TWI441961B - Hydrophobic conduction appliance with coating chromium carbide ceramic electroplating layer and manufacturing method thereof - Google Patents

Description

Hydrophobic conductor coated with chromium carbide-based cermet plating And its making method

The present invention relates to a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer and a method for fabricating the same, which is a method for coating a chromium carbide-based cermet on a surface of a tool by using a trivalent chromium plating method for hydrophobicity. Use of conductive tools, such as medical electrosurgical scalpels or battery plates.

The chromium carbide ceramic or chromium carbide ceramic has excellent mechanical strength and chemical stability, and has high hardness, high melting point, and good corrosion resistance, and is disclosed on the substrate as disclosed in Japanese Patent No. JP2010248595. A layer of 45-55wt.% chromium carbide and 30-40wt.% cobalt (Co) can still have good wear resistance under the use condition of 1000 ° C; Japanese Patent JP2003155538 discloses that tantalum carbide can be used for extremely hard A mold or a mold core which can be used for an optical glass, such as a ruthenium carbide, is disclosed in Japanese Patent No. JP 60264332 and JP2005231932; therefore, a chromium carbide-based cermet compound is mainly used as a reinforcing medium for a composite material and a protective layer in a corrosive environment.

The prior art can be applied to a method for preparing a chromium carbide layer, including a wet method and a dry method, and a dry method such as plasma-assisted chemical deposition. Method, vapor deposition method, high energy micro-arc technology, high temperature carbonization, low temperature carbonization, physical vapor deposition (PVD), powder bath, etc.; Taiwan patent TW I350220, PCT application number JP00/01342 (China application number CN00800144.8 Or Chinese patent application number CN200610068500.4 discloses that the cutting tool or mold is cemented or sintered into chromium carbide particles, which can significantly extend the service life of the tooling; Taiwan Patent TW I297365 discloses the use of chromium carbide powder material to produce tools by sputtering. Chromium-containing chromium-based alloy material; Taiwan Patent Publication No. TW200523219 discloses a multilayer film mold comprising a chromium carbide ceramic layer on a glass molded mold core; Taiwan Patent Publication No. TW200719986 uses a radio frequency sputtering method to deposit chromium carbide and the like Carbon film for making molds with high hardness and high wear resistance, good corrosion resistance, low friction coefficient and long service life; US Patent No. 5,960,762 uses chemical vapor deposition (CVD) to form chromium carbide (Cr) -C) surface layer; these chromium carbide layers prepared by the dry method have uniform distribution of chromium carbide, excellent corrosion resistance and wear resistance, but these are Process techniques are difficult to avoid complicated, expensive equipment or high-temperature high energy consumption and other shortcomings, and Cr-C due to the conductive surface layer is poor, not the hydrophobic conductive tool.

Different from the dry method, the wet method mainly uses a plating method to plate a layer of Cr-C on the surface of the workpiece. For example, Japanese patent JP59178155 coats the chromium carbide layer with a hexavalent chromium plating method on the casting mold to increase the resistance of the mold. mill. However, the traditional electroplating chrome mainly uses hexavalent chromium (Cr ⁶⁺ ) chromic acid, which is very toxic (about 100 times more than trivalent chromium). It is a very serious carcinogen. After chrome plating with hexavalent chromium The generated wastewater and products cannot be naturally degraded and eliminated in nature. When the concentration of hexavalent chromium in the air or drinking water exceeds the limit, it will cause perforation of the diaphragm in the nose, vomiting, damage to the intestines and kidneys, and in the organism. It accumulates in the body and has a long incubation period. Governments around the world have enacted relevant laws and regulations on hexavalent chromium plating to gradually limit the use of hexavalent chromium and reduce its emissions. However, trivalent chromium (Cr ³⁺ ) plating has low toxicity and is comparable to hexavalent chromium plating in both decorative and functional properties. Therefore, the use of trivalent chromium plating as an alternative to traditional hexavalent chromium plating has advantages in both industrial applications and environmental protection.

Since the toxicity of trivalent chromium plating is much lower than that of hexavalent chromium plating, it is the direction actively developed by the industry today, such as Yu-Qin Wang and Shu-Hong Cao in Electroplating and Environmental Protection Journal 2005 25 In the third phase, the "A Study of Formic Acid-Methanol-Urea Trivalent Chromium Plating System" was proposed to electroplate chromium with a trivalent chromium solution with formic acid-methanol-urea as an additive. The method can improve the cauterization phenomenon of the trivalent chromium electroplated chromium plating layer, and can gradually replace the electroplating of hexavalent chromium; and, as disclosed in Taiwan Patent Publication No. TW200911699, an alkaline chromium trioxide plating layer is used to form a chromium hydroxide plating layer.

For example, Chinese Patent Publication No. 200810142997.9 discloses the addition of a carbon nanotube (CNT) to a chromium chloride-containing trivalent chromium plating solution, and a chromium having a thickness of more than 50 μm, a flat surface, and a strong bond can be prepared by electroplating. - Composite plating of carbon nanotubes; Japanese patent JP04115421 uses chromium carbide to be added to the electroplating bath to co-deposit chromium carbide and metal on the surface of the metal to be plated; Liu Yuxi: Study on the plating of trivalent chromium-carbon alloy In 2005, electroplating was used to form a carbon alloy plating layer; for example, SCKwona, M. Kima, SU Parka, DYKima, D. Kima, KSNama, Y. Choib in Surface and Coatings Technology Volume 183, Issues 2-3, 2004 Presented the paper: "Characterization of intermediate Cr-C layer fabricated by electrodeposition in hexavalent and trivalent chromium baths", using a current density of 27.5 A/dm ² and formic acid as an additive, although electroplating can grow amorphous microstructure (amorphous type microstructure ) of Cr ₂₃ C ₆ and Cr ₇ C ₃ chromium carbide layer; however, the prior art growing out of the chromium carbide layer, the content of carbon is too low, about 5 ~ 8At% ( Ratio of the number of sub-atomic percent), poor conductivity, it is difficult to be applied to the conductive means a conductive requirements.

The conductive tool can be applied to various antistatic tools, nozzles for welding, battery electrodes, electrode patches, dental tools or scalpels in medical tools, and the like, such as Japanese Patent JP2006-000521, which uses chromium carbide materials for medical purposes. If you use a medical electrosurgical scalpel (Electrosurgical instrument, electrocautery), to achieve tissue cutting, coagulation, desiccating, fulgurating, biocompatibility and other functions, As shown in Fig. 1, when the current generator 92 is used to generate a radio frequency (Radio Frequency, RF) of 100 kHz to 10 MHz (or RF ablation (RFA)), the frequency is 40 kHz to 1250 kHz. The cable 94 and the electrosurgical scalpel 95 enter the human body, and a circuit is generated by the returning guard 92 and the return cable 91. The electrosurgical scalpel 95 generates high heat through the body impedance in the human tissue, thereby destroying the tissue. The purpose of cutting and coagulation. Another application is for electrocautery, electrocautery, similar to RF treatment RFA, which uses electric current to generate heat from a heater. The heat can be directly transmitted to the surrounding tissue through a heat-conductive scalpel, and the tissue is heated and cauterized; Patent Application Nos. 200920190181.3 and 200710133601.X disclose the use of an electrically conductive scalpel for resection of internal organs of the human body and for hemostasis of bleeding organs. However, the electrosurgical scalpel 95 of the prior art is often coated with Teflon (or fluorinated hydrocarbons), a chromium nitride film (CrN, Cr ₂ N), etc., among which Teflon has The problem of fluorine-containing toxic gas is released, while the general chromium nitride film is mainly CrN, but the surface contact angle of CrN is 78°, which is hydrophilic, and it is easy to cause sticking when cutting tissue; while the Cr ₂ N film is closer to hydrophobicity. The surface contact angle is about 101°, but the Cr ₂ N film is not easily produced. Due to the poor conductivity of Teflon and Chromium Nitride films, there are limitations on the use of electrosurgical scalpels. U.S. Patent No. 5,801,110 discloses the use of a dry method for spraying a chromium carbide ceramic onto a dental or surgical instrument to increase the gripping ability and wear resistance, but still due to spraying. The chromium carbide ceramic used is relatively expensive to manufacture, has a low yield, and has insufficient surface density, poor electrical conductivity and hydrophobicity, and has limitations in use.

