulate the pH=1.2 of plating bath behind the mixing, and supplementing water obtains plating bath 2 to 100ml.With the adjustment of plating bath 2 is 80 ℃, and mixes with the 10g Cu/Fe cladding powder that has made, opens agitator and carry out displacement reaction: Fe+Sn under the condition of 400r/min
2+→ Sn+Fe
2+, when treating that the Cu/Fe cladding powder becomes silvery white gradually fully by brownish red, reaction finishes, and cleaning, drying obtain the Cu/Sn coated iron powder.
After testing, the percentage composition of copper and tin is respectively in the Cu/Sn coated iron powder: 17.4%, 1.78%.Sn in the plating bath
2+The conversion ratio of ion is 70%.
Embodiment 2
Weighing 15g copper sulphate is dissolved in the low amounts of water, forms copper-bath, adds compound additive in described solution: the 1.5g sodium acetate, 0.05g the propenyl thiocarbamide, the 0.5g polyethylene glycol is fully behind the mixing, the pH of regulator solution is about 2, and supplementing water obtains blue plating bath 1 to 100ml.Plating bath 1 is remained on room temperature, and mix, open agitator and under the condition of 400r/min, carry out displacement reaction: Fe+Cu with pretreated 20g iron powder
2+→ Cu+Fe
2+The blueness for the treatment of plating bath fades away, and when iron powder became brownish red by canescence, reaction finished, and cleaned, and promptly got Cu/Fe core-shell type cladding powder.
Weighing 3g citric acid is dissolved in the low amounts of water, forms citric acid solution; Weighing 0.5g stannous chloride is dissolved in the above-mentioned solution under the edged stirring condition of limit, and adds the 0.5g polyethylene glycol; Fully regulate the pH=1.2 of plating bath behind the mixing, and supplementing water obtains plating bath 2 to 100ml.With the adjustment of plating bath 2 is 85 ℃, and mixes with the 10g Cu/Fe cladding powder that has made, opens agitator and carry out displacement reaction: Fe+Sn under the condition of 400r/min
2+→ Sn+Fe
2+, when treating that the Cu/Fe cladding powder becomes silvery white gradually fully by brownish red, reaction finishes, and cleaning, drying obtain the Cu/Sn coated iron powder.
After testing, the percentage composition of copper and tin is respectively in the Cu/Sn coated iron powder: 17.7%, 2.3%.Sn in the plating bath
2+The conversion ratio of ion is 90%.
Embodiment 3
Weighing 15g copper sulphate is dissolved in the low amounts of water, forms copper-bath, adds compound additive in described solution: the 1.5g sodium acetate, 0.05g the propenyl thiocarbamide, the 0.5g polyethylene glycol is fully behind the mixing, the pH of regulator solution is about 2, and supplementing water obtains blue plating bath 1 to 100ml.Plating bath 1 is remained on room temperature, and mix, open agitator and under the condition of 400r/min, carry out displacement reaction: Fe+Cu with pretreated 20g iron powder
2+→ Cu+Fe
2+The blueness for the treatment of plating bath fades away, and when iron powder became brownish red by canescence, reaction finished, and cleaned, and promptly got Cu/Fe core-shell type cladding powder.
Weighing 3g citric acid is dissolved in the low amounts of water, forms citric acid solution; Weighing 0.5g stannous chloride is dissolved in the above-mentioned solution under the edged stirring condition of limit, and adds the 0.5g polyethylene glycol; Fully regulate the pH=1.2 of plating bath behind the mixing, and supplementing water obtains plating bath 2 to 100ml.With the adjustment of plating bath 2 is 90 ℃, and mixes with the 10g Cu/Fe cladding powder that has made, opens agitator and carry out displacement reaction: Fe+Sn under the condition of 400r/min
2+→ Sn+Fe
2+, when treating that the Cu/Fe cladding powder becomes silvery white gradually fully by brownish red, reaction finishes, and cleaning, drying obtain the Cu/Sn coated iron powder.
After testing, the percentage composition of copper and tin is respectively in the Cu/Sn coated iron powder: 18.2%, 2.4%.Sn in the plating bath
2+The conversion ratio of ion is 93%.
Embodiment 4
Weighing 15g copper sulphate is dissolved in the low amounts of water, forms copper-bath, adds compound additive in described solution: the 1.5g sodium acetate, 0.05g the propenyl thiocarbamide, the 0.5g polyethylene glycol is fully behind the mixing, the pH of regulator solution is about 2, and supplementing water obtains blue plating bath 1 to 100ml.Plating bath 1 is remained on room temperature, and mix, open agitator and under the condition of 400r/min, carry out displacement reaction: Fe+Cu with pretreated 20g iron powder
2+→ Cu+Fe
2+The blueness for the treatment of plating bath fades away, and when iron powder became brownish red by canescence, reaction finished, and cleaned, and promptly got Cu/Fe core-shell type cladding powder.
