KR102206147B1 - High durability plated body - Google Patents

Abstract

In the present invention, the highly durable body to be plated as described above, the highly durable body to be plated, has hardness, abrasion resistance, corrosion resistance and chemical resistance equal to or higher than STS 316L through anodization treatment, and anodization to replace STS 316L material It provides an indicator of treatment technology, and based on this, it can be used not only in ships, shipbuilding, but also in the entire industry.It can be used as a substitute for STS 316L material, but welding work is possible with a general welding rod, and subsequent painting work is required even after dismantling. It has the advantage of not being. In addition, it relates to a highly durable plated body having an advantage of enabling productivity and cost reduction by replacing expensive STS 316L.
In the highly durable body to be plated according to an embodiment of the present disclosure, in the highly durable body to be plated, a plated body is formed by plating a base iron or aluminum, and anodizing treatment on the plating body to obtain the hardness of the body to be plated, Increases wear resistance, corrosion resistance and chemical resistance.

Description

High durability plated body

The content disclosed in this specification relates to a highly durable body to be plated, and in particular, to increase the hardness, abrasion resistance, corrosion resistance, and chemical resistance of the body to be plated through anodization treatment, and use this body to be used for petrochemical product carriers. Construction of chiefs for high place work in the cargo hold area or ballast tank area of all ships, or by replacing the expensive STS 316L used throughout the industry in a similar form, securing cost competitiveness and dismantling while welding work is possible with ordinary welding rods. It relates to a highly durable plated body that does not require subsequent treatment such as painting work even afterwards.

Unless otherwise indicated herein, the content described in this section is not prior art to the claims of this application, and inclusion in this section is not admitted to be prior art.

In general, some large ships, including petrochemical product carriers, manufacture a number of large blocks and assemble them to manufacture a cargo hold.The shape has a reverse slope that inclines toward the center as the upper part of the cargo hold goes upward. Have.

As the final process of manufacturing the cargo hold, special coating is performed for the protection of the cargo in the cargo hold and the anticorrosion of the hull. In the reverse slope formed at an elevated position, the multi-layered part is used to facilitate movement and work of workers for painting. You will install the chieftain.

At this time, considerable effort and time are required in the process of installing and disassembling the chief in performing work such as welding. In particular, STS 316L, which is a non-corrosive material for cargo, is applied because the members to be welded are not removed after welding work. . However, the material cost is relatively high, and a special welding process using a welding rod exclusively for STS 316L is required when welding for the installation of the chief in the work section, resulting in a problem of cost increase. In addition, even after dismantling the chief, a subsequent painting work is required on the part of the chief piece, so there is a problem in that the efficiency according to the working cost and working time is lowered.

As a prior art for solving the above problems, there is Korean Patent Publication No. 10-1516203,'Ship cargo hold system chief'. The prior art includes a lower chieftain module including a lower chieftain plate and a plurality of lower chieftain pipes supporting the lower chieftain plate; Arranged on the module installation surface on which the upper chieftain plate and the upper chieftain module and the lower chieftain module are installed, and have a plurality of upper chieftain pipes that support the upper chieftain plate and are assembled with the lower chieftain pipe. And an assembly position guide jig for guiding the assembly position of the lower chieftain module, and the assembly position guide jig is fixed to the module installation surface at regular intervals, and the lower chieftain pipe of the lower chieftain module A technology in which a plurality of pipe connection guide rods to be connected, and a through part for weight reduction is further formed in the inside of the jig body, and a plurality of cut-out notches for cutting the jig body are further formed around the through part There is a feature to disclose.

Another prior art is the Republic of Korea Patent Publication No. 10-2015-0021830'Ship building chief structure and its construction method'. The prior art includes a plurality of coupling holes formed in the walls to be spaced apart at predetermined intervals along the longitudinal direction of the walls forming the ship block; A support member that is detachably inserted and coupled to the coupling holes formed in the neighboring walls so that neighboring walls can be connected through, and a chieftain plate that is detachably coupled to the support member so as to be adjacent to the walls. There is a feature that discloses the technology being constructed. In addition, the steps of penetrating and coupling a plurality of support members to the coupling holes formed in the walls so that adjacent walls forming the ship block can be connected through; Mounting a chieftain plate on the upper part of the support member so as to be adjacent to the walls forming the ship block; And a step of fixing the chieftain plate mounted on the upper part of the support member to the support member so as to be detachably coupled using a plurality of fixing members.

Another prior art is Korean Patent Application Publication No. 10-2013-0042194'Special coating method for PC ships'. The similar prior art is the first step of constructing the cargo oil tank block of the PC ship in the preceding design step, but not performing the painting work on each block; A second step of transferring the cargo oil tank block to the dock; A third step of mounting and assembling the cargo oil tank block in the dock; The fourth step of performing blasting and painting work on the assembled block includes, and the fourth step includes painting work at once so that there is no difference in painting quality between the joints and the surface of the assembled block. There is a feature to disclose a technique characterized by implementing.

However, the above-described prior art secures cost competitiveness by replacing STS 316L, which is an expensive material, when constructing a chief for high place work in the cargo hold area of petrochemical product carriers and ballast tank areas of all ships, and welding work with general welding rods. It is possible to do this, and there is a regret that the practical problem of not requiring subsequent painting work even after the dismantling of the chieftain has not been considered.

On the other hand, in order to secure corrosion resistance, a plating method of aluminum is used for general steel.In the above plating method, it is difficult to secure the same or higher rigidity, corrosion resistance, chemical resistance, and abrasion resistance of STS 316L. It is practically impossible to cope with STS 316L, which is used as a material for, and use it.

