KR101715618B1 - Metal surface treating agent for descaling - Google Patents

Abstract

The present invention relates to a metal surface treating agent for descaling which is applied to surfaces of metals such as bronze and iron to perform functions of descaling, cleaning, and corrosion prevention, and comprises 1 to 10% by weight of inorganic acid selected from a group consisting of nitric acid, sulfuric acid, hydrochloric acid, and a mixture of two or more thereof, 35 to 50% by weight of 35% hydrogen peroxide, 5 to 15% by weight of benzotriazole, and water as the balance, wherein the metal surface treating agent provides an effect of providing corrosion removal ability of up to 99% or more.

Description

[0001] The present invention relates to a metal surface treating agent for descaling,

The present invention relates to a metal surface treatment agent for deodorization, and more particularly to a metal surface treatment agent for deodorization which is applied to a surface of a metal such as bronze and iron to perform a function of degreasing, cleaning and corrosion prevention.

Corrosion refers to a change in properties of a metal caused by a chemical reaction with a contact material under an environment in which the metal belongs and a reduction in the useful life as a metal. Ore is the most stable material in the world on energy. The metal that the present man has been using continuously since the Bronze Age is an unstable material refined by applying a lot of energy to the ore having the most stable energy state in the natural state. Therefore, the process of oxidation of metal is a natural phenomenon in which the metal itself returns to its most stable state. The metals that we use today are made through thousands of years of reduction, the endothermic process of heating up the oxides that have settled through the exothermic oxidation process in the ground to heat them. This unstable metal in the energy phase dissipates energy through oxidation, which is a heat generation process, and proceeds to return to the original state, that is, corrosion proceeds. This metal generally has a tendency to ionize, which is common in that it gives off electrons. Except for some metals other than platinum and gold, even the corrosion-resistant metals such as silver, copper, and stainless steel, the coating of the corrosion products is dense and prevents passage of air or water, thereby forming a passivation film , But almost all metals can be considered to undergo corrosion.

This is the main cause of the corrosion, as well as the tendency of the metal to return to the ore, as well as the ionization tendency. For example, iron oxide is the result of the most stable state of iron under the environment of water and air. The corrosion principle of metals is determined by the elution of metal ions, and the degree of metal elution depends on how easily the metal is liable to ionize in aqueous solution. That is, metals such as platinum, which have a low tendency to ionization, are known to be stable to oxidation because they emit less electrons and exhibit a higher standard electrode potential and are classified as noble metals. When a metal having a different standard electrode potential is electrically connected in a solution, the potential of the two metals is different, and the electric current (current) is generated due to the potential difference between the two metals. At this time, the lower side potential is eluted ^{(M → M n + + ne} -) of the metal ions occurs a phenomenon takes place on the other side that receives the emitted electrons react at the same time. As a result, only the metal having a low dislocation will be dissolved. This phenomenon exists on the same metal surface, and even on the same metal surface, a local potential difference can be generated due to the arrangement of atoms, the size of particles, the presence of impurities, the presence of defects, and the like. For these reasons, corrosion must occur. That is, oxidation must have four components: anode and cathode to which electrons are transferred, cathode to which ions can move, and electric circuit (return circuit). The anode is the part where the electrons come out. The oxidation occurs chemically, and the cathode absorbs the electrons from the anode, so that the reduction reaction does not occur and the corrosion does not occur.

Types of corrosion are divided into dry corrosion and wet corrosion. A typical type of dry type is that the metal inside the combustion furnace reacts directly with oxygen in a high-temperature gas containing oxygen, so that the corrosion that occurs when the metal is heated to 200 ° C or more in an environment free from moisture is called dry corrosion. The phenomenon of rapid change in weight of a metal sulfided or halogenated at high temperatures is a typical example of a dry process. Wet corrosion is a phenomenon in which iron is oxidized in the air at room temperature due to the phenomenon of corrosion due to the action of moisture in the environment where the metal surface is in contact.

