阅读说明：本技术 Ni－P－B系电镀皮膜的成膜方法、该皮膜和具备该皮膜的滑动构件 (Film build method, the epithelium and the sliding component for having the epithelium of Ni-P-B system plating epithelium ) 是由 笹山裕晃 于 2018-03-14 设计创作，主要内容包括：在Ni－P－B系镀敷皮膜的成膜方法中,在含有Ni离子、亚磷酸根离子、烷基胺硼烷、乙酸、至少一种初级光亮剂以及包含至少一种表面活性剂的次级光亮剂的镀浴中进行电镀。在上述镀浴中,烷基胺硼烷的浓度为1.37mmol/L以上,乙酸的浓度为0.70mol/L以上且小于2.80mol/L。由此,即便将电流密度提高至80A/dm<Sup>2</Sup>以上而提高成膜速度,也能够减少烧焦和异常析出等外观不良的产生,并且能够在不实施烘烤处理的情况下以高生产效率成膜具有Hv700以上的高硬度的镀敷皮膜。(In the film build method of Ni-P-B system plating epithelium, it is electroplated in the plating bath containing Ni ion, orthophosphite ions, alkyl amine borine, acetic acid, at least one primary brightener and the second-class brightener comprising at least one surfactant.In above-mentioned plating bath, the concentration of alkyl amine borine is 1.37mmol/L or more, and the concentration of acetic acid is 0.70mol/L more than and less than 2.80mol/L.Even if current density is improved to 80A/dm as a result, 2 Film forming speed is improved above, can also reduce the generation burnt with bad orders such as abnormal precipitations, and can be in the case where not implementing baking processing with the plating epithelium of high rigidity of the high efficiency film forming with Hv700 or more.)

1. a kind of film build method of Ni-P-B system plating epithelium, which is characterized in that

Containing Ni ion, orthophosphite ions, alkyl amine borine, acetic acid, at least one primary brightener and comprising at least It is electroplated in a kind of plating bath of the second-class brightener of surfactant,

The concentration of alkyl amine borine in the plating bath is 1.37mmol/L or more,

The concentration of acetic acid in the plating bath is 0.70mol/L more than and less than 2.80mol/L.

2. the film build method of Ni-P-B system plating epithelium according to claim 1, which is characterized in that the alkylamine boron Alkane be trialkylamine borane or dialkylamine boranes,

The surfactant is anionic surfactant.

3. the film build method of Ni-P-B system plating epithelium according to claim 2, which is characterized in that the alkylamine boron Alkane be trimethylamine borane or dimethylamine borane,

The surfactant is lauryl sodium sulfate.

4. the film build method of Ni-P-B system plating epithelium described in any one of claim 1 to 3, which is characterized in that Carrying out the current density when plating is 80A/dm²More than.

5. a kind of Ni-P-B system plating epithelium, which is characterized in that

In the Ni-P-B system plating epithelium,

The containing ratio of Ni be 90at% or more and 98at% hereinafter,

The containing ratio of P be 1at% or more and 9at% hereinafter,

The containing ratio of B is 0.1at% more than and less than 1at%,

The hardness of the Ni-P-B system plating epithelium is Hv700 or more,

The crystallite dimension of the Ni-P-B system plating epithelium found out by X-ray diffraction is 4nm or more and 10nm or less.

6. Ni-P-B system plating epithelium according to claim 5, which is characterized in that

In the Ni-P-B system plating epithelium,

The containing ratio of C is 0.1at% or more,

The containing ratio of S is 0.1at% or more.

7. a kind of sliding component, which is characterized in that be the sliding structure for having the plating epithelium at least formed on the surface of sliding part Part,

The plating epithelium is Ni-P-B system plating epithelium described in claim 5 or 6.

Technical field

The present invention relates to film build method, the epithelium and the sliding components for having the epithelium of Ni-P-B system plating epithelium.

Background technique

In this technical field, it is known that in order to improve such as corrosion resistance, wear resistance, fatigue strength and taste, In such as clutch hub, mix conjunction of the surface filming of the sliding components such as damper, piston and gear for example by containing nickel (Ni) The plating epithelium that gold is constituted.The film build method of such plating epithelium be roughly divided into electroless-plating (sometimes referred to as " chemical plating ") and Plating (sometimes referred to as " electrolysis is precipitated ").

