CN1051060A - Electric depositing solution of antiwear non-crystal alloy of iron, nickel, phosphorus and technology thereof - Google Patents

Electric depositing solution of antiwear non-crystal alloy of iron, nickel, phosphorus and technology thereof Download PDF

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Publication number
CN1051060A
CN1051060A CN 90109151 CN90109151A CN1051060A CN 1051060 A CN1051060 A CN 1051060A CN 90109151 CN90109151 CN 90109151 CN 90109151 A CN90109151 A CN 90109151A CN 1051060 A CN1051060 A CN 1051060A
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phosphorus
iron
nickel
alloy
coating
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高诚辉
雷天觉
赵源
张绪寿
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Open Laboratory Of Solid Lubrication Lanzhou Institute Of Chemical Physics Chinese Academy Of Sciences
Wuhan Institute Of Material Protection Ministry Of Mechanical And Electronic Industry
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Open Laboratory Of Solid Lubrication Lanzhou Institute Of Chemical Physics Chinese Academy Of Sciences
Wuhan Institute Of Material Protection Ministry Of Mechanical And Electronic Industry
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

The present invention is a kind of electroplating solution and technology for preparing high ferro, the attrition resistant amorphous iron ni-p alloy coating of high phosphorus.Electroplating solution is stable, and current density range is wide, and gained amorphous alloy coating iron-holder can reach 40%, and phosphorus content can reach 17%, coating surface light flawless, and thermostability is higher than the nickel phosphorus non-crystal alloy layer.Microhardness after its non-crystalline state and the crystallization, antifriction quality, wear resistance and resistance to marring are better than the nickel-phosphorus alloy coating after non-crystalline state and the crystallization respectively.