This corrosion can also be divided into frontal corrosion and localized corrosion. The frontal corrosion is the case where the surface of the metal is constantly oxidized and the metal thickness is the same and the same speed is applied. In the natural environment, the frontal corrosion does not occur. In an artificial condition, when the metal is exposed to high-temperature oxygen and corrosion occurs, the entire metal surface is uniformly eroded so that these can be regarded as frontal corrosion. Local corrosion (local corrosion) is, in short, corrosion which proceeds unevenly. (Erosion, pitting), selective corrosion due to alloying elements, intergranular erosion due to the formation of a corrugated form due to natural erosion activity, where the rate of erosion is very different due to the partial irregularity of the hole or groove- And corrosion cracking. Corrosion of zinc (Zn) in the brass, copper (Cu) in the metal, aluminum and aluminum (Al) in the bronze corresponds to the selective corrosion of only one component in the alloy, do. Such a corrosion is also referred to as a parting of an alloy component, and if the percentage of the corrosion-resistant component exceeds a certain value, corrosion occurs suddenly, and the limit is referred to as a "parting limit". Alloys that have been corroded by one component are hardly visible, but sudden destruction due to loss of strength, especially ductility. However, when iron containing aluminum (Al) or chromium (Cr) is oxidized, they may be selectively oxidized to form an oxide film with good adhesion, resulting in a good oxidation resistance. The grain boundary generally tends to corrode in comparison with the crystal elevation, but under certain circumstances, only the grain boundary may selectively corrode, which may result in a severe drop in the strength of the metal body. Such intergranular corrosion is caused by the fact that other phases of the metal structure that are likely to corrode have come to the grain boundaries, and when subjected to improper heat treatment such as stainless steel or aluminum alloy. The season cracking that occurs during the use of brass products is also caused by intergranular corrosion and residual stress in the metal body that is cracked. Cracks occurring as a result of such corrosive action are included in stress corrosion cracking, and the working stress does not change in residual stress or stress in use, and causes cracking. Stress corrosion cracking also occurs in stainless steels, copper alloys such as carbon steel, bronze, aluminum alloys and nickel alloys.

Corrosion in natural environments is divided into atmospheric corrosion, underground corrosion, seawater corrosion, and microbial corrosion. Atmospheric corrosion is a particularly important problem in bridges, roads, buildings, port facilities, transportation facilities and the like, as the exposed surface of the polished iron is exposed to the atmosphere, atmospheric corrosion. Characteristics Corrosion of metal by the atmosphere when no liquid water adheres to the metal surface appears due to the formation of an oxide film, and its thickness is stopped at about 10 to 40 Å, and it can not be discriminated by the naked eye. This is called dry atmospheric corrosion. When water vapor in the atmosphere condenses on the metal surface to form a water film, corrosion starts and is called moist atmospheric corrosion. Wet atmospheric corrosion is called wet atmospheric corrosion when the water surface becomes wet by the increase in the number of attachments and the water film is visually recognized as wet. Atmospheric erosion is affected by the thickness of the water film and the corrosion rate is affected with the passage of time. Therefore, in the case of atmospheric erosion, if a small amount of an alloy component is added to a metal to form a protective layer, corrosion resistance is improved. One of the factors affecting atmospheric corrosion is corrosion when water condenses on the metal surface and becomes water. In particular, atmospheric corrosion of indoor space is caused by condensation water only. Moisture condensation does not occur if the relative humidity is not 100%, but when the humidity is above about 60%, the corrosion rate suddenly increases. The humidity at which the atmospheric corrosion of the metal starts to increase at a relative humidity of the atmosphere is called a critical humidity. Critical humidity is 50 to 50 ppm for iron (Fe), copper (Cu), nickel (Ni) 70%. There are atmospheric corrosion by sulfur oxides (SO _x ), nitrogen oxides (NO _x ), ozone (O ₃ ), carbon monoxide (CO), carbon dioxide (CO ₂ ), peroxides and solid sodium chloride (NaCl). Among these pollutants, the combustion gas that most affects atmospheric corrosion is sulfur dioxide (SO ₂ ), the rate of atmospheric erosion increases in proportion to the amount of sulfur dioxide, and the critical humidity decreases. Sodium chloride sinks to the sea surface in the atmosphere by the waves of seawater, but some are sent inland by the wind to accelerate corrosion by attaching to the metal surface. As the distance from the coast increases, the degree of erosion decreases, but in the case of a sea breeze blowing inland from the sea, the erosion rate increases greatly despite the distance from the coast. The atmospheric temperature is also a very important factor, and the higher the annual average temperature of the place, the higher the corrosion rate. The solar radiation itself does not affect the corrosion of the metal, but the solar radiation shortens the drying time after rainfall. On the other hand, if there is a lot of sunny days, the temperature drops at night and there is a lot of opportunities for condensation, which indirectly affects atmospheric corrosion. In addition, ultraviolet rays in solar radiation cause deterioration of organic coating film, which is one of the important factors for corrosion of painted materials. Since underground corrosion is a mixture of soil particles, water droplets and air, underground corrosion is a type of wet, which is similar to atmospheric erosion due to the thin water film, but it differs from less oxygen supply and dry recurrence . Gas, water, sewage and communication cables, and metal cultural properties. Moisture in the ground dissolves various components, so the property differs depending on the place and acts as a factor affecting corrosion. Particularly important is the amount of oxygen diffusion to the metal surface, which is changed by the porosity of the soil, the water content, and the like. The higher the amount of oxygen, the more accelerated the corrosion. However, when the oxygen is hard to penetrate like the soil, the partial oxygen tendency is likely to occur. The properties of soil affecting are porosity, water content, electrical conductivity, contained salt concentration and pH. When the soil particles come into close contact with the metal surface, the corrosion is reduced because it interferes with the contact of water and oxygen, so that the smaller the porosity of the soil, the less corrosion. However, when the porosity is partially different, oxygen is hardly reachable at a portion having a small porosity, so that the oxygen becomes a positive electrode of the cell and the corrosion is promoted. The diffusion of oxygen in the soil is disturbed when there is a large amount of water, but oxygen diffusion easily occurs if the water content is small and a thin water film is present on the metal surface. The characteristics of seawater corrosion show that corrosion rate is maximized at about 1 to 5% when salt is added to water. Since the salt concentration of seawater is about 3%, seawater acts as acid fire which is corrosive even in natural environment. The composition of natural seawater is extremely complicated and its corrosion can not be represented by simple saline solution but varies depending on the place, but its corrosion is almost similar except for the influence of organisms. However, seawater near the city is highly polluted and contains hydrogen sulfide (H ₂ S), which shows a large difference in the corrosion of the metal, but the corrosion rate increases with the increase of the water flow rate. The corrosion rate of iron is significantly influenced by the distance from the sea surface. When the metal comes into contact with the sea, the splash zone is always the most corrosive, but near the water is the most negative because it is the cathode of the oxygen cell. Since the lower part is always in the seawater, it becomes cathodic, so it is corrosive as it goes downward and it shows maximum near the sea floor. The dissolved oxygen amount decreases linearly to the depth of the sea up to 800m, but if it is higher than that, the dissolved oxygen increases again with the decrease of temperature and salinity. Microbial corrosion refers to microbial corrosion where the product caused by the metabolism of microbes is caused by an indirect cause. Microorganisms do not directly erode metal bodies as a nutrient source, but metabolic products accelerate anodic reactions or cathodic reactions. Corrosion is caused by the microbial propagation itself, and oxygen itself or ionic bomb cells may cause corrosion have. Causative microorganisms are mainly bacteria and fungi. As bacterial corrosion, iron corrosion by iron bacteria and iron and copper corrosion by sulphate reducing bacteria are known, and corrosion of aluminum alloy by bacteria and fungi in air fuel has been reported. Measures to prevent corrosion include plating and painting, use of corrosion-resistant materials, environmental treatment, electrochemical method, coating method, and remodeling method.