For example, making the plating after proposing the plating epithelium by electroless-plating film forming Ni-P system and Ni-P-B system etc. Epithelium contacts with phosphate solution and forms phosphate coating on the plating epithelium, so as to improve (examples such as initial stage sliding properties As referring to patent document 1).However, since electroless-plating is to make metal ion by the chemical reaction of metal ion and reducing agent The method for restoring precipitation in a metallic form on blank, therefore, film forming speed (speed of separating out) is very slow, and production efficiency is low. In addition, needing to frequently replace bath foam, high production cost in order to which the match ratio of the various composition in plating bath is remained constant.In addition, In the case where needing sufficiently to improve hardness and the adaptation etc. of plating epithelium, need to carry out baking processing to plating epithelium, because This, production efficiency further decreases.Baking processing needs processing equipments and the regulations such as the heating device corresponding to its treatment conditions The processing time, therefore, can become production cost increase and production efficiency reduce principal element.

On the other hand, compared with electroless-plating, film forming speed (carrying out speed) fastly, can be by increasing current density for plating And improve film forming speed (referring for example to patent document 2).However, if excessively increasing current density, the epithelium to be formed a film Compactness reduce and hardness reduces, or generate the misgivings of the bad orders such as so-called " burning ".Therefore, increased based on current density The rising of big film forming speed is limited.In addition, in plating, in the hardness and adaptation etc. for needing sufficiently to improve plating epithelium In the case of, it is also desirable to baking processing is carried out to plating epithelium, therefore, the raising of the production efficiency based on plating is also limited.

Summary of the invention

As described above, in this technical field, in order to high efficiency film forming there is the plating epithelium of high rigidity to carry out Various trials, but be not yet determined to have both the hardness of plating epithelium and the technology of production efficiency with sufficiently high level.This One of invention, which is designed to provide one kind, to have height in the case where not implementing baking processing with high efficiency film forming The technology of the plating epithelium of hardness.

Present inventor has performed further investigations, as a result, it has been found that passing through the plating of plating film forming nickel (Ni)-phosphorus (P)-boron (B) system It applies in the method for epithelium, it, can by being controlled the concentration of alkyl amine borine and acetic acid in plating bath respectively in defined range The generation of the bad order such as so-called " burning " and abnormal precipitation is reduced, and can be improved current density and do not implementing to dry There is in the case where roasting processing with high efficiency film forming the plating epithelium of high rigidity.

Specifically, film build method (hereinafter sometimes referred to " the side of the present invention of Ni-P-B system plating epithelium of the invention Method ") it is containing Ni ion, orthophosphite ions, alkyl amine borine, acetic acid, at least one primary brightener and comprising extremely The film build method for the Ni-P-B system plating epithelium being electroplated in a kind of plating bath of the second-class brightener of few surfactant.In In above-mentioned plating bath, the concentration of alkyl amine borine is 1.37mmol/L or more, the concentration of acetic acid be 0.70mol/L more than and less than 2.80mol/L。

In addition, Ni's contains in Ni-P-B system plating epithelium (hereinafter sometimes referred to " epithelium of the present invention ") of the invention Having rate is 90at% or more and 98at% hereinafter, the containing ratio of P is 1at% or more and 9at% hereinafter, the containing ratio of B is 0.1at% is more than and less than 1at%.In addition, the hardness of epithelium of the present invention is Hv700 or more, epithelium of the present invention passes through X-ray The crystallite dimension that diffraction (XRD:X-Ray Diffraction) is found out is 4nm or more and 10nm or less.

In addition, sliding component (hereinafter sometimes referred to " component of the present invention ") of the invention is the surface shape at least in sliding part At the sliding component for having above-mentioned epithelium of the present invention.

According to the method for the present invention, the generation of the bad order such as burning and exception is precipitated can be reduced, and can be mentioned High current density has the plating epithelium of high rigidity with high efficiency film forming.In addition, detailed content is as described below, according to this Inventive method can realize high rigidity in the Ni-P-B system plating epithelium after rigid plating.That is, in the method for the present invention, it is above-mentioned Baking processing be not required constitutive requirements.Therefore, from the viewpoint, according to the method for the present invention, it can be improved plating The film forming speed of epithelium is applied, production efficiency is improved.