In the application of contact electrode material, for example, Taiwan patent TWI372484 discloses a fuel cell bipolar plate using a trivalent chromium passivation film, but since the passivation film can make the fuel cell bipolar plate conductive, the passivation film is dense. Insufficient corrosion resistance is not good; due to the conductive and corrosion-resistant properties of chromium carbide materials, as in the earlier European patent EPO0227973, a 250 μm chromium carbide material was infiltrated into a porous substrate using a vacuum interrupter. Electrode; US Published Patent US 20070117003 uses electron beam evaporation to attach carbides to stainless steel plates to produce conductive, stable and hydrophobic electrodes for use in fuel cell bipolar plates; The dry manufacturing method is expensive, requires high temperature, and the substrate is deformed by high temperature. The abstract of the paper published by Shen Shiyu in "Study on Trivalent Chromium Electroplating on Fuel Cell Metal Bipolar Plates" in 2011 reveals the use of trivalent chromium plating method, and in 2011, Xie Yuxuan's "Electroplating Chromium-Carbon Alloy for Fuel" Abstract of the published papers on the mechanism of battery bipolar plates It is disclosed that a chromium-carbon plating layer is plated on the surface of a metal material by using a trivalent chromium plating method to increase the corrosion resistance of the battery bipolar plate, but the hydrophobic properties of the bipolar plate are still unresolved.

Because the dry method produces a hydrophobic conductive tool using a high temperature process, in addition to tempering due to high temperature and damaging the hardness of the tool itself, the dry method is expensive to manufacture, and it is impossible to produce a high carbon content conductive layer and a highly hydrophobic Cr. -C layer, the lower compactness causes the tool substrate to be easily dissolved, resulting in poor biocompatibility. Therefore, how to make a high-carbon content hydrophobic conductive tool chromium carbide plating layer by electroplating wet method, in addition to having good surface hardness, wear resistance and corrosion resistance, it has conductivity (thermal conductivity) and is hydrophobic. Sexuality to apply to hydrophobic conductive tools, this is an urgent problem to be solved.

In view of the above problems in the prior art, the main object of the present invention is to provide a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer, the hydrophobic conductive tool comprising a tool substrate and a surface layer coated on the tool substrate a chromium carbide-based cermet plating layer; the tool substrate may be part of the hydrophobic conductive tool, for example, a tool base or a cut surface of a hydrophobic conductive tool as a tool base for plating a chromium carbide-based cermet layer The material of the tool substrate may be selected from one of the following two groups or a combination thereof: (1) conductive material group: conductive ceramic, iron, stainless steel, copper, chromium, nickel, silver, gold or alloy thereof One or a combination thereof; (2) a group of non-conductive materials: one of plastic, ceramic, glass or a combination thereof is coated with a conductive layer by electroplating or electroless plating, the conductive layer being selected from the group consisting of iron, copper, chromium, nickel , silver, gold or alloy thereof; for example, when the tool substrate is a conductive material, iron, stainless steel, copper, chromium, nickel, silver, gold or an alloy thereof may be used, or a conductive ceramic may be used as the tool substrate; Tool substrate is non-conductive material One of plastic, ceramic, glass or a combination thereof is coated with a conductive layer on the surface of the tool substrate by electroplating or electroless plating, such as a layer of iron, copper, chromium, nickel, silver, gold or alloy thereof (for example, using no Electroplating nickel) is not limited; the chromium carbide-based cermet plating layer is composed of chromium element and carbon element, and is an amorphous phase structure which is electroplated to the surface of the tool substrate, and the composition thereof includes at least One or a combination of six carbon trioxide (Cr ₂₃ C ₆ ), three carbon trichrome (Cr ₃ C ₂ ) or three carbonized seven chromium (Cr ₇ C ₃ ); for plating chromium carbide-based cermet The layer of the tool substrate has hydrophobicity and electrical conductivity. The chromium carbide-based cermet plating layer has a carbon content of more than 15 At%; in terms of conductivity, the specific resistance is 100 mΩ. Below mm ² /m (inclusive) (hereinafter the specific resistance unit is abbreviated as mΩ), in terms of hydrophobicity, the contact angle of pure water at 25 ° C is greater than 94 degrees and less than 120 degrees.

The thickness of the chromium carbide-based cermet plating layer can be selected by the plating time to control different conductivity, hardness and corrosion resistance. For precision hydrophobic conductive tools, the average thickness range can be selected from 0.5 μm to 15 μm.

Further, for non-limiting applications, the hydrophobic conductive tool coated with the chromium carbide-based cermet plating layer is more corrosion resistant, and its linear polarization corrosion current is below 1×10 ^-5 amps; or It has surface hardness and wear resistance, and its surface hardness is 1500Hv or more.

A further main object of the present invention is to provide a method for electrochemically forming a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer, which solves the problem that the prior art Cr-C tool has poor conductivity and hydrophobicity. Good question. The method comprises the following steps: S1: providing a tool substrate, the tool substrate comprises a conductive layer; if the tool substrate is a conductive material, the conductive layer is provided, if the tool substrate is non-conductive (such as non-metal) The surface of the tool substrate is electrolessly plated or plated with a conductive layer or coated with a conductive layer; in practical applications, the tool substrate is a hydrophobic conductive tool to be plated or a part thereof; S2: configuration of trivalent chromium The electroplating solution, the trivalent chromium plating solution comprises: an aqueous solution formed by a trivalent chromium salt, a chelating agent and an additive; the trivalent chromium salt is first dissolved in water, and then a chelating agent and an additive are added; wherein the trivalent chromium salt can be The sulfuric acid trivalent chromium salt and the chloric acid trivalent chromium salt are selected, wherein the sulfuric acid trivalent chromium salt is a compound formed by trivalent chromium (Cr ⁺³ ) and sulfate (SO ₄ ^-2 ). Such as chromium sulfate (Cr ₂ (SO ₄ ) ₃ ); the chloric acid trivalent chromium salt is trivalent chromium (Cr ⁺³ ) and chloride ion (Cl ^- ), perchloric acid ion (ClO ₄ ^- ) or a combination thereof of a compound, such as chromium (CrCl ₃ .6H ₂ O) chloride, chromium perchlorate, chromium _{(Cr (ClO 4) 3)} ; the chelating agent based optional Organic acids and salts thereof; the additive is selected one of an inorganic acid or ammonium salts or combinations thereof; mole per liter, the ratio of trivalent chromium plating solution of trivalent chromium (Cr ⁺³⁾ to carbon element ratio of 1 : between 5 and 1:40; S3: electroplating, the tool substrate is placed as a cathode, and immersed in a trivalent chromium plating solution; electroplating is performed under a plating temperature condition and a current density condition. In the electroplating, the trivalent chromium plating solution is simultaneously stirred; after a predetermined time, a chromium carbide-based cermet plating layer is formed on the surface of the conductive layer of the tool substrate; and the formed chromium carbide-based cermet plating layer is formed. It consists of at least chromium and carbon, and is an amorphous phase structure in which the content of carbon is in the range of 15 At% or more, and its specific resistance is 100 mΩ or less, which makes it have good electrical conductivity and is pure at 25 ° C. The contact angle of water is greater than 94 degrees to make it have good hydrophobicity.

