JPS61221395A - Electricity conducting roll for electroplating - Google Patents

Abstract

PURPOSE:To improve the corrosion resistance and hardness of a roll by consisting the roll of the compsn. contg. Ni, Si, Mn, Cr, Mo, Cu, Nb and Co at specified ratios and contg. Nb and C at the ratios of the specified relation. CONSTITUTION:The roll is made of the compsn. consisting of <=0.10wt% C, <=2.0% Si, <=1.5% Mn, 14-21% Cr, 16-30% Mo, 0.1-5.0% Cu, <=1.5% Nb, 5% or over and <=35% Co and the balance inevitable impurities and Ni and having the relation 1/10 (%Nb)>=(%C). <=3.0% W is incorporated therein if necessary and >=1 kinds among Ti, Ta, Zr and Hf are incorporated in the relation (1/10Nb+1/5Ti+1/15Ta+1/10Zr+1/15Hf)>=C(respectively %). The electricity conducting roll for electroplating having such compsn. has the overall resistance to corrosion and wear even in severe corrosive conditions during electrolytic corrosion under the conduction of electricity and severe abrasive conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an energizing roll for electroplating.

Conventional technology Conventionally, 1, TIS-
SC! 8/4! Ya1. TIS-SUS 3/A
However, these corrosion-resistant steels have poor corrosion resistance such as current-carrying corrosion and acidic solution corrosion, as well as wear resistance, causing significant roughness on the roll surface, resulting in Polishing of the reusable reservoir was required within a short period of time (eg, one week).

The present applicant has already solved the above-mentioned drawbacks of the conventionally used corrosion-resistant steel, and has developed a method that can be used as a current-carrying roll for electroplating without impairing its conductivity, by electrogalvanizing, electrolytic tin plating, or electroalloy plating. We have proposed a current-carrying roll for electroplating that has excellent corrosion resistance under particularly severe high-current conditions such as It has been confirmed through industrial implementation that the current-carrying rolls for electroplating according to these inventions can produce the desired effects.

Problems to be Solved by the Invention As described above, the previously proposed current-carrying roll for electroplating has achieved the desired effects, but as a result of industrial implementation, the current-carrying roll for electroplating has New problems have arisen in which it is desirable to further improve corrosion resistance and hardness. The present invention aims to solve this problem by
That is the purpose.

In order to overcome this problem, the roll according to the invention is characterized in that it comprises a range of chemical components that solve this problem. That is, in terms of chemical components, the roll according to the present invention contains MO in order to improve the hardness compared to the previously proposed roll.
is more than 16% and less than 30% and CO is more than 5% and less than 3%, and furthermore, in order to stabilize carbon and improve corrosion resistance, Nb is the main element, and as a composite additive element, Ti below 〇%, Mu! The major difference is that Ta, Zr, and Hf are added at r% or less.

EXAMPLES Hereinafter, the present invention will be described in detail based on examples and accompanying drawings showing test procedures.

First, as mentioned above, the roll according to the present invention includes Ni,
The main components are Or, Mo, co, C! u
and Nb1 or Cr, Mo as main components
, Co, W, C! It is characterized by containing u and Nb, but as will be explained in detail later, in order to have both corrosion resistance and wear resistance, CO
solid solution strengthening to the austenite base, and Ni, Mo, C! in the austenite base! The most significant feature is that the roll is made by uniformly dispersing a highly hard intermetallic compound containing r and co as main components.

Therefore, first, the reason why each common ingredient in the roll of the present invention is limited to the specific range as described above will be explained.

Ni, as a basic component, stabilizes the matrix as an austenitic structure, and as the amount of Mo increases,
Forms a highly hard intermetallic compound with Mo, contributing to an increase in hardness. Further, since Ni itself has a tendency to ionize metals, its corrosion dissolution rate is low, and the corrosion-generated film is dense, so it has a large protective effect and excellent passivation ability.

When MO is added to Ni, as its content increases, the capacity of high-hardness intermetallic compounds increases, and a decrease in toughness is unavoidable. and improves wear resistance. On the other hand, corrosion resistance is
Deterioration can be minimized by solution treatment. This tendency to increase hardness is proportional to the amount of Mo, and the effect appears at /Awt%, but when it exceeds 30wt%, corrosion resistance deteriorates,
Causes embrittlement.

Or has a low corrosion dissolution rate and forms a matrix with Ni, Mo, and Co, which also have passivation ability, forming a stronger protective film and providing passivation ability. The content of Or in this alloy is /
! At wt%, the effect is remarkable, but when it exceeds 2/wt%, it becomes saturated, resulting in brittleness due to the formation of weak intermetallic compounds, and furthermore, deteriorating corrosion resistance.

CO dissolves in solid solution in the austenite base, causes a solid solution strengthening effect, increases the hardness of the base, and replaces N1 in the intermetallic compound to change the form of the intermetallic compound. The content of CO in this alloy is limited to more than s% and less than 35%, since it has no effect if it is less than 5%, and if it is more than 35%, it will become brittle and become expensive.