Through anodizing treatment, we intend to provide a highly durable plated body with hardness, abrasion resistance, corrosion resistance and chemical resistance equal to or higher than STS 316L.

We provide an index of anodizing technology to replace STS 316L material, and based on this, we intend to provide a highly durable plated body that can be used not only in ships, ships, but also in the entire industry.

It can be used as a substitute for STS 316L material, but welding work is possible with a general welding rod, and it is intended to provide a highly durable plated body that does not require subsequent painting work even after disassembly.

As it can replace expensive STS 316L, we want to provide a highly durable plated body that can reduce productivity and cost.

In the highly durable body to be plated according to the embodiment, in the highly durable body to be plated, a plated body is formed by plating the base iron or aluminum, and the plating body is anodized to obtain the hardness, abrasion resistance of the body to be plated, Increases corrosion resistance and chemical resistance.

According to an embodiment, a plasma electrolytic oxidation treatment technique is applied to the object to be plated for the anodization treatment.

According to an embodiment, the diffusion heat treatment temperature for increasing the surface hardness of the object to be plated is 450 to 1200°C.

According to an embodiment, the plated body is welded to a steel structure for construction of a chief for high place work inside and outside the ship.

0.5~30 g/L이되, 상기

는

이온이 첨가되도록 하고, 상기

의 소스(source)는

,

,

,

및 그 수화물 형태로 단독 또는 혼합물로 이루어진다.According to an embodiment, the electrolyte for the plasma electrolytic oxidation treatment is Sodium Aluminate (SA) 1 to 30 g/L,

0.5~30 g/L, but above

Is

Allow ions to be added, and the

The source of is

,

,

,

And in the form of a hydrate thereof, alone or as a mixture.

According to an embodiment, the electrolyte solution further includes a colorant, and the colorant is Sodium Molybdate or Sodium Tungstate, and a mixture thereof, and is composed of 0.01 to 20 g/L.

According to an embodiment, the control parameters of the processing apparatus for the plasma electrolytic oxidation treatment are voltage, current, soft start, run time, frequency, and duty cycle.

According to an embodiment, the plasma electrolytic oxidation treatment is possible for aluminum (Al), aluminum plating, steel, and a combination of steel and aluminum.

이되, 상기 x는 0 또는 자연수이다.According to an embodiment, the metallurgical combination of the steel and the aluminum is oxidized to form a passivation layer, and the passivation layer is

However, the x is 0 or a natural number.

The highly durable object to be plated as described above has the advantage of having hardness, abrasion resistance, corrosion resistance, and chemical resistance equal to or higher than STS 316L through anodizing treatment.

It provides an index of anodizing technology to replace STS 316L material, and has the advantage that it can be used not only in ships, ships, but also in the entire industry.

It can be used in place of STS 316L material, but welding work is possible with a general welding rod, and it has the advantage that no subsequent painting work is required even after disassembly.

As it can replace expensive STS 316L, it has the advantage of reducing productivity and cost.

1 to 3 are views for explaining an electrolyte solution according to the present disclosure.
4 to 13 are experimental sites for realizing a highly durable plated body according to the present disclosure
Drawing to show the teeth.
14 is a diagram showing an experimental setup for a PEO experiment.
15 is a diagram showing the standard reduction potential.
16 is a diagram for describing a DUTY value in a PEO process.
17 is a view for showing a configuration for making an electrolyte.
18 is to monitor the electrical properties of the electrolyte through the treatment apparatus of the present disclosure
A drawing showing a table for.
19 is a diagram showing a correlation value according to an adjustment variable of a processing device.
20 is a view showing electrical characteristics according to the concentration of SA+1P electrolyte.
21 is a diagram showing characteristics according to frequency among electrical variables.
22 is a diagram showing the sensitivity of an electrolyte composition.
23 is a diagram showing an experiment for finding an optimum value of an electrolyte composition.
24 shows the voltage deviation while recording the value of the duty change during PEO processing
For drawings.
25 is a graph showing a correlation between duty and voltage.
26 is a diagram showing characteristics according to the amount of SA at the optimum value of 1P 3.5g/L.
27 is a table showing an optimal electrolyte composition according to the experimental results of FIG. 26;
28 shows the results of the cross-sectional hardness of the specimen by applying the electrolyte conditions and electrical parameters.
The ticket to show.
29 is a graph showing the correlation between frequency and hardness.
30 is a table showing the results such as the highest hardness according to the electrical conditions of the test piece.

Advantages and features of the present invention, and a method of achieving them will become apparent with reference to the embodiments described below in detail together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in a variety of different forms, only the present embodiments are intended to complete the disclosure of the present invention, and the general knowledge in the art It is provided to completely inform the scope of the invention to those who have it, and the invention is only defined by the scope of the claims. The same reference numerals refer to the same elements throughout the specification.

In describing embodiments of the present invention, if it is determined that a detailed description of a known function or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted. In addition, terms to be described later are terms defined in consideration of functions in an embodiment of the present invention, which may vary according to the intention or custom of users or operators. Therefore, the definition should be made based on the contents throughout this specification.

In the highly durable body to be plated according to an embodiment of the present disclosure, in the highly durable body to be plated, a plated body is formed by plating the base iron or aluminum, and the plating body is anodized to provide hardness and wear resistance of the body to be plated. , To increase corrosion resistance and chemical resistance.