Examples of the degreasing method include a physical treatment method and a chemical method in which an oxide is dissolved by immersion or application in a solution of an acid. In the case of difficulties such as building or large structures, it is dependent on mechanical methods that can simultaneously perform degreasing and watering. Physical detachment method is maneuvering method and mechanical method. Among them, manpower method is a method of removing blackening or redness by manpower using wire brush, scraper, hammer and abrasive paper. A representative method by mechanical method is widely used as machining surface by blast process. The spraying method is a sandblast method using short blast, short grit blast, grit blast, marine blast, bottom blast, silica sand, etc. depending on the type and type of particles to be sprayed. . In addition, it can be classified into dry type (low pressure, high pressure), mixed type (Water Blast), liquid pressure type (Hydro Blast), and paper blast by the spraying method. In general, metal decarburization is determined by judging the working conditions such as the shape of the substrate, the thickness of the substrate, the selection of the particles in consideration of the oxide generation state, the spraying speed, the distance, the angle and the reduction of the particles. Chemical degreasing is also called acid pickling, which means dissolving and removing oxides or hydroxides generated on the surface of metal. Compared to the physical degreasing method, there is an advantage of completely eliminating to the inside of the substrate, whereas if the post-picking treatment is bad, the acid is left on the surface of the metal, so reliable cleaning or neutralization is absolutely necessary. Acid pickling is usually called acid pickling, which is carried out in acid solution for a long time to remove dense and thick oxide formed on metal surface in acid pickling. On the other hand, pickling which finishes in a relatively short time is called acid dipping The degree of immersion is judged by the state of the substrate and the degree of corrosion before application.

(1) Removal using acid

The oxide formed on the iron surface is classified into a black oxide, a red oxide, and a non-detectable oxide film which can not be seen by the eye depending on the color. The black oxide, also called scale, is produced by high-temperature heating, which itself has some rust-inhibiting effect, but presents a problem of post-work. Though the scale is different from the oxidizing condition of steel, it forms a thick ferrous oxide layer on the iron crystal surface heated at 575 ° C or more, oxidizing iron is formed on the outer surface, and the intermediate layer is composed of iron oxide. Further, when such a layered oxidation film is further developed, clack enters the iron oxide layer in the oxidation process and the ferric oxide is incorporated therein. And the ferric oxide layer disappears and is formed into the iron oxide layer. The red oxide layer is easily formed as ferrous hydroxide as a function of water and oxygen at room temperature, and it develops to form ferric hydroxide or ferric oxide. Therefore, rust inhibition in iron is to prevent or eliminate the formation or development of red oxides.