Moreover, in step S3, the current density condition ranges from 10 A/dm ² to 30 A/dm ² ; wherein the plating temperature condition is an operation set temperature of 50 ° C or less, and the plating temperature condition is ± of the set temperature Within 3 °C. The carbon element content of the chromium carbide-based cermet plating layer is calculated according to the following equation by the atomic ratio At% (atomic percent).

Wherein, N _C is the number of carbon atoms of the chromium carbide-based cermet plating layer per unit volume, and N _tot is the total atomic number of the chromium carbide-based cermet plating layer per unit volume.

Furthermore, if a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer having better mechanical properties and corrosion resistance is obtained, the stress relieving step can be further performed as follows: S4: Plating of a chromium carbide-based cermet formed by electroplating The tool substrate of the layer is placed in an oven and baked at a stress-free temperature condition; wherein the stress-relieving temperature condition is 180 ° C or more.

Further, if it is desired to increase the surface hardness and improve the wear resistance, the surface hardening treatment step may be performed after the step S3 or the step S4, as follows: S5: the chromium carbide base completed in the step S3 or the step S4 The tool substrate of the cermet plating layer is placed in a flame furnace, and a flame of 1200 ° C or higher at the outer flame end is heated on the chromium carbide-based cermet plating layer for at least 0.5 second.

Further, the characteristics of the chromium carbide-based cermet plating layer may be one or a combination of the following: the plating layer can be extremely thin and the average thickness ranges from 0.5 μm (inclusive) to 15 μm (inclusive), and does not affect the mechanical mechanism of the tool substrate workpiece. Size; it has good corrosion resistance, linear polarization corrosion current is below 1 × 10 ^-5 amps; it has excellent hardness and wear resistance, after surface hardening, the surface hardness is above 1500Hv.

Further, if the additive is selected from one or a combination of the following additive groups: (1) a halogen ammonium salt, (2) a boric acid and a salt thereof, and the trivalent chromium plating solution of the trivalent chromium (Cr ⁺³⁾ ) The ratio of the molar ratio per liter of carbon element is between 1:1 and 1:20; the content of the carbon element of the chromium carbide-based cermet plating layer is increased to be greater than 32 At%, except that the specific resistance is 100 mΩ. (Inclusive) The following has good electrical conductivity, its linear polarization corrosion current is 1×10 ^-5 ampere or less, and has good corrosion resistance. The contact angle can be further increased to make the contact angle greater than 120 degrees, achieving superhydrophobicity. Characteristics.

According to the present invention, a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer according to the present invention and a method for fabricating the same can have one or more of the following advantages:

(1) The hydrophobic conductive tool coated with the chromium carbide-based cermet plating layer of the present invention can form a high carbon content chromium carbide-based cermet plating layer on the surface of the tool, and improve the conductivity of the plating layer by high carbon content With corrosion resistance, the shortcomings of the prior art can be improved for tools for electrical conductivity requirements. Furthermore, the hydrophobic conductive tool coated with the chromium carbide-based cermet plating layer of the present invention has better hydrophobicity and has no disadvantage of high temperature deterioration or release of organic substances or poisons; further, the coated chromium carbide of the present invention Base cermet plating In addition to being electrically conductive, the hydrophobic conductive tool has high corrosion resistance and wear resistance; it can improve the contact angle to achieve superhydrophobicity and has excellent biocompatibility for medical surgical tools. For example, medical electric scalpels are used to cut human tissue to avoid sticking of the surface of the device; or tools used in dentistry can avoid tissue sticking on the surface of the drilling and cutting equipment. .

(2) The method for preparing a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer of the present invention has good conductivity, hydrophobicity and corrosion resistance, and can be suitably applied to a battery plate or a fuel cell. The tool substrate of the hydrophobic conductive tool coated with the chromium carbide-based cermet plating layer of the invention can be made of metal material or non-metal material, and can be applied to various requirements requiring corrosion resistance, wear resistance, conductivity, and hydrophobicity. , biocompatible tools.

(3) The method for preparing the hydrophobic conductive tool coated with the chromium carbide-based cermet plating layer of the present invention is a trivalent chromium plating, which is much less toxic than hexavalent chromium, and can reduce the environmental burden for clean plating. method.

(4) The method for fabricating a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer of the present invention can control the film thickness of the chromium carbide-based cermet plating layer by the composition and operating conditions of the trivalent chromium plating solution, Carbon ratio, etc., to provide different mechanical properties, hydrophobicity, and electrical conductivity of the tool substrate (the workpiece to be plated), and can be applied to various fields of demand.

(5) The method for fabricating the hydrophobic conductive tool of the coated chromium carbide-based cermet plating layer of the present invention can further enhance the chromium carbide-based metal of the hydrophobic conductive tool by further eliminating the stress or increasing the surface hardness of the post-treatment step The mechanical properties of ceramic plating can be applied to high-precision mechanical parts or molds.

The above and other technical contents, features and advantages of the present invention will be apparent from the following description of the drawings and the appended claims.

2 is a schematic view of a surgical tool for medical use of a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer; in the figure, the electrosurgical scalpel 11 includes a surgical blade 11 and a surgical blade 12, The scalpel blade 12 is made of a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer according to the present invention. The tool substrate 121 is first coated with a conductive layer 1212, and then the surface of the conductive layer 1212 is covered with a layer of carbonization. The composition of the chromium-based cermet plating layer 122 and the chromium carbide-based cermet plating layer 122 is as shown in Fig. 5, which is a Cr-C structure in which an amorphous phase is formed by the carbon element 1222 and the chromium element 1221.