In addition, epithelium of the present invention has high rigidity in the case where not implementing baking processing, can be realized high wear-resistant Property and fatigue strength etc..Further, since component of the present invention is at least formed with epithelium of the present invention, therefore, energy on the surface of sliding part Enough play high sliding properties.According to the present invention, as described above, it is possible to have both the hardness and life of plating epithelium with sufficiently high level Produce efficiency.

Other purposes, other feature and subsidiary advantage of the invention can as referring to described in attached drawing below about this Invention each embodiment explanation and will be readily understood that.

Specific embodiment

" the 1st embodiment "

Hereinafter, (hereinafter sometimes referred to the film build method of the Ni-P-B system plating epithelium of the 1st embodiment of the invention " the 1st method ") it is illustrated.

< constitutes >

1st method is the film build method that nickel (Ni)-phosphorus (P)-boron (B) is plating epithelium.In the 1st method, contained There is the primary brightener of Ni ion, orthophosphite ions, alkyl amine borine, acetic acid, at least one and comprising at least one surface Plating in the plating bath of the second-class brightener of activating agent.

As the supply source of Ni ion, such as nickel sulfate (NiSO can be used₄), nickel sulfamic acid (Ni (NH₂SO₃)₂) and Nickel chloride (NiCl₂) etc. well known to a person skilled in the art substances.As the supply source of orthophosphite ions, such as can use Sodium phosphite (Na₂HPO₃) and potassium phosphite (K₂HPO₃) etc. well known to a person skilled in the art substances.

As the concrete example of alkyl amine borine, such as trialkylamine borane and dialkylamine boranes can be enumerated etc..As three The concrete example of alkyl amine borine, such as trimethylamine borane and triethylamine borane can be enumerated etc..As the specific of dialkylamine boranes Example, such as dimethylamine borane and diethylamine borane can be enumerated etc..

As primary brightener, such as can be using aromatic series such as aromatic sulphonic acids class, the para toluene sulfonamides such as benzene sulfonic acid Well known to a person skilled in the art substances for aromatic sulfonyls imines such as sulfonamides and saccharin and saccharin sodium etc..As secondary Brightener, such as can be using allyl compounds (vinyl compound), 2- fourth such as aldehydes, the allyl sulphonic acids such as formaldehyde The art technologies such as the nitriles such as the acetylides such as alkynes -1,4- glycol and ethyl cyanalcohol (エ チ Le シ ア Application ヒ De リ Application) Substance well known to personnel.But second-class brightener contained in plating bath used in the 1st method must comprising surfactant conduct The constituent needed.In other words, which includes at least one surfactant.

As above-mentioned surfactant, such as can be using nonionics (non-ionic) tables such as polyoxyethylene alkyl ethers The cationics such as face activating agent, lauryl amine and lauryl amine (cationic) surfactant and NaLS and ten Well known to a person skilled in the art surfactants for the anionic properties such as sodium dialkyl sulfate (anionic) surfactant etc..

In addition, the concentration of the alkyl amine borine in above-mentioned plating bath is 1.37mmol/L or more.For example, using trimethylamine borane When as alkyl amine borine, the concentration of the trimethylamine borane in above-mentioned plating bath is 0.1g/L or more.Promote boron (B) to plating as a result, The eutectoid in epithelium is applied, the ternary alloy three-partalloy epithelium of Ni-P-B system is formed more reliably, can be improved Ni-P-B system plating skin The hardness of film.

In addition, the concentration of the acetic acid in above-mentioned plating bath is 0.70mol/L more than and less than 2.80mol/L.In other words, above-mentioned The concentration of acetic acid in plating bath is 40mL/L more than and less than 160mL/L.By making the concentration 0.70mol/L or more of acetic acid, Even if current density when improving the film forming of plating epithelium, the generation burnt with bad orders such as abnormal precipitations can be also reduced. In other words, it can reduce and burn and abnormal electric current when the generation of bad orders such as being precipitated and improving the film forming of plating epithelium is close Degree.As a result, it is possible to improve the film forming speed of plating epithelium, production efficiency is improved.In addition, the concentration of acetic acid is 2.80mol/L When above, the supply source of Ni ion (such as nickel sulfate (NiSO₄) etc.) solubility in plating bath reduces, the supply source of Ni ion A part with solid state dissolve remain, it is difficult to improve the concentration of Ni ion, it is thus not preferred.