Generally, an aqueous solution of sulfuric acid and cold hydrochloric acid is used for descaling of steel surfaces. Its use is determined by the economics and ease of installation of the machine. Acid Dipping is mainly used for the removal of red oxides. Phosphoric acid may be used as a single solution or in combination with hydrofluoric acid and sulfuric acid. It is weak, but does not make rough the base, and it can produce the effect of temporary anti-rusting by creating a very thin rust preventive film on the surface where the rust is removed. Pickling of copper and its alloys is generally carried out using a 10 to 40% aqueous solution of sulfuric acid at about 80 ° C. When the oxide film is strong, a mixed solution of 0 to 30% of silicic acid and 15 to 60% of acetic acid is stirred at room temperature and sufficiently washed. The aluminum and the aluminum alloy are immersed in a 10% sulfuric acid aqueous solution at 50 캜 for several minutes and then in a 5% phosphoric acid solution at 90 캜 for 30 seconds to 5 minutes. Zinc and zinc alloys are immersed in 2 to 3% hydrochloric acid or hydrofluoric acid in strong acids or alkalis. The magnesium is immersed in a chromic acid solution of 18% concentration at 90 to 100 캜. When the oxide film is strong, it is immersed in an aqueous solution of chromic acid and acetic acid by immersing it in an aqueous solution of acetic acid and sulfuric acid at room temperature. As the additive in the pickling, nuclear sydisilylamine, rosin, alcohol and the like are used, and as the inhibitor, pyridine, quinoline, and zerazine are conventionally used. Generally, it is added in an amount of about 0.3 to 0.5% with respect to the acid solution. The temperature and the immersion time of the acid solution are determined in consideration of the adhesion state of the metal oxide, the concentration of the acid solution, the temperature and the environmental condition of the solution. After pickling, it is necessary to wash or neutralize or chemically treat.

(2) Salting out with salt

Scale removal methods using salts are classified into three methods: reduction method, oxidation method, and electrolysis method. Considering maintenance and installation costs, the most effective method is known as reduction and electrolysis. Although the electrolysis method is most useful for descaling, the reduction method is most common and useful because it is known that maintenance cost and installation cost are considerable. The reduction method is to reduce or reduce the metal to a low oxide form by removing scale from a sodium hydroxide (NaOH) solution containing 1.5 to 2.0% of sodium hydride. It is usually done at 370 ° C. When it is quenched, the reduced scales are removed from the metal surface due to the impact of the temperature change, and are then cleaned and completed. The oxidation method uses a solution of 60 to 90% of sodium hydroxide, 7 to 32% of sodium nitrate (NaNO ₃ ) and 1.5 to 6% of sodium chloride (NaCl), and the working temperature is about 480 ° C. Scale metals are rapidly heated in the treatment solution. Scales with a relatively low thermal expansion coefficient and relatively weak scales in the metal cause cracks to occur. The salt penetrates the adhesion surface to oxidize oxides having low oxidation degrees, Change it to water. This action changes the physical unit of the scale and swells to make it more flexible and pore-free. In the quenching process, too, cracks are generated more severely by steam, and the scale is removed. The electrolytic solution requires two tanks for the operation. The temperature of the tank having a similar composition is about 482 ℃ typical composition consists of a 75% sodium hydroxide, sodium chloride + sodium fluoride (NaF) 10%, sodium carbonate _{(Na 2 CO 3) 14%} , 1% other carbonate. In the first tank, a direct current flows, and the salt has a process of oxidizing the scale, and the action of the salt in the second tank and the removal of the high oxidation oxide from the surface of the strip by the release of hydrogen.

The cleaning is to remove the soils attached to the surface of the substrate so as to have the surface shape of the original pure object to be cleaned. The cleaning process consists of a complex system that includes several mechanisms such as wetting, solubilization, and dispersion maintenance. The condition of the cleaning agent having excellent cleaning performance in this system is that the cleaning agent easily adsorbs and penetrates into the contaminant so that the contaminant can easily be detached from the object to be cleaned and has sufficient solubilizing ability to contain many contaminants , The solubilized contaminants must be dispersed rapidly and continuously to the inside of the cleaning agent without re-adhering to the object to be cleaned.

As shown in Fig. 1, the interfacial tension ( _SL ) between the object to be cleaned and the cleaning agent is determined by the Young's equation

? _SL =? _SO +? _LO cos?

cos? = (? _SL -? _SO ) /? _LO

, Where

γ _SL is the interfacial tension between the object to be cleaned and the cleaning agent,

γ _SO is the interfacial tension of contaminants and objects to be cleaned, and

γ _LO is the interfacial tension between the contaminant and the cleaner.