Referring to FIG. 3, a schematic diagram of a method for fabricating a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer according to the present invention mainly utilizes the characteristics of an electrochemical reaction, and the tool substrate 121 is placed as a cathode, and the tool substrate 121 includes The conductive layer 1212 has a conductive layer 1212 if the tool substrate 1211 is metal. If the tool substrate 121 is non-metal, the conductive substrate 1212 is electrolessly plated or coated on the surface of the tool substrate 1121. The tool substrate 1121 is the workpiece to be electroplated; on the surface of the conductive layer 1212 of the tool substrate 1121, the electrochemical reaction of the carbon ions of the chelating agent in the trivalent chromium plating solution with the chromium ions on the cathode surface A chromium-carbon reduction nucleation reaction occurs, and due to the small gap existing between the tool substrate 121 and the trivalent chromium plating solution, the concentration difference of the trivalent chromium plating solution generates a chromium-carbon diffusion effect, so that the chromium-carbon will Naturally grown, a chromium carbide-based cermet plating layer 122 is formed. The cathodic chemical reaction formula is: [C r ( H ₂ O ) ₆ ] ³⁺ + XCOOH → [ Cr ( H ₂ O ) ₅ COOH ] ²⁺ + X ^- + H ₂ O

[ Cr ( H ₂ O ) ₅ COOH ] ²⁺ → [ Cr ( H ₂ O ) ₄ COOH ] ²⁺ + H ₂ O

[ Cr ( H ₂ O ) ₄ COOH ] ²⁺ + e ^- → [ Cr ( H ₂ O ) ₄ COOH ] ⁺ → Cr _{( S )}

COOH ^- → HCHO → CH ₃ OH → CO → C _{( S )}

The tool substrate 1 used in the following embodiments of the present invention may use a conductive metal material tool substrate 1121, a conductive ceramic tool substrate 1121, or a non-metal tool substrate 1121 coated with a conductive layer 1212, etc. limit. In the subsequent examples, it is useful to understand that a copper tool substrate (a workpiece containing a steel material, a copper plated on the surface of the workpiece) or a glass tool substrate (on the surface of the glass workpiece, an electroless nickel layer, As a conductive layer for covering). The anode may be made of a carbon plate or a high-potential passive metal plate (such as titanium alloy, gold, platinum, etc.), and the following examples use a platinum material as an anode, which is one of the modes adopted by the embodiment, but Not limited.

The trivalent chromium plating solution for forming a chromium carbide-based cermet plating layer of the present invention comprises: an aqueous solution formed by a trivalent chromium salt, a chelating agent and an additive; and the source of the trivalent chromium salt may be a trivalent chromium salt of a sulfuric acid or a chlorine. a water-soluble salt of an acid-based trivalent chromium salt; a sulfuric acid-based trivalent chromium salt such as one of or a combination of chromium sulfate, ammonium sulfate, potassium sulfate, or the like, and a trivalent chromium salt such as chromium chloride or perchloric acid. One or a combination of chromium, etc.; not limited.

For the chelation of the trivalent chromium plating solution and the carbon source for providing the plating layer, the chelating agent of the present invention may be formic acid (HCOOH), acetic acid (CH ₃ COOH) or a salt thereof such as formic acid or ammonium formate ( HCOONH ₄ ), sodium formate (HCOONa), acetic acid, ammonium acetate (CH ₃ COONH ₄ ), sodium acetate (CH ₃ COONa) or a combination thereof, the total concentration of carbon added to the chelating agent is between 0.1M and 5M When the relative concentration of the chelating agent is increased, the carbon content of the chromium carbide-based cermet plating layer can be increased and the conductivity can be improved.

The additive of the trivalent chromium plating solution is used as an additive for adjusting the plating solution. Generally, a salt having a low degree of dissociation can be used to have a function as a buffer agent, and a commonly used additive is a salt of a mineral acid. Classes, sulfates, boric acid (H ₃ BO ₃ ) or salts thereof, halogen salts, etc., such as boric acid, ammonium sulfate ((NH ₄ ) ₂ SO ₄ ), ammonium chloride (NH ₄ Cl) or ammonium bromide One or a combination of (NH ₄ Br), and the additive concentration of the additive is between 0.1 M and 0.5 M; when the relative concentration of the additive is increased, the corrosion resistance of the chromium carbide-based cermet plating layer can be improved.

Since many commercially available compounds may be doped with organic compounds, which will affect the operation and maintenance of the trivalent chromium plating solution, in the trivalent chromium plating solution, in order to reduce the influence of the organic compound, it is possible to use less organic compounds. Sulfate, boric acid or borate, chloride salt, bromine salt, ammonium salt, etc.; the formulation of trivalent chromium plating solution is shown in Table 1.

The above concentration is expressed by M (mole/l) as the molar number of the pure substance per liter of the trivalent chromium plating solution, which does not contain the mass of the impurity; the following are the same.

The chromium carbide-based cermet plating layer 122 of the hydrophobic conductive tool of the present invention is composed of a chromium element 1221 and a carbon element 1222, which contains a small amount of oxygen element or simple chromium element, and is plated on a tool substrate 121 ( The surface of the part workpiece. The method of the present invention and the formed chromium carbide-based cermet plating layer 122 provide a high carbon content and improve the conventional carbon element 1222 content of up to about 10 At%. The composition of the chromium carbide-based cermet plating layer 122 of the present invention comprises one or a combination of Cr ₂₃ C ₆ , Cr ₃ C ₂ or Cr ₇ C ₃ , and the content of the carbon element 1222 is in the range of 15 At% or more. The chromium carbide-based cermet plating layer 122 of the hydrophobic conductive tool has high carbon content, and therefore has good electrical conductivity, and has a specific resistance of 100 mΩ or less, a contact angle of pure water of more than 94 degrees at 25 ° C, and a linear pole thereof. The corrosion current is 1×10 ^-5 ampere or less; it is more conductive, corrosion resistant, hydrophobic and wear resistant.

To increase the corrosion resistance, the tool substrate 121 of the chromium carbide-based cermet plating layer 122 formed by electroplating may be subjected to stress-relieving annealing treatment, which is to form a tool substrate 121 of the chromium carbide-based cermet plating layer 122. It is placed in an oven and baked at a stress relief temperature condition of 180 ° C or more for a predetermined period of time.

In order to increase the wear resistance, the step of increasing the surface hardness of the chromium carbide-based cermet plating layer 122 formed by electroplating may be performed by using a high-temperature flame to rapidly heat the surface of the chromium carbide-based cermet plating layer 122. The step of hardness may be after the plating is completed or after the stress-relieving annealing treatment is completed. The following embodiments of the present invention employ an oxyacetylene flame, but are not limited thereto, and oxygen B The acetylene flame is a flame formed by the combustion of oxygen and acetylene. It consists of a flame core, an inner flame and an outer flame. When the ratio of oxygen to acetylene is 1 to 1.2, the flame is generated, and the inner flame is about 2760~3500. °C, the outer flame center is about 2100 ° C, and the outer flame end is about 1250 ° C.

To further illustrate the hydrophobic conductive tool of the present invention coated with a chromium carbide-based cermet plating layer and a method for fabricating the same, the following examples are described. In the following embodiments, a hydrophobic conductive tool made by the method for coating a chromium carbide-based cermet plating layer of the present invention will be described for use in various conductive tools, scalpel blades for scalpels, and bipolar plates for fuel cells. The plate of a general battery or a porous membrane of a spray nozzle, etc., but the field of application thereof is not limited by the foregoing embodiments.