It should be noted that as described above, according in the 1st method as the Ni-P-B of the various embodiments of the invention of representative It is the film build method (the method for the present invention) of plating epithelium, can be realized in the Ni-P-B system plating epithelium after rigid plating high hard Degree.That is, baking processing above-mentioned in the 1st method is not required constitutive requirements.Therefore, from the viewpoint, according to the 1st Method can be improved the film forming speed of plating epithelium, improve production efficiency.

< effect >

As described above, the generation of the bad order such as burning and exception is precipitated can be reduced according to the 1st method, and It improves current density and improves production efficiency, and the Ni-P-B system plating epithelium with high rigidity that can form a film.That is, according to 1 method can have both the hardness and production efficiency of plating epithelium with sufficiently high level.

" the 2nd embodiment "

Hereinafter, (hereinafter sometimes referred to the film build method of the Ni-P-B system plating epithelium of the 2nd embodiment of the invention " the 2nd method ") it is illustrated.

< constitutes >

2nd method is one of the preferred embodiment of the 1st above-mentioned method, is a kind of Ni-P-B system plating epithelium Film build method, which is characterized in that using trialkylamine borane or dialkylamine boranes as alkyl amine borine, using anion Property surfactant is as surfactant.

< effect >

According to the 2nd method, the generation of the bad order such as burning and exception is precipitated can be reduced, and can be improved electricity Current density and improve production efficiency, and the Ni-P-B system plating epithelium with high rigidity that can more reliably form a film.That is, according to 2nd method can have both the hardness and production efficiency of plating epithelium with higher level.

" the 3rd embodiment "

Hereinafter, (hereinafter sometimes referred to the film build method of the Ni-P-B system plating epithelium of the 3rd embodiment of the invention " the 3rd method ") it is illustrated.

< constitutes >

3rd method is one of the preferred embodiment of the 2nd above-mentioned method, is a kind of Ni-P-B system plating epithelium Film build method, which is characterized in that using trimethylamine borane or dimethylamine borane as alkyl amine borine, using dodecyl sulphur Sour sodium is as surfactant.

< effect >

According to the 3rd method, the generation of the bad order such as burning and exception is precipitated can be reduced, and can be improved electricity Current density and improve production efficiency, and the Ni-P-B system plating epithelium with high rigidity that further can more reliably form a film. That is, the hardness and production efficiency of plating epithelium can be had both according to the 3rd method with further higher level.

" the 4th embodiment "

Hereinafter, (hereinafter sometimes referred to the film build method of the Ni-P-B system plating epithelium of the 4th embodiment of the invention " the 4th method ") it is illustrated.

It is plated by the Ni-P-B system of the various embodiments of the invention of representative of above-mentioned the 1st method~the 3rd method It applies in the film build method (the method for the present invention) of epithelium, by controlling the concentration of the acetic acid in plating bath in above-mentioned prescribed limit (specifically 0.70mol/L is more than and less than 2.80mol/L), even if current density when improving the film forming of plating epithelium, Also the generation burnt with bad orders such as abnormal precipitations can be reduced.

Present inventor has performed further investigations, as a result, it has been found that according to the method for the present invention, even if it is especially surprising that with up to 80A/dm²Above current density is electroplated, and the generation of the bad order such as burning and exception is precipitated can be also reduced, and And the Ni-P-B system plating epithelium with high rigidity that can form a film.

< constitutes >

Therefore, the 4th method is above-mentioned the 1st method~the 3rd method one of preferred embodiment, is a kind of Ni- The film build method of P-B system plating epithelium, which is characterized in that current density when being electroplated is 80A/dm²More than.