In order to remove contaminants attached to the object to be cleaned, the system should proceed in the direction of increasing the value of the contact angle?. In order to completely remove contaminants, cos θ = -1 when the contact angle is 180 °

cos? = (? _SL- ? _SO ) /? _LO = -1

, The interfacial tension between the object to be cleaned and the cleaning agent should be close to zero (γ _SL = 0) and γ _SO = γ _LO . As a result, it can be explained that the interfacial tension (γ _SO ) between the object to be cleaned and the contaminant becomes equal to the interfacial tension (γ _LO ) between the detergent and the contaminant, and the contaminant is removed from the object to be cleaned. The increase in the contact angle depends on parameters such as the wetting ability of the cleaning agent, the nature of the contaminant, the adhesion state of the contaminant, the cleaning temperature, and the external mechanical energy, and the rate of increase is related to the time required for cleaning have. Therefore, for effective cleaning operations, the formulation and selection of suitable cleaning agents for the target contaminants and an efficient cleaning system should be established.

The cleaning agents that are used both domestically and internationally can be classified into water system, compliance system, hydrocarbon system, alcohol system and chlorine system. The water-based cleaning agent is pure water, such as tap water, or is a cleaning agent mainly composed of water and added with a small amount of acid, alkali, or surfactant. Aqueous detergents are generally more environmentally friendly than other detergents because they are suitable for cleaning inorganic or polar pollutants, which are hydrophilic contaminants, with little or no risk of fire or human health. However, it is difficult to clean the silicone oil or the non-aqueous flux, and measures against corrosion are required depending on the type of the object to be cleaned, and the drying process is slow and the cleaning process time is long. Further, in the case of precision cleaning which is difficult to use industrial water directly, a water refining and supplying facility is required, and in some cases, a wastewater treatment facility is additionally installed. Compliant cleaners are cleaned with undiluted solution without the addition of N-methyl-pyrrolidone (NMP) or glycol ether detergent and water, which are mixed with a considerable amount of water at the time of cleaning, It is divided into hydrocarbons, terpenes and silicones used. NMP and glycol ethers among the compliance cleaners have high cleaning power against flux, wax, grease, etc., though they are expensive and have all the advantages of water-based cleaning agents. Hydrocarbons, terpenes and silicones are excellent in cleaning power and are used without water in the cleaning process, so that it is easy to separate and refine and reuse, and it is possible to use for a long time. However, a cleaning agent is expensive and firefighting equipment is needed for fire prevention. Also, since the compliant cleaner uses water in the course of washing or rinsing like water-based cleaner, anti-rusting and wastewater treatment measures are needed. Ethanol and isopropyl alcohol (IPA) are used as alcohol cleaners. They are relatively toxic, have high polarity and solubility, and are comparatively excellent in cleaning property and good compatibility with non-metallic materials. In particular, IPA is widely used as an extraction solvent in standard ion cleanliness tests due to its excellent solubility. However, alcohol has low boiling point and good volatility and good drying, but it has high flammability due to low evaporation loss and low flash point. In addition, there is a fear of corrosion due to weak cleaning of oil and hygroscopicity. Hydrocarbon cleaner is a petroleum based material such as mineral oil and kerosene. It has low toxicity and low cost. It has excellent cleaning property against pollutants such as grease, tar, wax, etc. It has good compatibility with metals and can be regenerated by distillation . However, since the boiling point is relatively high, the distillation loss is small, but the drying time is comparatively long and explosive, which makes it impossible to degrease the steam and is regulated by the Fire Service Act. The chlorine-based cleaning agent is excellent in cleaning power, has excellent compatibility with metals and nonmetals, is easy to dry, consumes less energy, and can be used with a conventional steam degreasing and cleaning device. However, 1,1,1-trichloroethane (1,1,1-trichloroethane) and CFC-113 in chlorine cleaners are detergents that are used transiently as ozone-depleting substances, There are disadvantages. Among the chlorine cleaners, there are trichlorethylene (TCE) and methylenechloride (MC) which are not regulated in the Montreal Protocol. These detergents have good penetrability and are excellent in detergency and nonflammable, so that steam degreasing is possible. In addition, relatively low operating ratios and very low ozone depletion indices. However, these detergents are classified as hazardous substances and are regulated by the Water Pollution Prevention Act, the Air Quality Preservation Act, and the Industrial Safety and Health Law. When comparing these detergents, the most environmentally friendly and safe detergents can be seen as water / abrasive cleaners. Although a wastewater treatment system is required, the introduction of a recycling process is also feasible.