To this end, in the present disclosure, a plasma electrolytic oxidation treatment technique is applied for anodizing treatment on a plated body.

The electrolyte solution for the plasma electrolytic oxidation treatment of the present disclosure,

0.5~30 g/L이되,Sodium Aluminate(SA)1~30 g/L,

0.5~30 g/L,

는

이온이 첨가되도록 하고,remind

Is

Allow ions to be added,

의 소스(source)는

,

,

,

및 그 수화물 형태로 단독 또는 혼합물로 이루어질 수 있다.remind

The source of is

,

,

,

And in the form of the hydrate may be formed alone or in a mixture.

Such, the present disclosure may further include a colorant in the electrolyte.

At this time, the colorant of the present disclosure is Sodium Molybdate or Sodium Tungstate, and a mixture thereof, and is preferably made of 0.01 to 20 g/L, but is not limited thereto.

In this disclosure, the control parameters of the processing apparatus for the plasma electrolytic oxidation treatment include voltage, current, soft start, run time, frequency, and duty cycle, It is not limited thereto.

In particular, in the present disclosure, the plasma electrolytic oxidation treatment is possible for aluminum (Al), aluminum plating, steel, and a combination of steel and aluminum, and the metallurgical combination of steel and aluminum is oxidized to form a passivation layer. and,

이되, 상기 x는 0 또는 자연수인 것임에 의해 실현가능하며, 이에 국한되는 것은 아니다.The passivation layer

However, it is possible to realize that x is 0 or a natural number, but is not limited thereto.

The diffusion heat treatment temperature for increasing the surface hardness of the plated body of the present disclosure is made within the range of 450 to 1200°C, whereby the plated body is made of iron for the construction of the chief for high place work inside and outside the ship. It is possible to be welded to the structure, and based on the above, it is possible to replace STS 316L, thereby enabling grafting and application according to the above technical idea throughout the industrial field in which STS 316L is used.

An electrolyte solution and a processing apparatus for the plasma electrolytic oxidation treatment according to the present disclosure as described above will be described.

First, the electrolyte solution for plasma electrolytic oxidation treatment of the present disclosure may be considered as follows.

1. Electrolyte requirements

-Good electrical conductivity

-No erosion of aluminum material

-Good oxygen activity at the positive electrode

-Remnant heavy metal ions and eluted metal ions must be removed

-Good electrolyte wettability

-Open system-Consideration of reactivity with carbon dioxide in the atmosphere (liquid pollution)

-Easy to manage and economical

2. Electrolyte depletion (exhaustion) model

-Gas generation by electrolysis

)(

)

-Pyrolysis of the anode overheated part

Nonionic surfactant Ethylene Oxide/Propylene Oxide imposed type

-Evaporation by temperature increase of electrolyte

-

-Open system-Reaction with CO2 in the atmosphere to form a product

_

-Exhausted by metallurgical reaction

-

-Eluted metal and heavy metal ion aggregation exhaustion

3. Estimated electrolyte depletion

-Moisture evaporation and exhaustion increase pH

소진으로 액비중 감소-

Reduction of liquid specific gravity due to exhaustion

-Increased surface tension due to exhaustion of surfactant

4. One point of electrolyte management

-Insufficient electrolyte: replenish water

-pH measurement: LiOH supplementation

보충-Weight reduction:

supplement

-Increased surface tension: supplemented with surfactant

-Filter filter clogged: Replace filter

: 용존산소측정-

: Dissolved oxygen measurement

: 제품의 표면 거칠기 및 표면관찰-

: Surface roughness and surface observation of products

The configuration of the electrolyte solution as described above is as shown in FIG. 1, and in this case, the mixture ratio of the electrolyte solution is as shown in FIG. 2.

,

등 구성 변화 및 첨가시 영향으로 전해액은 달라질 수 있으므로 이에 한정되는 것은 아니다. 상기된 바에 따른 전해액 약품 소요는 도 3과 같다.However, Sodium silicate, Potassium silicate,

,

Since the electrolyte may be changed due to changes in the composition and effects of addition, it is not limited thereto. The electrolyte chemical requirement according to the above is shown in FIG. 3.

The electrolyte management method as described above is as follows.

1. Electrolyzer Flushing procedure

end. Water supply to the filtration tank

I. After sufficient water supply to the filtration tank (a head formed above the filter)

All. Air vent check on the inlet side

la. Run the cooler's circulation pump

hemp. Water supply to prevent overflow in the filtration tank

bar. If the electrolyzer (inside) is overflowed, the rate of water supply to the filtration tank is reduced

four. Stop water supply to the filtration tank when 2/3 of the head is full

Ah. Circulate continuously for more than 1 hour and flush.

character. Disposal of water after completion of flushing (sewerage)

2. Drug injection procedure

end. Addition of surfactant (75g) and LiOH (600g) to storage tank (300liter)

I. Operate the stirrer until the surfactant is sufficiently dissolved and LiOH is completely ionic (hydration reaction complete), and the water temperature is checked.

All. Stabilizes until cooling to room temperature when the water temperature stops rising

la. Stir sufficiently after adding Li-Silicate (12Kg)

hemp. pH measurement and pH measurement, specific gravity, and viscosity recording using a hydrometer and viscometer

bar. If the pH is less than 12.8, add LiOH in 5g increments.

four. Cooling outlet v/v OFF

Ah. Completed electrolyte transferred to the electrolyzer (inside) using the Aircon drain pump

character. If the electrolyzer (others) is sufficiently filled with electrolyte,

car. Electrolyzer-filtration tank v/v ON, filtration tank cooler v/v ON, cooling outlet v/v ON

K. Cooler circulation pump operation

Get on. Completed transfer of electrolyte in storage tank

wave. Cool down by running the cooler (20 degrees) circulation.