Description

Electric depositing solution of antiwear non-crystal alloy of iron, nickel, phosphorus and technology thereof
The invention belongs to field of electroplating.
The present invention relates to the solution and the technology of the higher non-crystal alloy of iron, nickel, phosphorus galvanic deposit of iron-holder.
Amorphous alloy has special physicals and chemical property and excellent corrosion resistance nature and tribological property.Amorphous phosphorus-nickel alloy coating is common a kind of in the non-crystaline amorphous metal coating.Its feature is, reaches and necessarily closes its corrosion resistance excellent of phosphorus amount, and antifriction and wear resistance are better after the crystallization, but easily produces more serious adhesive wear under non-crystalline state.In most cases wear resistance is not so good as chromium coating, and the nickel price is higher.
In existing amorphous ferronickel phosphorus alloy electro-deposition techniques, the iron level of its electric depositing solution is few, and is low with the relative proportion of nickel, and the iron level of the amorphous nickel ferrophosphor(us) deposition layer that is obtained is all very low.For example, people such as Gao Juan, natural pond Tian Boxiong are about " galvanic deposit of amorphous ferronickel phosphorus alloy " (sufacing Vol.40, No.3,1989) research, ferrous sulfate content is 10g/L in the solution, iron level only is 0.2%(Wt in its amorphous alloy coating), they once attempted to improve the iron-holder in the coating, but failed to obtain amorphous alloy coating.People such as Vitkova.S are at 7th.Galvanotech.Symp.(1985, in " Ni-Fe-phosphorus amorphous alloy galvanic deposit " research of delivering 381-6), summary has been reported solution compolision and processing condition, ortho phosphorous acid sodium content in the solution has been described especially, the phosphorus content of current density and coating, the iron level of not mentioned this amorphous alloy, but according to ferrous sulfate content (10g/l) in its solution and with the proportion grading of single nickel salt, the iron level of its non-crystaline amorphous metal is low-down.In the existing amorphous nickel ferrophosphor(us) deposition layer iron level low mainly be because iron level and the Fe that causes in the unresolved increase plating bath 3+Problem, so solution instability, Fe 3+Cause crisp, the easy decortication of coating more, and blackstreak is arranged; Next is that phosphorus content then is accompanied by decline, can not form non-crystalline state because iron level increases in the alloy layer, because the inhibition that unresolved phosphorus is separated out iron, therefore fails to realize improving simultaneously the problem of phosphorus and iron level in the amorphous alloy coating.And iron level is the key that improves the alloy layer wear resistance in the raising coating.
The objective of the invention is to develop the antiwear non-crystal alloy of iron, nickel, phosphorus deposition layer of a kind of high ferro, high phosphorus, the antifriction performance after its non-crystalline state and the crystallization, wear resisting property, hardness and thermostability be corresponding respectively to be better than nickel-phosphorus alloy coating after non-crystalline state and the crystallization.
The feature of antiwear non-crystal alloy of iron, nickel, phosphorus galvanic deposit of the present invention is that this electric depositing solution is made up of following component:
NiSO 4.6H 2O 50-200g/l
NiCl 2.6H 2O 0-100g/l
FeSO 4.7H 2O 50-150g/l
NaH 2PO 2.H 2O 1-10g/l
H 3PO 410-40g/l
Asccharin 2-4g/l
Main complexing agent 10-80g/l
Auxiliary complex-former 0.1-2g/l
Wherein said main complexing agent is the hydroxyl acids and the salt thereof with ortho position structure of following general formula:
Figure 901091510_IMG2
In the formula: R 1-H, OH
R 2-H，COOZ
R 3-H，CH 2-COO2，CHOH-CHOH-CH 2OH
Z-H，Na，K
Auxiliary complex-former is a phenol.
Another feature of antiwear non-crystal alloy of iron, nickel, phosphorus galvanic deposit of the present invention is that the electroplating technology standard that obtains amorphous alloy layer of the present invention in the electric depositing solution of the above-mentioned composition of the present invention is:
Tank liquor temperature 60-75 ℃
PH 0.8-1.5
Current density 5-20A/dm 2
Do not have and stir
Iron level height in the electric depositing solution of the present invention, also high with the ratio of nickel, its component and reasonable ratio, and added main and auxiliary two kinds of complexing agents that synergistic effect is arranged, current density range is wide.Can obtain iron-holder up to 40% by the present invention, phosphorus content is up to 17% non-crystal alloy of iron, nickel, phosphorus settled layer.By the present invention, iron level in the gained alloy layer is in≤40% scope, phosphorus content is all controlled in≤17% scope, i.e. iron, phosphorus content two controllable parameters in the alloy layer, thus can obtain the amorphous iron nickel-phosphorus alloy settled layer of needed different iron, phosphorus content ratio.
Ring piece wearing test shows that compare with Ni-P coating, amorphous alloy layer wear resistance of the present invention has improved 2 times, frictional coefficient low 20%; Wear resistance is high by 35% after 400 ℃ of crystallization, and frictional coefficient is low by 18%, and resistance to marring is high by 117%.
Fixed-abrasive wearing and tearing (Taber) test shows, compares with Ni-P coating, and wear resistance improved 60%, 400% crystallization 1 hour (400 ℃/th), correspondingly after 600 ℃/lh and the 400 ℃/4h crystallization improved 1.5,2.8,1.2 times under the non-crystalline state; Simultaneously respectively than the wear resistance high 84%, 82% and 131% of chromium coating.
Advantage of the present invention is:
1, electric depositing solution ingredient stability of the present invention, processing range is wide, and gained amorphous alloy coating iron level can reach 40%, and phosphorus content can reach 17%.The surface-brightening flawless.
2, the microhardness of alloy of iron, nickel, phosphorus coating of the present invention is higher than nickel-phosphorus alloy.
3, the tribological property of alloy of iron, nickel, phosphorus coating of the present invention is better than nickel-phosphorus alloy coating.
When 4, phosphorus content was identical, the crystallization temperature of non-crystal alloy of iron, nickel, phosphorus coating was higher than amorphous phosphorus-nickel alloy coating, and promptly the former thermostability is better than the latter.
Description of drawings:
Fig. 1 is the X-ray diffraction curve of the present invention's iron, nickel, phosphorus non-crystaline amorphous metal.
Curve 1 iron content 25.0 ± 2.0Wt%, phosphorous 15Wt%
Curve 2 iron content 25.0 ± 2.0Wt%, phosphorous 12.8Wt%
Curve 3 iron content 25 ± 2.0Wt%, phosphorous 10.2Wt%
Curve 4 iron content 25 ± 2.0Wt%, phosphorous 7.0Wt%
Embodiment 1
Tank liquor component content (g/l)
NiSO 4，6H 2O 70
NiCl 2，6H 2O 100
FeSO 4，7H 2O 80
NaH 2PO 2，H 2O 5
H 3PO 430
Asccharin 2
Tartaric acid 20
Phosphorus dihydroxy-benzene 0.5
PHI.4
70 ℃ of temperature
Dk 10A/dm 2
Do not have and stir
The gained alloy layer contains Ni75.5Wt%, Fe11.7Wt%, and P12.8wt%, coating surface light, X-ray diffraction are determined as non-crystalline state.
Embodiment 2
Tank liquor component content (g/l)
NiSO 4.6H 2O 80
Nicl 2.6H 2O 30
FeSO 4.7H 2O 140
NaH 2PO 2.H 2O 3.5
H 3PO 425
Asccharin 4
Tartrate 30
Citric acid 20
Pyrocatechol 1.5
PH1.2 T65℃ DK20A/dm 2
Do not have and stir
Gained coating light contains Ni48.3Wt%, and Fe41.4Wt%, P10.3Wt% are non-crystalline state.
Embodiment 3
Tank liquor component content (g/t)
NiSO 4.6H 2O 130
FeSO 4.7H 2O 120
NaH 2PO 2.H 2O 4
H 3PO 420
Tartrate 30
Pyrocatechol 1.0
Asccharin 4
PH1.3 T75℃ DK13A/dm 2
Do not have and stir
Gained coating light, non-crystalline state contains Ni66.0Wt%, Fe23.Wt%, P10.2Wt%.