Since the ultimate goal of cleaning is to remove contaminants attached to the object to be cleaned, it is essential to confirm the source of the contaminant before cleaning and the nature of the contaminant. As for the metal and electric / electronic pollutants, metal parts include hydrocarbon oils, hydrocarbon waxes, hydrocarbon greases, silicone oils, organic waxes, But are not limited to, organic solvents, buffing compounds, mold-release agents, metallic complexes, metal oxides, trace metals, particulates, scale, and salts. Electronic parts include resins, rosins, fluxes, conductive residues, particles, salts, and the like. Particularly, flux is used for facilitating soldering in the process of assembling printed circuit board (Printed circuit board) and printed wiring board (printed wiring board). The soldering flux has various kinds of compositions depending on the type of the printed circuit / wiring assembly substrate to be processed, the soldering process, and the flux residue remover system. Currently commonly used brazing fluxes are rosin-based formulations. The flux is composed of abietic acid, the main component being 10% to 40% organic phase solids, and the remaining 60% to 90% consisted of a solvent and activator to dissolve the solids. The activator of the brazing flux is used to remove oxide layers and contaminants of the metallic lead on the substrate and electronic components, such as diethyl ammonium chloride, butyl amine hydrogen bromide salts, etc. Abietic acid It is used to apply cleaned lead to prevent recontamination before soldering. Therefore, they correspond to contaminants that must be removed after the process. The most common pollutants in oil are cutting oil, non-water-soluble cutting oil for lubricating purpose and water-soluble cutting oil for cooling purpose. Mineral oils, natural oils, emulsions ), Semi-synthetics, synthetics, and the like. Mineral oil is composed of a compound of paraffinic hydrocarbon and naphthenic hydrocarbon, and the lubrication is the main purpose. Paraffin oil has a high viscosity index which is not sensitive to temperature change. It is widely used in engine oil. Naphthene oil does not have high viscosity index but it has good solubility in various kinds of additives. Natural oil can distinguish between animal oil and plant oil. Vegetable oils are mostly composed of saturated and unsaturated carboxylic acids and usually have 12 to 18 carbon atoms. Animal oil is generally a mixture of triglycerides and fatty acids. Natural oils have the advantage of low cost but they are not effective except for boundary lubrication and should be mixed with other kinds of base oil. Emerald oil is composed of naphthenic base oil, surfactant, stabilizer, extreme pressure additive and so on. This emulsion oil is called macro-emulsion and is relatively stable. If the emulsion breaks over time and fine metal chips or other impurities are present, this process is promoted and the dispersed base oil is aggregated, It creates floating oil. In addition, Emerald Oil has the advantage of excellent lubricity by the emulsified oil and also has the cooling function by the water contained. Semi-synthetic oils are micro-emulsions, which are more stable than macro-emulsion oils and contain emulsified oils from 0.01 to 0.2 microns in size and are transparent or translucent. Semi-synthetic oil contains water and is commercially available in the form of micro-emulsion, unlike the emulsion oil composition, and has a cooling effect rather than a lubrication effect because it is diluted 30 to 100 times. Synthetic oils contain no base oils such as mineral oil or fatty oil and are typically composed of polyglycol, polyisobutylene, or poly alpha-olefin. Color is transparent and contains emulsifier, amine, dispersant, antifoaming agent. This synthetic oil is effective where cooling action is required rather than lubrication.

Based on the Material Safety Data Sheet (MSDS), the manufacturer, application, material to be used, cleaning conditions, detergent component, price and toxicity were examined and analyzed. As a result, Spraying / showering, and ultrasonic cleaning. In the case of the concentration, the water-based cleaning agent is used at a concentration of 3 to 10%, and the compliance-based cleaning agent is used as it is as it is. In cleaning, the temperature condition is specified to be used by adjusting the temperature according to the type of contaminants and the adhesion state of contaminants in the range of room temperature to 80 ° C. The analysis of MSDS data showed that the main surfactants of most detergents are relatively sensitive to temperature changes but are not sensitive to pH and water hardness. They have a relatively low CMC compared to ionic surfactants and have excellent environmental properties And some anionic surfactants are used as cosurfactants. In addition, the builder is added. In the case of water content, the water-based detergent contains more than 70% and the compliance-based detergent is generally less than 10%.

Patents related to metal surface cleaning have been filed as patents related to oxide removal, organic removal, and oxidation degradation, and oxide removal and organic removal are in almost the same context. Korean Patent Laid-Open Publication No. 1996-705079 entitled " METAL PROCESSING METHOD USING AN ACID RARE EARTHQUAKE ION CLEANER "(Commer-Walls Scientific & Institutional Research Institute, Korean Patent No. 0447429 "Cleaning Agent Composition" (LG Household & Health Care, Kangseong Outdoor), Korean Patent Publication 2000-005370 "Method for Removing Coating from Metal Surface Using Electrolysis and Cavitation Action" Korean Patent No. 0692603 "Water Soluble Aerosol Cleaning Agent Composition" (Aekyung Industrial Co., Ltd., White Inc.), Korean Laid Open Patent Application 2002-000796 "Composition and Method for Removing Rust and Scale" (KALKON CORPORATION, Korea Patent Publication 2006-0006504 "Degreasing Cleaning Agent for Machinery" (Chang Chang), Korean Patent 0654299 "Antifouling Functional Ceramic Coating Composition" Korean Unexamined Patent Publication No. 2007-0039199 discloses "a surface treatment method of an aluminum material and an aluminum material produced by the surface treatment method" &Quot; (Method of Coating Tin and Tin and Method of Manufacturing the Same) " (Semicreen, Sang Keun et al.), Korean Patent No. 0970133 "Process for the Production of Cycloalkyl Ether Compound" (Xion Corporation, Kindern et al), Korean Patent Publication No. 2014-0087689 (Sechang Chemical Co., Ltd., Kwang Soo et al.), Korean Patent 1359942 "Method for preparing water-based rust inhibitor composition" (Sechang Chemical Co., Ltd., Korea), Korean Patent No. 1343208 "Non- And others).