<Example 1>

In order to increase the service life of the conventional welding nozzle, the hexavalent chromium hard chrome layer is often plated on the surface to have a better surface hardness and can be electrically conductive; in this embodiment, the chromium carbide-based cermet formed by electroplating is used. The welding nozzle of the electroplated layer has electrical conductivity, hydrophobicity, good surface hardness and corrosion resistance. Please refer to Fig. 7, Fig. 8, Fig. 11, and Fig. 13, Fig. 7 is a cross-sectional view of the lateral plating layer; Fig. 8 is a surface topography of the electroplated layer; and Fig. 11 is a composition diagram of the electroplated layer (vertical The coordinates are the angles of the energy intensity and the lateral coordinate scanning range; the 13th is the contact angle diagram. The trivalent chromium plating solution used in this embodiment is a sulfate plating bath, and its composition and operating conditions are as shown in Table 2. The chromium carbide-based cermet plating layer 122 formed by electroplating using the trivalent chromium plating solution and the operating conditions is as follows. three. The hydrophobic conductive tool of this embodiment is a copper welding nozzle, the tool substrate 1 is made of copper, and the current density is 10 A/dm ^{2 at an} operating temperature of 25 ° C, and the operation time is 10 minutes; The chromium carbide-based cermet plating layer 122 on the tool substrate 121 is observed by a microscope, and the carbon content in the plating layer is measured by EPMA (ELECTRON PROBE X-RAY MICROANALYZER), and the carbon content is about It is 28At%. The obtained chromium carbide-based cermet plating layer 122 is obviously flat, and the plating layer is plated to a thickness of about 3 μm or less, and the electrical conductivity is about 10 mΩ, indicating that the plating layer has good conductivity; the pure water contact angle is 94.9. Degree (at 25 ° C, the same below), showing that its hydrophobicity is good; because the plating layer is flat, the defects are less, the workpiece parts have high corrosion resistance, and the service life of the workpiece parts can be improved, and the plating layer of the embodiment is not After the stress is removed and the surface hardness is increased, the hardness is about 1000 Hv; see Figure 11, the composition of the plating layer includes a mixed plating layer of Cr, Cr ₂₃ C ₆ , Cr ₃ C ₂ and Cr ₇ C ₃ .

Among them, the corrosion resistance test is based on AutoLAB impedance spectrum analysis linear polarization test, the evaluation criteria are as follows: Level 1, linear polarization corrosion current (Amp.) less than 1 × 10 ^-7 amps or less, level 2 1 × 10 ^-6 ampere or less, 3 grades, 1 × 10 ^-5 ampere or less, 4 grades, 1 × 10 ^-4 ampere or more; the following examples show the same method.

<Example 2>

The anti-static retaining plate can be applied to an electronic manufacturing production line or a pyrotechnic manufacturing line, and its electrical conductivity and corrosion resistance are highly demanded. The antistatic trays conventionally used are often made of metal, such as stainless steel or beryllium copper used in the production line of explosives, but such materials are poor in hydrophobicity and insufficient in corrosion resistance. In this embodiment, a glass substrate tool substrate is used to electroplate the formed anti-static disk of the chromium carbide-based cermet plating layer to have conductivity, hydrophobicity, good surface hardness and corrosion resistance. The trivalent chromium plating solution used in this embodiment is a sulfate plating bath, and its composition and operating conditions are as shown in Table 4. The chromium carbide-based cermet plating layer formed by electroplating using the trivalent chromium plating solution and operating conditions is as shown in Table 5. . The hydrophobic conductive tool of the embodiment is an antistatic disk, and the surface of the glass or ceramic material is electroless nickel-plated as a tool substrate, and the current density is 30 A/dm ^{2 and the} operating temperature is 25 ° C, and the operation time is 30. Minutes, the chromium carbide-based cermet plating layer on the tool substrate was observed with a scanning electron microscope, and the carbon content in the plating layer was measured by EPMA to be about 22.4 At%. The sulphate chromium carbide-based cermet plating layer has a thickness of about 13 μm and a specific resistance of about 12 mΩ in electrical conductivity, and the electroplating layer has good conductivity; the pure water contact angle is 98.7 degrees, indicating that the hydrophobicity is good. The corrosion resistance of the present embodiment is evaluated to be 2 grades. The electroplated layer of the present embodiment is processed after the stress is not relieved and the surface hardness is increased, and the hardness is about 1000 Hv. The composition of the plating layer in the composition includes Cr, Cr ₂₃ C ₆ , Cr. A mixed plating layer of ₃ C ₂ and Cr ₇ C ₃ .

<Example 3>

As mentioned above, the conventional electrosurgical scalpel often coats Teflon or chromium nitride film on the surface. Since Teflon has the problem of releasing fluorine-containing toxic gas, the surface contact angle of the chromium nitride film is 78°. It is hydrophilic and easy to stick when cutting tissue. In addition, due to the poor conductivity of Teflon and Chromium Nitride films, there are restrictions on the use of electrosurgical scalpels. 2 is a schematic view of a surgical tool for a medical conductive tool of the present embodiment; the scalpel blade 12 is attached to a tool substrate 121 by plating a layer of chromium carbide-based cermet plating layer 122, chromium carbide. The composition analysis of the base cermet plating layer 122 is as shown in Fig. 5, and is a Cr-C structure in which an amorphous phase is formed by the carbon element 1222 and the chromium element 1221.

The trivalent chromium plating solution used in this embodiment is a sulfate plating bath, and its composition and operating conditions are as shown in Table 6. The chromium carbide-based cermet plating layer 122 formed by electroplating using the trivalent chromium plating solution and operating conditions is as shown in the table. Seven. The hydrophobic conductive tool of the present embodiment is a medical electrosurgical scalpel 1 with stainless steel as the tool substrate 121, and the electroplating operation parameters are the same as those in the first embodiment. Since the electroplating is performed on the stainless steel, the electroplating is performed at 350 ° C for 60 minutes after electroplating. To eliminate the stress, the chromium carbide-based cermet plating layer 122 on the tool substrate 121 was observed by a scanning electron microscope, and the carbon content in the plating layer was measured by EPMA to be about 32.7 At%. The obtained chromium carbide-based cermet plating layer 122 is obviously flat, the plating layer is plated to a thickness of about 8 μm or less, and the electrical conductivity is about 6 mΩ, indicating that the plating layer has good conductivity; the pure water contact angle is 107.4 degrees; Because the plating layer is flat and has fewer defects, the workpiece parts have high corrosion resistance and can improve the service life of the workpiece parts. The plating layer is treated without increasing the surface hardness, and the hardness is about 1200Hv; the composition of the plating layer includes Cr, A mixed plating layer of Cr ₂₃ C ₆ , Cr ₃ C ₂ and Cr ₇ C ₃ , the electroplating layer is mainly composed of Cr, C, O, and has biocompatibility, and since the plating layer has good tight coverage, the tool substrate is not easily dissolved and harmful. The metal makes the electrosurgical scalpel 1 biocompatible.

In Examples 1 to 3, the carbon content of the plating layer is higher than 15 At% to 33 At%, and the conductivity of the plating layer is maintained at 5 to 15 mΩ; in the corrosion resistance, referring to Examples 1 to 3, the plating The linear polarization corrosion current of the layer corrosion resistance is maintained between 1 × 10 ^-5 and 1 × 10 ^-7 (A). With reference to the first to third embodiments, the present invention improves the carbon content of the electroplated layer by greatly improving the carbon content of the electroplated layer, thereby improving the electroconductivity, the hydrophobicity, the corrosion resistance of the electroplated layer, and the hardness of the electroplated layer. efficacy. It has been verified that the medical electrosurgical scalpel 1 using the chromium carbide-based cermet plating layer 122 of the present embodiment is biocompatible, and can reduce thermal damage to the tissue caused by current, avoid tissue burning and smoking, and electric burn surgery. The surface of the scalpel blade 12 of the knife 1 does not cause sticking of blood clots or tissues.