Claims (1)

1, a kind of antiwear non-crystal alloy of iron, nickel, phosphorus galvanic deposit is characterized in that this electric depositing solution is made up of following component:
NiSO 4·6H 2O 50-200g/l
Nicl 2·6H 2O 0-100g/l
FeSO 4·7H 2O 50-150g/l
NaH 2PO 2·H 2O 1-10g/l
H 3PO 410-40g/l
Asccharin 2-4g/l
Main complexing agent 10-80g/l
Auxiliary complex-former 0.1-2g/l
Wherein said main network contains hydroxyl acids and the salt thereof with ortho position structure that agent is following general formula:
Figure 901091510_IMG1
In the formula: R 1-H, OH
R 2-H，COOZ
R 3-H，CH 2-COOZ，CHOH-CHOH-CH 2OH
Z-H，Na，K
Auxiliary complex-former is a phenol;
In above-mentioned electric depositing solution, the technological specification that obtains the non-crystal alloy of iron, nickel, phosphorus settled layer is: tank liquor temperature 60-75 ℃, and PH0.8-1.5, current density 5-20A/dm 2, do not have and stir.
CN 90109151 1990-11-10 1990-11-10 Electric depositing solution of antiwear non-crystal alloy of iron, nickel, phosphorus and technology thereof Pending CN1051060A (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100408713C (en) * 2006-11-04 2008-08-06 燕山大学 Binary NiP amorphous alloy bulk and method for preparing same
CN100441749C (en) * 2004-10-29 2008-12-10 中国科学院兰州化学物理研究所 Antiwear nickel phosphor functionalized gradient plate preparation method
CN1926265B (en) * 2004-03-01 2010-09-22 爱托特奇德国股份有限公司 Iron-phosphorus electroplating bath and method
CN101311322B (en) * 2008-02-02 2010-12-15 湖南纳菲尔新材料科技股份有限公司 Surface treatment process for electroplating iron-nickel alloy and electroplating solution thereof
CN101906624B (en) * 2009-06-05 2012-02-08 中国科学院金属研究所 Method for preparing iron-nickel-phosphorus chemical plating
CN102839402A (en) * 2012-09-27 2012-12-26 厦门大学 Iron tin stibium phosphorus alloy with high phosphorus content and preparation method thereof
WO2015054930A1 (en) * 2013-10-16 2015-04-23 中国科学院金属研究所 Fe-ni-p-re multicomponent alloy plating layer, and electrodeposition preparation method and application thereof
CN106863659A (en) * 2017-03-13 2017-06-20 歌尔股份有限公司 The processing mold and its manufacture method of macromolecule component
CN107268018A (en) * 2017-06-19 2017-10-20 长沙理工大学 A kind of Fe-based amorphous alloy catalysis electrode and production method
CN108265243A (en) * 2017-01-02 2018-07-10 罗奕兵 A kind of iron-nickel-phosphor non-crystaline amorphous metal composite fibre and preparation method thereof
CN109136888A (en) * 2017-06-28 2019-01-04 罗奕兵 A kind of Fe-Ni-P amorphous alloy catalytic reactor and production method

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1926265B (en) * 2004-03-01 2010-09-22 爱托特奇德国股份有限公司 Iron-phosphorus electroplating bath and method
CN100441749C (en) * 2004-10-29 2008-12-10 中国科学院兰州化学物理研究所 Antiwear nickel phosphor functionalized gradient plate preparation method
CN100408713C (en) * 2006-11-04 2008-08-06 燕山大学 Binary NiP amorphous alloy bulk and method for preparing same
CN101311322B (en) * 2008-02-02 2010-12-15 湖南纳菲尔新材料科技股份有限公司 Surface treatment process for electroplating iron-nickel alloy and electroplating solution thereof
CN101906624B (en) * 2009-06-05 2012-02-08 中国科学院金属研究所 Method for preparing iron-nickel-phosphorus chemical plating
CN102839402A (en) * 2012-09-27 2012-12-26 厦门大学 Iron tin stibium phosphorus alloy with high phosphorus content and preparation method thereof
WO2015054930A1 (en) * 2013-10-16 2015-04-23 中国科学院金属研究所 Fe-ni-p-re multicomponent alloy plating layer, and electrodeposition preparation method and application thereof
US10344391B2 (en) 2013-10-16 2019-07-09 Institute Of Metal Research, Chinese Academy Of Sciences Fe-Ni-P-RE multicomponent alloy plating layer, and electrodeposition preparation method and application thereof
CN108265243A (en) * 2017-01-02 2018-07-10 罗奕兵 A kind of iron-nickel-phosphor non-crystaline amorphous metal composite fibre and preparation method thereof
CN106863659A (en) * 2017-03-13 2017-06-20 歌尔股份有限公司 The processing mold and its manufacture method of macromolecule component
CN107268018A (en) * 2017-06-19 2017-10-20 长沙理工大学 A kind of Fe-based amorphous alloy catalysis electrode and production method
CN109136888A (en) * 2017-06-28 2019-01-04 罗奕兵 A kind of Fe-Ni-P amorphous alloy catalytic reactor and production method

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