O constitutes a matrix due to the coexistence of Ni, Mo, and CO, forms a strong protective film on the surface layer, and provides passivation ability. However, the content of Cu is 0.
The effect is observed even with the addition of a trace amount of /wt%, but
%, embrittlement occurs and no effect is observed in improving corrosion resistance.
It is limited to 5 wt % or more and 5 wt % or less.

Although the presence of C is unavoidable in manufacturing, it is preferable that the amount of C is as small as possible. In other words, the presence of C precipitates carbides, and these carbides deteriorate corrosion resistance. Therefore, it is preferable that C is 0.0 Awt% or less, but even if it is less than θ,i wt%, complete solution treatment can improve practical use. It can be made irresistible.

Nb is effective in stabilizing excess carbides,
It also has the effect of strengthening passivation ability. In order to obtain this effect, it is necessary that Nb≧io x c wt, so in this alloy, the content is limited to 1.5 wt% or less.

In addition, in order to stabilize this excess carbide, T
Composite addition of elements such as i, Ta, Zr, and Hf is also effective. To obtain this effect, T1≧! ;
X Cwt%, Ta≧/! ; X Cwt%, Zr≧1
0x c wtchi and Hf≧/! ; X Cwt% is required.

Therefore, in this alloy, Ti is less than □ wt %, Ta, Zr and Hf are each less than □ wt %
% or less. However, for the first and second claims, the formula '/10(%N1))≧<%C), and for the third and fourth claims, '
/, o (%Nb) -+-7, (STg 10' Otsu, (%
Ta) Ten begging, (% ZrJ +7/house%Hfl≧(%C
) shall be satisfied.

As for grass, it improves corrosion resistance and strength as well as MO, but if it exceeds 3 wt%, solution treatment at 220°C or higher is required to make it a uniform solid solution. In this alloy, it is limited to 3 wt or less.

Although the Si content varies depending on the manufacturing method, it is necessary to contain 2.0 wt% or less from the viewpoint of deoxidation, melt flow, etc. In addition, when the amount of Si increases, precipitation of intermetallic compounds is promoted and hardness increases, but corrosion resistance decreases.
．． Limited to 0wt% or less.

Note that, instead of Si, it is also effective to use AJ or the like as a deoxidizing element as much as possible from the viewpoint of manufacturing.

Mn widens the region of the γ phase, stabilizes it, and improves hot workability, but the effective content is less than group wt%.

Next, an example of the current-carrying roll for electroplating according to the present invention will be described based on the results of experiments conducted in comparison with conventional roll materials.

Table 1 shows the chemical components (wt%) of the test materials, and Table 2 shows the
It shows the relationship between electrical corrosion resistance, abrasion resistance, etc., and hardness. In addition, this electrical corrosion resistance and abrasion resistance are as shown in the attached drawings.
2so4, PH7.2, current density ti.

Immerse the test roll 2 in a solution l under the conditions of AAm2,
A brake roll 3 and a drive roll were placed before and after this, and a constant tension was applied through a mild steel stripper to conduct the test. In addition, this corrosion resistance/wear resistance test was conducted based on the roll life ratio (refer to Note 2 in Table 2, after one week of energized use,
Comparisons were made based on the scratches generated on the roll surface due to mechanical factors and the incidence of scratches such as press marks (see Note 3 in Table 2).

As shown in Table 1, the sample material is J-S-SC! as a conventional alloy. S/da and SUS 3/l, and the invention related to the above-mentioned patent application of the present applicant [Electrifying roll for electroplating] Examples of ni?, 10, //, /lI, /A and /7
The alloy was adopted. Examples of the alloy of the present invention include &72g and 9, in which the Co content of the basic component was changed within the limited range of the present alloy. In addition, the basic components with different amounts of Mo and W added are referred to as &/θ, // and 12, and A
The components of g (Co and Ti in the middle (Nb and Ti to stabilize the excess carbide in the middle).

Ta, Ti, Zr and Hf are added together,
Respectively, &/3. /'A,/! r and /A. In Boiled Nos. 17 to 20, W was added to 4 g of ingredients, and Ti was added to 4 g of ingredients.
, Ta, Ti, Zr, and Hf, respectively.

Regarding the amount of corrosion shown in Table 2, the test piece was immersed in a boiling sulfuric acid solution with a concentration of 50%, and the degree of corrosion -2/day was determined.

As can be seen from Table 2, the alloy of the present invention (solution treatment temperature i
, t7o℃) is J Engineering S-8O8/Hiroshi, SUS
3/A and A/, 2, 3, 'I,
Compared to alloys No. 3 and 6, it has better corrosion resistance and high hardness even in wear resistance, so it can prevent scratches and pressure marks on the roll surface caused by mechanical factors.
The wear caused by the mild steel strip is small, the roll surface is less prone to roughness, and relatively the corrosion and wear resistance properties required for energized rolls are obtained. As is clear from the table, the roll according to the present invention has a lifespan ratio of 2 in terms of corrosion resistance and wear resistance compared to the conventional roll using J-K S-8U83/L. The scratch rate is between 13 and 20%, but this is because the hardness of the substrate improves due to the increase in the amount of Co, and the high hardness of Mo in the matrix. This is thought to be because the formation of intermetallic compounds increases the overall hardness and prevents scratches, press damage, etc. from occurring on the roll surface.