3. Procedure for managing electrolyte during use

Storage before starting and after use When reusing electrolyte

A. Filter tank front valve OFF

B. Circulation pump ON

C. Completed transfer of electrolyte in the filtration tank

D. Circulation pump OFF

E. Circulation pump rear valve OFF

F. Solution amount measurement: Electrolyzer (inside) (outside) head match? Replenish water if necessary

G. Circulation pump rear valve ON

H. Filter tank front valve ON

I. Pump circulation

J. Measurement of liquid viscosity in liquid specific gravity: If insufficient, supplement 500g of Li-Silicate

K. If pH measurement is less than 12.8, supplement LiOH 5g unit

L. Observation of filtration tank filter drainage while the circulation pump is running: If necessary, stop and replace

4. Electrolyte discharge (waste liquid replacement and electrolyte replacement) Procedure

A. Install a tray under the 10A discharge v/v in the front of the cooler.

B. Install 1~2 Aircon drainage pumps inside the tray.

C. Connect the discharge side tube of the drainage pump to an extra storage tank (300liter).

D. Cooler outlet v/v OFF (filter tank overflow prevention)

E. Electrolyzer-filtration tank v/v and filtration tank-cooler v/v ON

F. Open 10A discharge v/v little by little and fill the tray with electrolyte.

G. Operate the Aircon drain pump.

H. Perform the transfer by finely adjusting 10A v/v.

I. After completion of transfer work of electrolyzer (other) and filtration tank

J. Filter tank-cooler v/v OFF and cooler outlet v/v ON.

K. After transfer of all electrolyte

L. Connect the drain pump discharge tube to a separate (washing liquid) container

M. Repeat operation D~I for cleaning the electrolyzer (outside) and filtration tank and J~K for cleaning the electrolyzer (inside)

N. Repeat the operation of M several times to complete the cleaning operation.

O. Replace with a new filter.

5. Equipment required for electrolyte management

A. Liquid specific gravity relay

B. Thermometer

C. pH meter

D. Viscometer

E. Infrared thermometer (measures the temperature of the energized part)

F. Surface electron microscope, dissolved oxygen analyzer (required when adding phosphoric acid or hydrogen peroxide later)

The treatment apparatus for realizing the plasma electrolytic oxidation treatment using the electrolytic solution of the present disclosure as described above, that is, the PEO apparatus will be replaced with the drawings of FIGS. 4 to 13. At this time, in the drawings of the present disclosure, the equipment configuration diagram of the treatment apparatus, the electrolytic cell unit configuration conceptual diagram, the electrolytic cell configuration, the electrolytic cell grating configuration, the electrolytic cell plate configuration, the filtration tank configuration, the electrolytic cell chamber configuration, the anode jig, the heat treatment furnace, etc. The specifications (names, specifications, reference numerals, materials, standards, features) are also shown in detail, so that they can be sufficiently understood from the drawings, so they are not described as separate descriptions.

Hereinafter, based on the foregoing, the PEO experiment of the present disclosure is as follows.

The experimental variables are as follows.

A. Current density (A/dm2). 5 A/dm2, 10 A/dm2, 15 A/dm2

B. Frequency (Hz). 100Hz, 200Hz, 300Hz

C. Duty (%). 40%, 60%, 80%

D. Power-on time (Min). 30min, 60min, 90min

At this time, the experiment setting is as shown in Fig. 14, and the experimental evaluation is 1 to 3, ... … After setting the optimal PEO variable by evaluating a total of 27 sets of 79~81, it is executed on the chief piece and additionally evaluates each material property.

These results are summarized as follows according to the present disclosure.

이온을 받아드려 표면에서 산화 즉,

가 부동태 코팅되어 표면 전압을 상승케 하여 플라즈마 양극산화를 가능하게 한다. 전해액에 공급은,1. As a result of plasma electrolytic oxidation under various conditions, the LiOH + Li-silicate base electrolyte has no data comparable to that of NaOH + Na-silicate or KOH + Na-silicate base electrolytes found in various references, so relative evaluation is impossible. , Referring to the standard reduction potential of FIG. 15, it shows superior properties than Potassium (K), but it is considered that it is worth evaluating in terms of price versus performance. In addition, the function of LiOH, KOH, NaOH alkaline electrolyte is limited to the role of electric transmission, and the higher the reduction potential, the smaller resistance is applied to the electrolyte, reducing the temperature rise of the electrolyte. And the role of silicate on the treated surface

It receives ions and is oxidized on the surface, that is,

Is passively coated to increase the surface voltage to enable plasma anodization. Supply to the electrolyte,

1.1 Ultrafine silica (nano ~ several tens of μm) and anionic surfactant (+ antifoam) are used to disperse in electrolyte to give negative charge to the silica surface

1.2 Colloidal silica added

1.3 Add Meta-silicate

1.4 Water glass: (Na, K, Li)-silicate input

There are methods such as, etc., and it is not limited to the above as it may vary depending on the economic aspect and the relationship of its utility.

The effect of introducing a silicone surfactant is advantageous in PEO treatment by lowering the energy of the interface. In the initial test, the relative surface condition was very good under the same conditions after adding one specimen without surfactant.

2. Variables that can be adjusted in the power supply in the plasma electrolytic oxidation process include voltage, current, soft start, run time, frequency, and duty, and the effects on the process are summarized below.