It is an object of the present invention to provide a metal surface treatment agent which is applied to surfaces of metals such as bronze and iron to perform functions of degreasing, cleaning and corrosion prevention.

The metal surface treatment agent for deodorizing according to the present invention is characterized by comprising 1 to 10% by weight of inorganic acid selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid and a mixture of two or more thereof, 35 to 50% by weight of 35% hydrogen peroxide, 15% by weight, and water as a remainder.

The inorganic acid may preferably be nitric acid.

The metal surface treatment agent may further comprise 0.1 to 5% by weight of nickel chloride (NiCl ₂ ) based on the total weight of the metal surface treatment agent.

The metal surface treatment agent may further comprise 0.1 to 5% by weight of iron chloride (FeCl ₃ ) based on the total weight of the metal surface treatment agent.

The metal surface treatment agent may further comprise 0.1 to 5% by weight of iron nitrate (Fe (NO ₃ ) ₃ ) based on the total weight of the metal surface treatment agent.

The metal surface treatment agent may further comprise 0.1 to 1% by weight of copper chloride (CuCl ₂ ) based on the total weight of the metal surface treatment agent.

According to the present invention, there is provided a metal surface treatment agent which is applied to surfaces of metals such as bronze and iron to perform functions of degreasing, cleaning and corrosion prevention, and this metal surface treatment agent has an effect of providing corrosion removal ability of not less than 99% have.

Fig. 1 is a diagram schematically showing the principle of cleaning.
FIGS. 2 to 11 are photographs of the surface of each specimen, which is corroded by acid treatment of hydrochloric acid, nitric acid and sulfuric acid, using the metal surface treatment agents of Examples 1 to 10 according to the present invention.

Hereinafter, specific embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The metal surface treatment agent for deodorizing according to the present invention is characterized by comprising 1 to 10% by weight of inorganic acid selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid and a mixture of two or more thereof, 35 to 50% by weight of 35% hydrogen peroxide, 15% by weight, and water as a remainder.

The inorganic acid is selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, and a mixture of two or more thereof, and provides an effect of removing (degasifying) and cleaning the metal surface. The inorganic acid is preferably used in an amount within a range of 1 to 10% by weight based on the total weight of the metal surface treatment agent, and if it is contained in an amount of less than 1% by weight, On the other hand, if the content exceeds 10% by weight, the surface of the metal may be excessively eroded and the surface may be deteriorated.

The hydrogen peroxide solution is preferably dilute hydrogen peroxide at a concentration of 35%, which is applied to the metal surface to enhance the cleaning effect of the metal surface. The hydrogen peroxide solution is preferably used in an amount within a range of 40 to 50 wt% based on the total weight of the metal surface treatment agent, and when it is used in an amount of less than 40 wt%, the cleaning effect may be deteriorated, If it is used in an excess amount exceeding 50% by weight, it may cause a corrosion effect on the metal surface to lower the surface of the metal surface.

The benzotriazole functions to provide a corrosion inhibiting effect on the metal, and is preferably used in an amount within a range of 5 to 15 wt% based on the total weight of the metal surface treatment agent, and may be used in an amount of less than 5 wt% There may be a problem that the corrosion inhibiting effect becomes insufficient. On the other hand, when it is used in excess of 15 wt%, there may be a problem in safety against human body and environment.

The inorganic acid may be preferably nitric acid, and when nitric acid is used, the corrosion-removing effect is most excellent.

The metal surface treatment agent may further comprise 0.1 to 5% by weight of nickel chloride (NiCl ₂ ) based on the total weight of the metal surface treatment agent.

The metal surface treatment agent may further comprise 0.1 to 5% by weight of iron chloride (FeCl ₃ ) based on the total weight of the metal surface treatment agent.

The metal surface treatment agent may further comprise 0.1 to 5% by weight of iron nitrate (Fe (NO ₃ ) ₃ ) based on the total weight of the metal surface treatment agent.

The metal surface treatment agent may further comprise 0.1 to 1% by weight of copper chloride (CuCl ₂ ) based on the total weight of the metal surface treatment agent.

Nickel chloride, iron chloride, iron nitrate, and copper chloride exhibit a metal etching effect to help remove oxides.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described.

The following examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention.

Example  1 to 10

A metal surface treatment agent according to the present invention was prepared in the composition shown in Table 1 below (unit: g).