<Example 4>

A typical atomizer first atomizes a liquid into tiny droplets, and then sprays the atomized droplets directly onto a specified surface via a nozzle. The spray particle size is about 10 to 50 μm, and the nozzle is provided with a microplate at the outlet. (porous membrane), often made of metal materials such as PTFE or stainless steel. Since the microporous plate made of PTFE has a short service life, and the microplate made of stainless steel is hydrophilic, the droplets are easily blocked during use.

For even smaller droplet requirements, such as an average spray particle size below 10 μm, the conventional technique is to install an ultrasonic generator at the tip of the nozzle of the nozzle, when the atomized droplet hits the ultrasonic generator at high speed, immediately Producing high-frequency oscillations and ultrasonic waves, the spray particle size will be more micro-atomized, and the microplate is usually made of metal, and a nickel layer is plated for the purpose of corrosion prevention; but practically, since the microplate is hydrophilic, When used, the droplets are more likely to clog, and the nickel metal will dissolve in the mist-drop, resulting in non-biocompatibility and inability to be supplied to medical instruments.

As shown in Fig. 5, a schematic diagram of the chromium carbide-based cermet electroplating layer hydrophobic conductive tool of the present invention applied to the microplate 3 to have conductivity, hydrophobicity, good surface hardness and corrosion resistance; and due to chromium carbide base The microporous plate 3 made of the cermet electroplated hydrophobic conductive tool does not release harmful toxic substances or metal ions, is biocompatible, and can be used for medical purposes. The tool substrate 31 of the microplate 3 is made of stainless steel and is fixed to the nozzle tip of the atomizer nozzle by four fixing screw holes 33; in the present embodiment, the tool substrate 31 attached to the microplate 3 is covered with electroplating. A layer of chromium carbide-based cermet plating layer 32, a chromium carbide-based cermet plating layer 32 is a Cr-C structure in which an amorphous phase is formed by carbon element 321 and chromium element 322; see Fig. 9, Fig. 10, Fig. 12 Figure 14 is a cross-sectional view of the electroplated layer of the present embodiment; Fig. 10 is a surface topography of the electroplated layer; and Fig. 12 is a structural diagram of the electroplated layer (the ordinate is the energy intensity and the lateral coordinate scan) The angle of the aiming range); Figure 14 is the contact angle diagram. The trivalent chromium plating solution used in this embodiment is a chlorate plating bath, and its composition and operating conditions are as shown in Table 8. The chromium carbide-based cermet plating layer 32 formed by electroplating using the trivalent chromium plating solution and operating conditions is as follows. nine. The hydrophobic conductive tool of this embodiment is also a stainless steel copper tool substrate 31. The electroplating has a current density of 10 A/dm ^{2 and an} operating temperature of 25 ° C, an operation time of 10 minutes, and a heat treatment at 350 ° C for 30 minutes after electroplating to eliminate Stress, and then the chromium carbide-based cermet plating layer 32 on the tool substrate 31 was observed by a scanning electron microscope, and the carbon content in the plating layer was measured by EPMA to be 54.3 At% up to about 55 At% or more. The obtained chromium carbide-based cermet plating layer 32 is flat, the plating layer is plated to a thickness of about 2 μm or less, and the electrical conductivity is about 2 mΩ, and the pure water contact angle is 131.6 degrees, which is a superhydrophobicity with a contact angle of more than 120 degrees. The electroplated layer is treated without increasing the surface hardness, and has a hardness of about 1000 Hv; the composition of the electroplated layer includes a mixed plating layer of Cr, Cr ₂₃ C ₆ , Cr ₃ C ₂ and Cr ₇ C ₃ .

The carbon element 321 of the chromium carbide-based cermet plating layer 32 of the present embodiment is mainly derived from the carbon source of the chelating agent, and the carbon content of the chromium carbide amorphous phase structure with higher carbon content formed by the carbon content is increased, and the surface hydrophobicity is increased. .

<Example 5>

Referring to FIG. 4, a schematic diagram of a battery bipolar plate made in the present embodiment, a fuel cell is a type of hydrogen, methane. Or a fuel such as methanol and a gas undergo a combustion chemical reaction to release heat energy and convert it into a battery for electric energy. The main component of the fuel cell is a two-piece battery bipolar plate composed of a chemical reaction substance layer of the interlayer; wherein the battery bipolar plate Composition 2, as shown in Fig. 4, in the battery bipolar plate composition 2 is provided with a plurality of strip-shaped circulation pipes 23 for gas and generated water to enter and exit, and the battery bipolar plate composition 2 is mainly for separating the oxidant from the reducing agent, current By the battery bipolar plate composition 2 is conducted to the outside, gas generated by the chemical reaction for better efficiency can be uniformly and rapidly circulated in the circulation pipe 23, and the battery bipolar plate composition 2 needs to reduce heat accumulation, so the battery The bipolar plate composition 2 must have characteristics such as electrical conductivity, temperature resistance, corrosion resistance, and hydrophobicity.

The battery bipolar plate made in this embodiment is composed of a nickel-plated steel plate as a bipolar plate substrate 21, and a chromium carbide-based cermet plating layer 22 is formed on the bipolar plate substrate 21 by a trivalent chromium plating bath. The composition of the layer constitutes a mixed plating layer of Cr, Cr ₂₃ C ₆ , Cr ₃ C ₂ and Cr ₇ C ₃ formed by the carbon element 221 and the chromium element 222. The trivalent chromium plating solution used in this embodiment is a chlorate plating bath, and its composition and operating conditions are as shown in Table 10. The chromium carbide-based cermet plating layer 122 formed by electroplating using the trivalent chromium plating solution and operating conditions is as follows. eleven. In the hydrophobic conductive tool of the present embodiment, the plate of the battery is plated with nickel as the tool substrate 121, and the operating temperature is 25 ° C at a current density of 30 A/dm ² and the operation time is 10 minutes. The chromium carbide-based cermet plating layer 122 on the tool substrate 121 is observed by a scanning electron microscope, and the carbon content in the plating layer is measured by EPMA, and the obtained chromium carbide-based cermet plated layer 122 has a carbon content of about 34.2 At%. The plating layer is plated to a thickness of about 4 μm, and has a conductivity of about 7 mΩ. The conductivity of the plating layer is good. The pure water contact angle is 120.7 degrees, and the contact angle is more than 120 degrees. Sex. The plating layer is not post-treated and has a hardness of about 750 Hv. Referring to Figure 12, the composition of the plating layer in the composition includes Cr, Cr ₂₃ C ₆ , Cr ₃ C ₂ and Cr ₇ C ₃ .