2.1 Voltage: This is the most important performance indicator for power supply devices. In particular, in low duty conditions, the spark discharge voltage is higher than that in the high duty condition, so the plasma electrolysis voltage is also higher. In the process, the maximum voltage, which is the limit of the device, is fixed at 700V.

2.2 Current: Current densities: 4.4, 8.8, 13.2, 17.6, 22, 26.4 A/dm2 The higher the value is, the more advantageous it is, but there is a limit due to overheating of the titanium electrode. In this experiment, it is limited to 20A per electrode contact without overheating. The design of the titanium jig is important

2.3 Soft Start: Power supply protection function by preventing power supply, and 30 seconds per 5 A/dm2 of current density is sufficient

,

등의 복합적 반응을 일으키며, 표면의 경우는

층을

으로 변화시킴.2.4 Run Time: There is a relationship inversely proportional to the current density, but the lower the current density, the more time it takes for spark to occur, so the actual plasma discharge time or the time must be set in relation to the plasma strength. In the case of this aluminum plating, the limit for the thinnest plating thickness at the top and corner of the product due to the hot-dip aluminized process is 20 minutes at 4.4 A/dm² 50% duty condition. Further proceeding causes an oxidation reaction at the same time as the part exposed to the iron base and the silicate of the electrolyte. In other words, due to the high heat of plasma, the exposed area

,

It causes complex reactions such as, and in the case of the surface

Layer

Changed to.

2.5 Frequency: It is the least influential factor in PEO quality, less affects the coating thickness or coating properties, only affects the surface roughness. Compared to the plasma treatment conditions observed during the experiment at 100, 200, and 1000Hz, the plasma duration becomes shorter as the frequency increases and the frequency of simultaneous plasma generation also increases, and as a result of the dense treatment, the surface roughness is affected. It is difficult to observe. If the surface roughness or surface condition is adjusted later, it is believed that nano-micro composite surface formation + hydrophobic coating = superhydrophobic surface can be realized. In the case of high frequency (10A 1000Hz), tremendous noise is observed during work. Consideration of the work environment or high frequency disturbances in surrounding electronic products (especially electronic watches) should be sufficiently considered.

2.6 Duty: This is the factor that most affects the PEO process. As a result of testing at 10, 20, and 50% duty, the quality was the best at low duty and the spark generation time was also the shortest. However, as illustrated in the graph shown in FIG. 16, in the case of 10% duty by raising the spark generation voltage, the power supply specification reaches 700V for a short time, and the constant voltage mode is converted to a constant current mode, so that the current value becomes 10A -> 6A As it is lowered, the limit of current density is limited to about 5 A/dm2. The optimum duty according to the power supply is judged to be 10~20%, and additional experiments to find the optimum value must be carried out, and a power supply of at least 1000V specification is recommended for future production applications.

,

의 복합적 반응 및 표면의

경우 으로 반응이 지속되나 표면의 mill scale이 완벽하게 제거되지 않은 부분에서 그 정도가 심했다. 따라서 현재의 공법의 HAD steel의 PEO의 경우 도금 전 전처리 과정에서 모서리 chamfering 및 소둔처리나 Shot Blasting 처리를 실시하여 표면의 mill scale 제거 및 모서리 부위의 round 형상을 유지시키는 것이 필요하며, 도금 후 공정간 제품의 이동시 도금표면의 mechanical damage를 없애는 노력에도 불구하고 상하부의 도금두께 단차를 없애는 것은 공정상 불가능하다. 도금두께가 얇은쪽을 기준으로 PEO 공정변수를 맞춘다 하여도 품질안정화를 위한 공정관리상 불가능하다 사료된다.3. In the case of hot dip aluminized steel (HAD steel) PEO, as shown above, in the case of the corners due to the base iron rising from the thin film plating area during the PEO process due to the deviation of the plating thickness.

,

Of complex reactions and surface

In some cases, the reaction continued, but the degree was severe in the part where the mill scale of the surface was not completely removed. Therefore, in the case of PEO of HAD steel of the current method, it is necessary to remove the mill scale of the surface and maintain the round shape of the corner by performing edge chamfering and annealing treatment or shot blasting treatment in the pre-treatment process before plating. Despite efforts to eliminate mechanical damage on the plating surface during product movement, it is impossible to eliminate the difference in plating thickness of the upper and lower parts in the process. Even if the PEO process parameters are adjusted based on the thinner plating thickness, it is considered impossible due to the process management for quality stabilization.

)로 용해제거 공정을 위한 전압강하와 전압상승 후 spark 발생 이라는 PEO공정 변수가 발생하였으며, 700V, 15A(13.2A/d㎡), 50% duty의 경우 개시전압(186V)→최저전압(164V, 12분)→전압회복(186V, 21분)→spark 발생전압(470V, 25분)→PEO 진행→CC mode 전환(700V, 14A, 36분)→PEO진행→PEO코팅터짐(전압강하)→PEO진행 반복의 형식으로 PEO공정이 구성되었다. 코팅 터짐 부위는 mill scale 표면과 경계에서 주로 이루어 졌다. 그리고 저 duty(10%)에서는 전압상승 후 spark 발생 이라는 PEO공정 변수가 발생하지 않았으며, 전해산세만 계속 진행되었다.4. HAD + Diffusion treatment (750°C 1Hr and 880°C 5Hr) PEO was tried as an alternative. Iron (Fe) is oxidized and removed from alloy components through initial electrolytic oxidation, which is completely different from existing aluminum PEO or HAD steel PEO.