Weighing 3g citric acid is dissolved in the low amounts of water, forms citric acid solution; Weighing 0.5g stannous chloride is dissolved in the above-mentioned solution under the edged stirring condition of limit, and adds the 0.5g polyethylene glycol; Fully regulate the pH=1.5 of plating bath behind the mixing, and supplementing water obtains plating bath 2 to 100ml.With the adjustment of plating bath 2 is 90 ℃, and mixes with the 10g Cu/Fe cladding powder that has made, opens agitator and carry out displacement reaction: Fe+Sn under the condition of 400r/min
2+→ Sn+Fe
2+, when treating that the Cu/Fe cladding powder becomes silvery white gradually fully by brownish red, reaction finishes, and cleaning, drying obtain the Cu/Sn coated iron powder.
After testing, the percentage composition of copper and tin is respectively in the Cu/Sn coated iron powder: 17.6%, 2.2%.Sn in the plating bath
2+The conversion ratio of ion is 88%.
Conclusion:
The foregoing description shows, adopts technology provided by the invention, and the percentage composition of copper and tin is respectively in the Cu/Sn coated iron powder of preparing: 18 ± 2% and 2 ± 0.3%, reached industrial requirements.The conversion ratio of mantoquita and pink salt reaches more than 90% in the plating bath simultaneously, has saved cost.
Embodiment measures with metallographic microscope, ESEM (SEM) and X-ray diffraction methods such as (XRD), and gained clad even compact contains elemental copper and tin.
Referring to Fig. 2, scanning electron microscopic observation, the result: coating has certain thickness, and dense and complete.
Referring to Fig. 3, Fig. 4, the metallography microscope sem observation, the result: the internal layer of composite powder is the iron particle, skin is a copper tin clad, and clad is comparatively continuous, complete.
Referring to Fig. 5, X-ray diffraction (XRD) analysis result: composite powder mainly contains the thing phase of fe, elemental copper and simple substance tin.
Claims (1)
1. method for preparing the Cu/Sn coated iron powder is characterized in that having following step:
(1) iron powder is stirred in watery hydrochloric acid under pickling, with greasy dirt and the impurity of removing the iron powder surface;
(2) preparation of Cu/Fe cladding powder:
The copper sulphate of amount of calculation is dissolved in the water, be formulated as the copper-bath of 0.4～0.6mol/L, add additive sodium acetate, propenyl thiocarbamide, polyethylene glycol in the described solution, the mass ratio of its sodium acetate, propenyl thiocarbamide, polyethylene glycol is 30: 1: 10, under the room temperature, about the pH=2-3 of regulator solution, promptly get plating bath 1; The iron powder of plating bath 1 with step (1) gained mixed, stir, displacement reaction: Fe+Cu takes place in the iron powder surface
2+→ Cu+Fe
2+The blueness for the treatment of plating bath fades away, and when iron powder became brownish red by canescence, reaction finished, and powder is separated with solution, and gained powder water cleans, and makes the Cu/Fe cladding powder
(3) preparation of Cu/Sn coated iron powder:
Stir in the acid solution and add SnCl down
22H
2O, making the protochloride solution concentration is 2.5g/L～10g/L, in protochloride solution, add polyethylene glycol, the pH value of adjusting solution is 1.2～1.5, temperature is 80～90 ℃, obtains plating bath 2, and the Cu/Fe cladding powder of plating bath 2 with step (2) gained mixed, stir, and displacement reaction: Fe+Sn takes place on the cladding powder surface
2+→ Sn+Fe
2+, when treating that the Cu/Fe cladding powder becomes silvery white gradually fully by brownish red, reaction finishes, and separates composite powder and solution, and water cleans, and carries out vacuum drying at 80～100 ℃, promptly gets the Cu/Sn coated iron powder.
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|---|---|---|---|
| CN2008102328142A CN101362201B (en) | 2008-09-28 | 2008-09-28 | Method for preparing Cu/Sn coated iron powder |
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|---|---|---|---|
| CN2008102328142A CN101362201B (en) | 2008-09-28 | 2008-09-28 | Method for preparing Cu/Sn coated iron powder |
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| CN101362201B true CN101362201B (en) | 2011-03-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102689011A (en) * | 2012-06-14 | 2012-09-26 | 湖南顶融科技有限公司 | Preparation method for copper-coated composite powder |
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|---|---|---|---|---|
| RU2629416C2 (en) * | 2016-02-16 | 2017-08-29 | Федеральное государственное бюджетное учреждение науки Институт металлургии Уральского отделения Российской академии наук (ИМЕТ УрО РАН) | Method for producing composite powder material by cladding |
| CN108746602A (en) * | 2018-05-26 | 2018-11-06 | 烟台大学 | A method of preparing copper-clad iron powder using copper-containing wastewater |
| RU2760010C2 (en) * | 2020-04-03 | 2021-11-22 | федеральное государственное автономное образовательное учреждение высшего образования "Самарский национальный исследовательский университет имени академика С.П. Королева" | Method for cladding a powder composition with molten metal |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102689011A (en) * | 2012-06-14 | 2012-09-26 | 湖南顶融科技有限公司 | Preparation method for copper-coated composite powder |
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