< effect >

According to the 4th method, the generation of the bad order such as burning and exception is precipitated can be reduced, and can be with higher Production efficiency film forming have high rigidity Ni-P-B system plating epithelium.That is, according to the 4th method, it can be with higher production Efficiency film forming has the Ni-P-B system plating epithelium of high rigidity and quality.

" the 5th embodiment "

As described in the beginning part of this specification, the present invention is directed not only to the film forming of above-mentioned Ni-P-B system plating epithelium Method further relates to Ni-P-B system plating epithelium.Hereinafter, to the Ni-P-B system plating epithelium of the 5th embodiment of the invention (hereinafter sometimes referred to " the 5th epithelium ") is illustrated.

< constitutes >

5th epithelium is the plating epithelium being made of the ternary alloy three-partalloy of Ni-P-B system.In the 5th epithelium, nickel (Ni's) contains Having rate is 90at% or more and 98at% hereinafter, the containing ratio of phosphorus (P) is 1at% or more and 9at% hereinafter, boron (B's) contains Rate is 0.1at% more than and less than 1at%.The containing ratio of each ingredient contained in such epithelium can for example, by it is secondary from Well known to a person skilled in the art analysis methods for sub- mass spectrography (SIMS:Secondary Ion Mass Spectrometry) etc. To measure.

In addition, the hardness of the 5th epithelium is Hv700 or more.That is, by using the Vickers hardness test of Vickers The hardness of 5th epithelium of (JIS Z 2244) measurement is Hv700 or more.In addition, the 5th epithelium is found out by X-ray diffraction Crystallite dimension is 4nm or more and 10nm or less.

It should be noted that having the 5th epithelium constituted as described above can be for example, by with the 1st above-mentioned method~4th Method be representative various embodiments of the invention Ni-P-B system plating epithelium film build method (the method for the present invention) into Row film forming.

< effect >

As described above, the 5th epithelium has the fine and close structure being made of minimum crystallite.As a result, the 5th epithelium has height Hardness can be realized high wear resistance and fatigue strength etc..Therefore, for example, by the surface of the sliding part in sliding component at The 5th epithelium of film, can be improved the sliding properties of the sliding component.

" the 6th embodiment "

Hereinafter, to the Ni-P-B system plating epithelium (hereinafter sometimes referred to " the 6th epithelium ") of the 6th embodiment of the invention It is illustrated.

< constitutes >

6th epithelium is the 5th above-mentioned epithelium, and in Ni-P-B system plating epithelium, the containing ratio of carbon (C) is 0.1at% More than, and the containing ratio of sulphur (S) is 0.1at% or more.The containing ratio of carbon contained in such epithelium (C) and sulphur (S) can also With for example, by secondary ion mass spectrometry (SIMS) etc., well known to a person skilled in the art analysis methods to measure.

In the 6th epithelium, in a manner of controlling the containing ratio of carbon (C) and sulphur (S) in epithelium in above range It forms a film, the crystal structure for constituting plating epithelium can be miniaturize, can more reliably realize high rigidity.

< effect >

As described above, can more reliably realize the fine and close structure being made of minimum crystallite according to the 6th epithelium.Its As a result, the 6th epithelium has high rigidity, high wear resistance and fatigue strength etc. can be realized.Therefore, for example, by sliding structure The 6th epithelium of surface filming of the sliding part of part, can be improved the sliding properties of the sliding component.

" the 7th embodiment "

As described in the beginning part of this specification, the present invention is directed not only to the film forming of above-mentioned Ni-P-B system plating epithelium Method and the epithelium further relate to the sliding component for having Ni-P-B system plating epithelium.Hereinafter, to the 7th embodiment party of the invention The sliding component (hereinafter sometimes referred to " the 7th component ") of formula is illustrated.

< constitutes >

7th component is the sliding component for having the plating epithelium at least formed on the surface of sliding part, which is Using above-mentioned the 5th epithelium and the 6th epithelium as Ni-P-B system plating epithelium (this hair of the various embodiments of the invention of representative Bright epithelium).

< effect >

As described above, epithelium of the present invention has high rigidity, high wear resistance and fatigue strength etc. can be realized.Therefore, The 7th component for having the epithelium of the present invention on the surface at least formed on sliding part can play high sliding properties.