<Example 6>

This embodiment is the same as that of the third embodiment, and is applied to a medical electrosurgical scalpel, as shown in Fig. 2. The trivalent chromium plating solution used in this embodiment is a chlorate plating bath, and its composition and operating conditions are as shown in Table 12, and the chromium carbide-based cermet plating layer 122 formed by electroplating using the trivalent chromium plating solution and operating conditions is as Table XIII. This embodiment is used for the medical electrosurgical scalpel 1. The medical electrosurgical scalpel 1 needs to meet the requirement of superhydrophobicity. The tool substrate 121 of the present embodiment is made of stainless steel. The same operating conditions as in the embodiment of the present embodiment, the only difference is the post-treatment, after the electroplating, heat treatment at 350 ° C for 60 minutes to eliminate stress, and sprayed on the electroplated layer at 1200 ° C for 2 seconds to increase the surface hardness, and then scan The chromium carbide-based cermet plating layer 3 on the tool substrate 121 was observed by an electron microscope, and the carbon content in the plating layer was measured by EPMA to be about 55 At%. The obtained chromium carbide-based cermet plating layer 122 is flat, the plating layer is plated to a thickness of about 2 μm, and the electrical conductivity is about 3 mΩ; the pure water contact angle is 124.8 degrees, and the contact angle is more than 120 degrees, which is superhydrophobic; Because the plating layer is flat and has fewer defects, the workpiece parts have high corrosion resistance and can improve the service life of the workpiece parts. The plating layer is post-treated and has a hardness of about 1500Hv; the composition of the plating layer includes Cr, Cr ₂₃ C ₆ , Mixed plating layer of Cr ₃ C ₂ and Cr ₇ C ₃ , the electroplating layer is mainly composed of Cr, C, O, and has biocompatibility, and because the plating layer has good tight coverage, the tool substrate is not easy to dissolve harmful metals to cause electrocautery operation. Knife 1 is biocompatible.

It has been verified that the medical electrosurgical scalpel using the chromium carbide-based cermet plating layer of the present embodiment has super conductivity, good corrosion resistance and biocompatibility, and is superhydrophobic, which can reduce the current resistance. Thermal damage to the tissue, avoiding tissue burning and smoking, and burning of the scalpel surface will not cause blood clots or tissue stickiness.

<Example 7>

The trivalent chromium plating solution used in this embodiment is a chlorate plating bath, and its composition and operating conditions are as shown in Table 14. The chromium carbide-based cermet plating layer formed by electroplating using the trivalent chromium plating solution and operating conditions is as follows. fifteen. The hydrophobic conductive tool of the embodiment is an electrode patch, which is made of electroless nickel on the surface of the PU plastic. The operating temperature is 25 ° C at a current density of 30 A/dm ² and the operation time is 60 minutes. The heat treatment was performed at 350 ° C for 60 minutes to eliminate stress, and the chromium carbide-based cermet plating layer on the tool substrate was observed by a scanning electron microscope, and the carbon content in the plating layer was measured by EPMA to be about 55 At%. The obtained chromium carbide-based cermet plating layer is flat, the plating layer is plated to a thickness of about 15 μm, the electrical conductivity is about 83 mΩ, and the pure water contact angle is 71.6 degrees; since the plating layer is thick, the defects are small, and the defect is small. The workpiece parts have high corrosion resistance and can improve the service life of the workpiece parts. The untreated hardness of the electroplated layer is about 1100Hv; the composition of the electroplated layer includes mixed plating of Cr, Cr ₂₃ C ₆ , Cr ₃ C ₂ and Cr ₇ C ₃ Floor.

According to Embodiments 1-7, suitable trivalent chromium plating baths, operating conditions, suitable current densities of controlled current densities between 10 A/dm ² and 50 A/dm ² , and operating times can be used for different application purposes. The chromium carbide-based cermet plating layer has a carbon content which is most suitable for the purpose of use, and forms physical properties such as conductivity, corrosion resistance, hydrophobicity, and hardness in accordance with the use requirements.

As mentioned above, it is known that the chrome plating technique only produces a pure chrome plating layer, but the pure chrome plating layer has low conductivity and corrosion resistance, is not high precision, and requires conductivity, hydrophobicity, hardness and resistance. Use of abrasive properties. The invention utilizes the principle of chromiumation of trivalent chromium to convert the metal state of chromium element and carbon element deposited in the electroplating process into a ceramic-like state, which can improve the conductivity, hydrophobicity and corrosion resistance of the electroplated layer of the invention, and is more suitable for various needs. It is used for tools, molds, hydrophobic conductive tools, medical equipment, etc., which have both conductive and hydrophobic properties and have ceramic properties.

The above is intended to be illustrative only and not limiting. any Equivalent modifications or variations of the present invention are intended to be included within the scope of the appended claims.

1‧‧‧Electric Burning Scalpel

11‧‧‧Surgical handle

12‧‧‧Surgical blade

121‧‧‧Tool substrate

1212‧‧‧ Conductive layer

122‧‧‧Chromium carbide based cermet plating

1222‧‧‧carbon elements

1221‧‧‧Chromium

2‧‧‧Battery bipolar plate composition

21‧‧‧Bipolar plate substrate

22‧‧‧Chromium carbide-based cermet plating

221‧‧‧carbon elements

222‧‧‧Chromium

23‧‧‧Circulation pipeline

3‧‧‧Microplate

31‧‧‧Tool substrate

32‧‧‧Chromium carbide-based cermet plating

321‧‧‧carbon elements

322‧‧‧Chromium

33‧‧‧Fixed screw holes

91‧‧‧Return cable

92‧‧‧Return guard

93‧‧‧current generator

94‧‧‧Main cable

95‧‧‧Electric Burning Scalpel

S1~S5‧‧‧ method steps

1 is a schematic view of a conductive scalpel of the prior art; FIG. 2 is a schematic view of a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer applied to a scalpel according to the present invention; and FIG. 3 is a cladding chromium carbide of the present invention. Schematic diagram of a method for fabricating a hydrophobic conductive tool of a base metal ceramic plating layer; FIG. 4 is a schematic view showing a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer applied to a fuel cell bipolar plate; The invention discloses a schematic diagram of a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer applied to a microporous plate; and FIG. 6 is a composition analysis diagram of a chromium carbide-based cermet plating layer, which assists in explaining a chromium carbide-based cermet plating layer of Table 3. The chemical composition; Figure 7 is a cross-sectional view of the chromium carbide-based cermet plating layer, which assists in explaining the cross-sectional microstructure of the chromium carbide-based cermet plating layer of Table 2; Figure 8 is the chromium carbide-based cermet plating. Layer surface topography, auxiliary description of the chromium carbide-based cermet coating of Table 2. The surface topography; Figure 9 is a cross-sectional view of the chromium carbide-based cermet plating layer, which assists in explaining the cross-sectional microstructure of the chromium carbide-based cermet plating layer of Table 8; Figure 10 is the chromium carbide-based cermet plating. The surface topography of the layer is used to explain the surface morphology of the chromium carbide-based cermet plating layer of Table 8. The eleventh figure is the composition analysis of the chromium carbide-based cermet plating layer of Examples 1 to 3. And the chemical composition of the chrome-plated cermet plating layer of the seven; the 12th is the composition analysis diagram of the chromium carbide-based cermet plating layer of Examples 4 to 7, which assists in the carbonization of Tables 9, 11, 13, and 15. The chemical composition of the chromium-based cermet plating layer; the 13th is the contact angle of the chromium carbide-based cermet plating layer to help explain the contact angle of Table 3; and the 14th is the chrome-plated cermet plating layer contact angle diagram. The contact angle of the nine.