Example One 2 3 4 5 6 7 8 9 10 Deionized water 500 500 500 500 500 500 500 500 500 500 Hydrochloric acid 50 50 50 Sulfuric acid 50 50 50 nitric acid 50 50 50 50 35% hydrogen peroxide 43 43 43 43 43 43 43 43 43 43 Benzotriazole 10 10 10 10 10 10 10 10 10 10 FeCl ₃ One One One 0.5 0.5 0.5 0.5 Fe (NO _{3) 3} One One One NiCl ₂ One One One 0.5 0.5 0.5 0.5 CuCl ₂ 0.5 0.5 0.5 D.W. 396 396 396 396 396 396 395.5 395.5 395.5 396 SUM 606 607 608 608 609 610 611.5 612.5 613.5 614

Experimental Example

The specimens were made of bronze of 21% tin and 99.96% of iron plate, which were immersed in 1.0M hydrochloric acid, 1.0M nitric acid and 1.0M sulfuric acid for 2 weeks. The metal surface treatment agents of Examples 1 to 10 were used as the treatment solutions. After the treatment with the metal surface treatment agent, the final optimum composition was confirmed after observing the surface level. Other experimental conditions are as follows.

1. Reagents and equipment

It is also possible to use an acid such as hydrogen peroxide, ammonium fluoride, citric acid, copper chloride, ethylenediamine tetraacetate-2 sodium salt, mono ethanol amine, Phosphoric acid, sodium gluconate, sodium metasilicate and 1,2,3-benzotriazole are commercially available from OCI, Inc., Seoul, Korea. Buthyl diglycol and potassium hydroxide used reagents from Junsei, Tokyo, Japan. Iron chloride, Ethyl alcohol, Acetone, Diethanol amine, Nickel chloride hexahydrate and Iron nitrate are available from Aldrich, St. Louis, Mo. (Aldrich) were used. Sulfuric acid, hydrochloric acid, and nitric acid were used as the reagents of Daeshwa Gold Co., Ltd., Siheung, Gyeonggi-do, Korea. All other reagents used reagents above analytical grade. Ultrasonic cleaner was manufactured by using Sehan electools of Seongnam-si, Gyeonggi-do, Korea. The microscope was made by Nikon SMZ-745T model of a multinational company.

2. Preparation and Corrosion of Specimen

Bronze and iron pieces were used for the specimen, and 21% of the tin bronze was ordered and ordered from Taejungbong Organic Village, Daegu, Korea. As the iron piece, a steel piece made by POSCO of Pohang city, Korea was used. Each specimen was cut to a size of 40.0 mm x 40.0 mm x 4.0 mm, immersed in acetone for 1 day, and then the surface was again rinsed with gauze. The specimens were immersed in 50 ml of sulfuric acid, hydrochloric acid and nitric acid at a temperature of 25 ℃ for 2 weeks, and 10 ml of each acid solution was added at 3 - day intervals. The state of the corrosion was confirmed. After a maximum of 20 days, each specimen was subjected to ultrasonic cleaning of 28 kHz with distilled water for 5 minutes, and then used as a finished sample.

3. Preparation of treatment liquid

As shown in the above examples, the treatment liquid was prepared by mixing nitric acid, copper chloride, nickel nitrate, and iron nitrate based on 95% sulfuric acid, 35% hydrogen peroxide, and benzotriazole. The pH was in the range of 1.2 to 1.9 depending on the amount of the additive and the composition ratio. The solution was prepared by varying the presence or absence of components and the composition ratio, and the final optimum composition was confirmed by observing the surface of the solution.

After surface treatment, the surface was observed, and the surface was observed, photographed and recorded while varying the kind of treatment liquid, treatment time, treatment temperature, and the result. (Example 4), Fig. 6 (Example 5), Fig. 7 (Example 6), and Fig. 8 (Example 7), Fig. 9 (Example 8), Fig. 10 (Example 9) and Fig. 11 (Example 10).

As a result of analyzing the above-mentioned embodiments, it was confirmed that corrosion of the above Examples was efficient for removing corrosion. Particularly, Example 6 showed the best corrosion removal from both iron and copper, so that 99% .

(Without reference numerals)

Claims (6)

Characterized in that it further comprises 1 to 10% by weight of nitric acid as an inorganic acid, 40 to 50% by weight of 35% hydrogen peroxide water, 5 to 15% by weight of benzotriazole and water as a balance and 0.1 to 5% by weight of nickel chloride. Metal surface treatment agent for degreasing.
delete delete The method according to claim 1,
Wherein the metal surface treating agent further comprises 0.1 to 5% by weight of iron chloride based on the total weight of the metal surface treating agent.
The method according to claim 1,
Wherein the metal surface treating agent further comprises 0.1 to 5% by weight of iron nitrate based on the total weight of the metal surface treating agent.
The method according to claim 1,
Wherein the metal surface treating agent further comprises 0.1 to 1% by weight of copper chloride based on the total weight of the metal surface treating agent.

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