), a PEO process variable such as voltage drop for the dissolution and removal process and spark generation after voltage rise occurred, and in the case of 700V, 15A (13.2A/dm2), 50% duty, starting voltage (186V) → lowest voltage (164V, 12 minutes) → voltage recovery (186V, 21 minutes) → spark generation voltage (470V, 25 minutes) → PEO progress → CC mode change (700V, 14A, 36 minutes) → PEO progress → PEO coating burst (voltage drop) → PEO The PEO process was constructed in the form of progress iteration. The rupture of the coating was mainly made at the mill scale surface and boundary. And at low duty (10%), the PEO process variable, such as spark generation after voltage increase, did not occur, and only electrolytic pickling continued.

therefore,

4.1 Plating of specimen with mill scale completely removed

4.2 Diffusion treatment

4.3 Starting voltage → voltage drop → voltage recovery process at high duty

4.4 It is necessary to proceed with PEO treatment at low duty and consider the results.

It is believed that it is possible to develop a new technology (non-skid surface treatment with high corrosion resistance) according to the above results.

의 source가 충분하여 추가의 Aluminum source가 필요 없다. 하지만 HAD steel PEO의 경우 추가의 Aluminum source의 필요성이 대두되었다. 수산화알루미늄

의 경우 강알칼리용액(pH 11이상)에서

로 잘 용해되며, 표준환원전위도5. There is a need to develop an alternative electrolyte, and the core of which is to replace silicate → aluminum, and it is considered that there is a possibility of solving the substrate exposure and thin film area as Alumina rather than Silica. Silicate was substituted with AlOH, and the base metal It was non-aluminum, and the reason is that

As the source of is sufficient, there is no need for an additional aluminum source. However, in the case of HAD steel PEO, the need for an additional aluminum source emerged. Aluminum hydroxide

In the case of strong alkali solution (pH 11 or more)

It dissolves well with the standard reduction potential

One)

2)

의 source가 되어 줄 수가 있다.More efficient on the anode surface

It can be a source of.

Therefore, it is considered to be a solution to the problems raised in the above 4. and 5. in electrolyte development.

On the other hand, FIG. 17 is a diagram showing a configuration for making an electrolyte solution, and the results of the execution of the plasma anodic oxidation electrolyte development are summarized as follows by creating an electrolyte solution based on the configuration of the table shown in FIG. 17.

,

의 복합적 반응 및 표면의 경우

으로 반응이 지속되어 좌측의 사진처럼 도금 두께가 얇은 쪽부터

로 추정되는 scale이 누적되어 제품적 관점에서 아무리 성능이 좋아도 부가가치가 없어진다. 그리고 공정간 제품의 이동시 도금표면의 mechanical damage를 없애는 노력에도 불구하고 상하부의 도금두께 단차를 없애는 것은 공정상 불가능하다. 도금두께가 얇은쪽을 기준으로 PEO 공정변수를 맞춘다 하여도 품질안정화를 위한 공정관리상 불가능하다 사료된다. 따라서 상기의 공정변수 및 human factor를 극복 가능한 신규의 전해액이 절실히 필요하게 되었다. 규산염이온이 아닌 알루미늄산염, 붕산염, 수산염, 인산염, 질산염, 크롬산염 등으로 대치가 가능한지 실험을 무수히 실행한 결과 KOH or NaOH, LiOH 등 전기전도도를 좋게하는 물질로 Sodium Aluminate

로 규산염을 대신하여 1인산

, 또는 2인산

으로부터

(인산이온)을 적용하여 알루미늄뿐 아니라 알루미늄 도금시편 그리고 도금이 되지 않은 bare steel에도 PEO가 가능한 전해액 개발을 완료하였다.In the case of hot dip aluminized steel (HAD steel) PEO, in the case of a corner due to the variation in plating thickness in the electrolyte solution (KOH or NaOH, LiOH + sodium silicate) in the related literature

,

In the case of complex reactions and surfaces

The reaction continues, starting with the thinner plating as shown in the picture on the left.

As the estimated scale is accumulated, the added value disappears no matter how good the performance is from a product point of view. And, despite efforts to eliminate mechanical damage on the plating surface when moving products between processes, it is impossible to eliminate the difference in plating thickness on the upper and lower parts of the process. Even if the PEO process parameters are adjusted based on the thinner plating thickness, it is considered impossible due to the process management for quality stabilization. Therefore, there is an urgent need for a new electrolyte solution capable of overcoming the above process parameters and human factors. Sodium Aluminate is a material that improves electrical conductivity such as KOH, NaOH, LiOH, etc. as a result of numerous experiments to see if it can be replaced with aluminum acid salt, borate, oxalate, phosphate, nitrate, chromate, etc. instead of silicate ion.

Monophosphate in place of silicate

, Or diphosphate

From

(Phosphate ion) was applied to complete the development of an electrolytic solution capable of PEO for not only aluminum, but also aluminum-plated specimens and unplated bare steel.

전해액 개발과정 및 결과 SA: 10g/L + 1P: 1.5g/L의 전해액에서 그 가능성을 발견함.Sodium Aluminate(SA) +

Electrolyte development process and results SA: 10g/L + 1P: We found the possibility in an electrolyte of 1.5g/L.

At 5A, 1800sec, 700Hz, duty 10% condition, spark start voltage 550V, maximum 607V was recorded.