Furthermore, the conductivity is J-S-SO8/DA and 5US-p.
3/A electrical resistance of 7 g μΩ- vs. 72 g/II
/μΩ-1, but in practice it is considered acceptable up to 170μΩ-1, so this point is not a problem.

Next, considering Table 2, it can be seen that between &72g and 9 where the content of CO, the basic component, is changed, A9, which is the upper limit of CO, has slightly inferior corrosion resistance, but high hardness can be obtained. Compared to J-Eng S-8US3/6, it has a lifespan that is twice as high, and a scratch rate that is twice as high.

In addition, the life ratio of 7io, ii and /2, in which W is added to each component of A7, g and wo, is J Engineering S-5U.
It showed a value of 27 to 12 times higher than EI3/A, and a value of 2 times higher than 1I for the scratch rate, and the corrosion resistance was improved compared to &72g and 9. , the hardness was also slightly improved, and the effect of the addition of W was recognized.

Next, in order to stabilize excess carbide in the Ag component with the median Co content, Ti, Ta, Ti, Zr, and Hf were added in combination to Nb, respectively.
, /3 and 16 life ratios are J Engineering S-SUS 3
/A is 32 to 3q times higher, and the scratch incidence rate is also /7 to tg times higher than the basic component Jf5. It is almost the same as g.

A /7, 1g, /q and 20 add W,
Ti, Ta, Ti and Zr and Hf in Nb to stabilize excess carbides to median CO content &//
and are added in combination. A/7
The life ratio of +1g, /q and 20 is J Engineering S-8US
, 35 to 37 times higher than that of 7/49, and the wound incidence rate was also 15 to 16 times higher than that of boiled/7/4.
It is almost the same as l.

Effects of the Invention As described above, the basic component of the roll according to the present invention is Ni
-C! r-Mo-Co-C! Although it is a u-Nb type roll, the roll according to the present invention has comprehensive corrosion and wear resistance even under severe corrosion conditions during current-carrying galvanic corrosion and even under severe wear conditions. This is even better than the previous patent application □ filed by the present applicant. Therefore, the current-carrying roll according to the present invention satisfies the current-carrying corrosion resistance conditions PHO, A, which could not be obtained with J-K S-6O8/4 or SUS 3/A.
It can also be used in ~/, B, and is particularly effective when wear is a problem, exhibiting excellent corrosion and abrasion resistance, and also has no electrical conductivity. It can be put to practical use without any problem.

As described above, the present invention provides a current-carrying roll for electroplating that is essential for these properties and is more suitable than that previously proposed in a patent application.

[Brief explanation of drawings]

The figure is an explanatory diagram showing the outline of the electrical corrosion resistance and wear resistance test method. /...Solution; Co...Test roll; 3...Brake roll; Hiroshi...Drive roll; Ri...Mild steel strip.

Claims (1)

[Claims] 1. In weight %: C 0.10% or less Si 2.0% or less Mn 1.5% or less Cr 14% or more and 21% or less Mo More than 16% and 30% or less Cu 0. % to 5.0% Nb 1.5% to Co An energizing roll for electroplating characterized by being made of Ni. 2% by weight Co 0.10% or less Si 2.0% or less Mn 1.5% or less Cr 14% or more and 21% or less Mo More than 16% and 30% or less Cu 0.1% or more and 5.0% or less Nb 1 .5% or less W 3.0% or less Co Contains more than 5% and less than 35% (however, 1/10 (%Nb) ≧ (%C)), the remainder consisting of inevitable impurities and substantially Ni An energizing roll for electroplating characterized by: 3 By weight: C 0.10% or less Si 2.0% or less Mn 1.5% or less Cr 14% or more and 21% or less Mo More than 16% and 30% or less Cu 0.1% or more and 5.0% or less Nb 1 .5% or less Co more than 5% and 35% or less, including Ti 1.0% or less, Ta 1.5% or less,
Contains one or more of the following components: Zr 1.5% or less, Hf 1.5% or less (However, 1/10 (%Nb) +
1/5 (%Ti) + 1/15 (%Ta) + 1/10 (%
1. A current-carrying roll for electroplating, characterized in that Zr) + 1/15 (%Hf)≧(%C)), and the remainder essentially consists of unavoidable impurities and Ni. 4. In weight%: C 0.10% or less Si 2.0% or less Mn 1.5% or less Cr 14% or more and 21% or less MO More than 16% and 30% or less Cu 0.1% or more and 5.0% or less Nb 1.5% or less W 3.0% or less Co more than 5% and 35% or less, including Ti 1.0% or less, Ta 1.5% or less,
Contains one or more of the following components: Zr 1.5% or less, Hf 1.5% or less (However, 1/10 (%Nb)
+1/5(%Ti)+1/15(%Ta)+1/10(
%Zr)+1/15(%Hf)≧(%C)), and the remainder inevitably consists of impurities and substantially Ni.