5A, 2700sec, 700Hz, 10% duty condition, up to 620V,

5A, 3600sec, 700Hz, 10% duty condition, up to 633V,

Under conditions of 10A, 900sec, 700Hz, duty 10%, spark start voltage: 580V, maximum 700V, converted to constant voltage mode due to equipment limitations.

Under conditions of 10A, 1800sec, 700Hz, duty 10%, spark start voltage: 580V, maximum 700V, converted to constant voltage mode due to equipment limitations.

Under the above conditions, the starting voltage (about 440V) was higher than that of the conventional KOH+silicate electrolyte, and about 200V was recorded than the starting voltage (about 380V) of sodium carbonate + silicate, which recorded the lowest starting voltage. Charge + cooling cost) Efforts have been made to overcome this.

를 첨가하여 양극산화를 촉진하여 silica scale문제 극복연구2. Hydrogen peroxide to overcome the above problems

A study on overcoming the silica scale problem by promoting anodic oxidation by adding

: 100cc/L의 전해액 조성으로 시험결과

분해에 의한 냉각기 내부의 배관에서 산소기포가 발생하여 배관을 폐쇄시키는 문제가 발생하였다.KOH: 3g/L + K-silicate: 30g/L + 35%

: Test result with 100cc/L electrolyte composition

Oxygen bubbles are generated in the piping inside the cooler due to decomposition, causing a problem of closing the piping.

의 공급원으로서 안전성이 좋은 sodium percabonate

를 이용연구And

Sodium percabonate with good safety as a source of

Research using

에 PEO 촉진 현상은 느낄 수가 없었다. 그리고

의 분해 안전성은 많이 개선이 되었으나 다음날 냉각기를 가동 후 냉각기 내부 배관에서 분해 산소가 배관을 폐쇄하여

첨가 시도는 부정적으로 마무리 되었다.Sodium percabonate: 20g/L + K-silicate was applied to lower the starting voltage to 380V.

I could not feel the PEO promotion phenomenon. And

The decomposition safety of the refrigerator was improved a lot, but after the chiller was operated the next day, decomposition oxygen in the pipe inside the chiller closed the pipe

The addition attempt ended negatively.

3. Diffusion heat treatment of aluminum plated specimen at 870°C for 1 hour + KOH: 10g/L + Li-silicate: 20g/L electrolyte using electrolytic solution at 20A, 60% duty, 700Hz, 1200sec, 433V spark The silica was coated on the aluminum diffusion specimen at the starting voltage and the highest voltage of about 580V, put it in a furnace heated to 760°C and heat-treated for 10 minutes, and then air-cooled to obtain a high hardness silica coating.

가장 적합한 후보군으로 올리고 이를 최적화 하는 방향으로 개발 진행을 결정하였다.4. Sodium Aluminate (SA) + by synthesizing the previously mentioned PEO experimental variables and the development experiences of 1 to 3 above.

The development progress was decided in the direction of raising it as the most suitable candidate group and optimizing it.

5. SA: 10g/L + 1P: 1.5g/L To monitor the electrical properties of the electrolyte, PEO was performed as shown in the table below.

Water temperature 20°C, frequency 700Hz, D: duty cycle(%), C: Current(A), RT: Run Time(sec), SV: Spark voltage(V), ST: Spark Time(sec), MV: Maximum Voltage(V)

On the other hand, referring to FIGS. 18 to 19, in FIG. 18, there may be an error (a section in which voltage fluctuations rapidly changes) due to a time delay from observing sparks to reading the instrument panel when recording the data. The overall correlation is shown in Fig. 19.

6. Investigate the electrical characteristics according to the SA + 1P electrolyte concentration

Duty 10% 700Hz, C:5A, RT:1800sec, water temperature 30°C

Referring to FIG. 20, electrical characteristics vary according to the composition of the electrolyte, and the SV is low, ST is fast, and MV is low.

7. Investigate the characteristics according to frequency among electrical variables.

Electrolyte: SA 10g/L + 1P 1.5g/L, C: 10A, D: 60%, water temperature: 30°C

Referring to FIG. 21, except for 1000Hz, as the frequency increases, SV decreases, ST decreases, and MV shows irrelevant characteristics.

8. To investigate the sensitivity of the composition of the electrolyte, the following experiment was conducted.

Referring to FIG. 22, the above result is that the golden composition of SA+1P exists, and a close experiment is required.

9. PEO was tested on unplated steel.

Simultaneously insert a non-plated steel specimen and an aluminum plated specimen into the electrolyzer,

700Hz, 10A per piece, total 20A, 1800sec, 60% duty, at 15°C water temperature

Steel specimen SV: 380V ST: 100sec; For aluminum plated specimens, PEO is performed at SV: 432V, ST: 135sec and final voltage 551V.

In other words, we found an important point that PEO treatment is possible for Aluminum, Aluminum plating (metallurgical defect), Steel alone or Steel + Aluminum assembly at the same time.

,

,

조합 전해액에 대해 실험을 실시 하였으나, 특징할 사항이 없었다.10. Borax +

,

,

Experiments were conducted on the combination electrolyte, but there were no features to be characterized.

11. PEO was conducted for the pre-verification of weldability for 4 real chief pieces (2 10mm plating holders for the welded part, 2 total plating).

Electrolyte SA 10g/L + 1P 1.5g/L, 30A 1800sec, 100Hz, at 60% duty condition

SV 430V, ST 144sec, MV 623V, and the plating holding product of the weld was in the same condition as general mild steel welding, but for the entire plating product, stable welding was possible after ARC dissolved alumina at the start of welding.

12. An experiment was conducted to find the optimum value of the electrolyte composition.

Referring to FIG. 23, the appropriate amount of 1P was 3.5 g/L, and the ST and the highest voltage within the standard deviation were recorded.

13. Equivalent voltage by duty

As the duty value increases, the voltage drop occurs.

The value of the duty change during PEO processing is recorded below, and the deviation is predicted to be within about 3%, as shown in FIG. 24.

To FIG. 25, considerations in terms of power rates in the above values are

Considering that the power rate = time * current * average voltage, the lower the duty, the more advantageous, but the higher the voltage, the more the electrolyte will overheat, so considering the energy required for cooling, the energy efficiency is expected to be the most in the 20-40% range.

14. The characteristics according to the amount of SA were tested at the optimum value of 1P 3.5g/L in item 12.

Referring to FIG. 26, the optimum electrolyte composition is estimated as shown in FIG. 27 according to the above experimental results.

15. Check the estimated electrolyte solution

As a result of requesting cross-sectional hardness by producing a specimen by applying the following electrolyte conditions and electrical parameters

SM: Sodium Molybdate Na2MoO4·2H2O

That is, as shown in FIG. 28.

The result is inferred as follows.

A. In low current (5A) short time (30 minutes), the higher the duty, the higher the hardness

B. Low current (5A) For a long time (60 minutes), high hardness is obtained at a duty of 30% or more.

C. Medium current (10A) In a short time (30 minutes), high hardness is obtained at a duty of 30% or more.

D. In the medium current (10A) for a long time (60 minutes), there was no increase in hardness compared to the short time.

E. High current (15A) In a short time (30 minutes), the maximum value is obtained at a low duty 30%.

F. The effect of increasing hardness is good at high concentration (SA 20g/L + 1P 3.0g/L) compared to low concentration (SA 10g/L + 1P 1.5g/L).

G. The effect due to frequency is

As shown in the graph in FIG. 29, the maximum value can be obtained at 370 Hz.

H. The highest hardness exists in 15A treatment within 30 minutes.

16. Reinforcing the above conclusion and inferring the result,

As shown in Figure 30,

A. SA 15g/L + 1P 3.5g/L + SM 5g/L (colorant) Optimized electrolyte is confirmed.

B. The optimization frequency is confirmed as 370Hz.

C. After this treatment, tempering treatment at 2/3 current for 1/2 hour will increase the hardness.

D. Looking at the electrical characteristics of the PEO treatment of the 0217-1 specimen showing the highest hardness,

When soft start 60 seconds is applied, spark is generated at 370V in about 40 seconds (10A), and we observed that the PEO progresses at 410V in 50 seconds (12.5A), and the maximum voltage of 15A 1200sec, maximum voltage 582V and tempering 10A 600sec is 574V.

The disclosed contents are only examples, and various changes can be made by those of ordinary skill in the art without departing from the gist of the claims claimed in the claims, so the scope of protection of the disclosed contents is It is not limited to the examples.

In the present invention, the highly durable body to be plated as described above, the highly durable body to be plated, has hardness, abrasion resistance, corrosion resistance and chemical resistance equal to or higher than STS 316L through anodization treatment, and anodization to replace STS 316L material It provides an indicator of treatment technology, and based on this, it can be used not only in ships, shipbuilding, but also in the entire industry.It can be used as a substitute for STS 316L material, but welding work is possible with a general welding rod, and subsequent painting work is required even after dismantling. It has the advantage of not being able to. In addition, it relates to a highly durable plated body having an advantage of enabling productivity and cost reduction by replacing expensive STS 316L.

In the highly durable body to be plated according to an embodiment of the present disclosure, in the highly durable body to be plated, a plated body is formed by plating a base iron or aluminum, and anodizing treatment on the plating body to obtain the hardness of the body to be plated, Increases wear resistance, corrosion resistance and chemical resistance.

Claims (9)

In the highly durable plated body,
Plating is performed on base iron or aluminum to create a plated body, and anodizing the plated body,
A plasma electrolytic oxidation treatment technique is applied to the object to be plated for the anodization treatment,
The electrolyte of the plasma electrolytic oxidation treatment is
Of the total weight of 302.675 kg, lithium-silicate (Li-Silicate) 12 kg; 0.6 kg of lithium-hydroxide; 0.075 kg of sulfactant; It consists of 290 kg of water,
The control parameter of the treatment apparatus for the plasma electrolytic oxidation treatment is a current density of 5-15 A/m ² ; Frequency 100Hz-300Hz; Duty 40-80%; Highly durable plated body, characterized in that the energization time is 30 minutes-90 minutes.
delete The method according to claim 1,
The high durability plated body, characterized in that the diffusion heat treatment temperature for increasing the surface hardness of the plated body is 450 to 1200 ℃. The method according to claim 1,
The plated body is a highly durable plated body, characterized in that the plated body is welded to a steel structure for construction of a chief for work inside and outside the ship.
delete The method according to claim 1,
The electrolyte solution further comprises a colorant,
The colorant is Sodium Molybdate or Sodium Tungstate, and a mixture thereof, and a highly durable body to be plated, characterized in that consisting of 0.01 to 20 g/L.
delete The method according to claim 1,
The plasma electrolytic oxidation treatment is possible for aluminum (Al), aluminum plating, steel, and a combination of steel and aluminum. The method of claim 8,
The metallurgical combination of the steel and the aluminum is oxidized to form a passivation layer,
The passivation layer

However, the highly durable plated body, characterized in that the x is 0 or a natural number.

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