1‧‧‧Electrosurgical blade

11‧‧‧Surgical holder

12‧‧‧Surgical Blade (Blade edge)

121‧‧‧Tool substrate (substrate)

1212‧‧‧Conductivity layer

122‧‧‧Chromium carbide ceramic electroplating layer

1222‧‧‧carbon atom

1221‧‧‧chromium atom

Claims (11)

A hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer, comprising: a tool substrate and a chromium carbide-based cermet plating layer coated on a surface layer of the tool substrate; wherein the material of the tool substrate is selected from the group consisting of In one or a combination of the following groups: (1) conductive material: one or a combination of conductive ceramics, iron, stainless steel, copper, chromium, nickel, silver, gold or alloys thereof; (2) non-conductive material: plastic, One or a combination of ceramics or glass, and coating a conductive layer by electroplating or electroless plating, the conductive layer being selected from the group consisting of iron, copper, chromium, nickel, silver, gold or alloys thereof; wherein the chromium carbide-based metal The ceramic plating layer is adhered to the surface of the tool substrate by electroplating to form an amorphous phase structure, and the composition thereof is composed of chromium element and carbon element, and at least includes chromium trichloride (Cr ₂₃ C ₆ ) and tri-chromium tri-carbon. One or a combination of (Cr ₃ C ₂ ) or hexachromic (Cr ₇ C ₃ ); the chromium carbide-based cermet plating layer has a carbon content of more than 15 At%; the coated chromium carbide-based cermet plating The layer of hydrophobic conductive tool has a specific resistance of 100mΩ . Below mm ² /m (inclusive), the contact angle of pure water at 25 ° C is greater than 94 degrees and less than 120 degrees. A chromium carbide-based cermet plating layer of a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer as described in claim 1 has a linear polarization corrosion current of 1 × 10 ^-5 ampere or less. The chromium carbide-based cermet plating layer of the hydrophobic conductive tool coated with the chromium carbide-based cermet plating layer according to claim 2, when the content of the carbon element of the chromium carbide-based cermet plating layer is greater than 32 At% At 25 ° C, the contact angle of its pure water is greater than 120 degrees. A chromium carbide-based cermet plating layer of a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer as described in claim 1 has an average thickness ranging from 0.5 μm to 15 μm. The chromium carbide-based cermet plating layer described in claim 1 has a surface hardness of 1500 Hv or more. A method for manufacturing a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer for coating a tool substrate with a chromium carbide-based cermet plating layer, comprising the steps of: providing a tool substrate, the tool base The surface of the material comprises at least one conductive layer; the tool substrate is used as a cathode, and is immersed in a trivalent chromium plating solution; electroplating is performed on a plating temperature condition and a current density condition on the tool substrate. Forming a chromium carbide-based cermet plating layer; wherein the trivalent chromium plating solution comprises at least: an aqueous solution formed by a trivalent chromium salt, a chelating agent, and an additive; wherein the trivalent chromium salt is a sulfuric acid system a trivalent chromium salt or a monovalent chromium salt of monochloro acid; wherein the sulfuric acid trivalent chromium salt comprises a compound formed by trivalent chromium (Cr ⁺³ ) and sulfate (SO ₄ ^-2 ), The chloric acid-based trivalent chromium salt comprises a compound formed by one or a combination of trivalent chromium (Cr ⁺³ ) and chloride ion (Cl ⁻ ), perchloric acid ion (ClO ₄ ⁻ ); wherein the chelate The mixture is selected from organic acids and salts thereof, and the total amount of the chelating agent is added. The concentration of the carbon element is between 0.1 M and 5 M; the additive is selected from the group consisting of inorganic acids or ammonium salts thereof, and the additive concentration of the additive is between 0.2 M and 1 M; the third of the trivalent chromium plating solution The chrome (Cr ⁺³ ) and the carbon element have a molar ratio of 1:1 to 1:20; the chromium carbide-based cermet plating layer is composed of chromium and carbon. An amorphous phase structure, which is coated on the surface of the conductive layer of the tool substrate, and whose composition is composed of chromium element and carbon element, and has an amorphous phase structure, and includes at least hexachlorochrome (Cr ₂₃ C ₆ ) Or one or a combination of trichromium (Cr ₃ C ₂ ) or hexachromic (Cr ₇ C ₃ ); wherein the content of carbon is in the range of more than 15 At%; the coated chromium carbide-based cermet coating The hydrophobic conductive tool has a specific resistance of 100mΩ. mm ² / m (inclusive), which at 25 deg.] C pure water contact angle greater than 94 degrees and less than 120 degrees. A method for manufacturing a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer for coating a tool substrate with a chromium carbide-based cermet plating layer, comprising the steps of: providing a tool substrate, the tool base The surface of the material comprises at least one conductive layer; the tool substrate is used as a cathode, and is immersed in a trivalent chromium plating solution; electroplating is performed on a plating temperature condition and a current density condition on the tool substrate. Forming a chromium carbide-based cermet plating layer; wherein the trivalent chromium plating solution comprises at least: an aqueous solution formed by a trivalent chromium salt, a chelating agent, and an additive; wherein the trivalent chromium salt is a sulfuric acid system a trivalent chromium salt or a monovalent chromium salt of monochloro acid; wherein the sulfuric acid trivalent chromium salt comprises a compound formed by trivalent chromium (Cr ⁺³ ) and sulfate (SO ₄ ^-2 ), The chloric acid-based trivalent chromium salt comprises a compound formed by one or a combination of trivalent chromium (Cr ⁺³ ) and chloride ion (Cl ⁻ ), perchloric acid ion (ClO ₄ ⁻ ); wherein the chelate Mixtures are selected from organic acids and their salts, and the total amount of the chelating agent is added. The carbon element concentration is between 0.1 M and 5 M; the additive is selected from one or a combination of the following additive groups: (1) a halogen ammonium salt, (2) a boric acid and a salt thereof, and the additive is added. The concentration is between 0.1 M and 1 M; the trivalent chromium (Cr ⁺³ ) of the trivalent chromium plating solution and the molar ratio of the carbon element per liter are between 1:1 and 1:20; The chromium carbide-based cermet plating layer is coated on the surface of the conductive layer of the tool substrate, and the composition thereof is composed of chromium element and carbon element, and is an amorphous phase structure, and at least includes hexachlorochrome (Cr _{23 )} One or a combination of C ₆ ), trichromium (Cr ₃ C ₂ ) or hexachromic (Cr ₇ C ₃ ); wherein the content of carbon is in the range of more than 32 At%; the coated chromium carbide-based metal The specific resistance of the hydrophobic conductive tool of the ceramic plating layer is 100mΩ. Below mm ² /m (inclusive), its linear polarization corrosion current is 1 × 10 ^-5 ampere or less, and its pure water contact angle is greater than 120 degrees. The method for manufacturing a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer according to any one of claims 6 to 7, further comprising a stress relieving step of plating The tool substrate forming the chromium carbide-based cermet plating layer is placed in an oven for baking at a stress-relieving temperature condition; wherein the stress-relieving temperature condition is 180 ° C or more. The method for manufacturing a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer according to any one of claims 6 to 7, further comprising an increase a surface hardness step of placing the tool substrate of the chromium carbide-based cermet plating layer in a flame, and heating the flame at a temperature of 1200 ° C or higher at the outer flame end for at least 0.5 seconds on the chromium carbide-based cermet plating layer. . The method for producing a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer according to any one of claims 6 to 7, wherein the current density condition ranges from 10 A/dm ² to 30 A. / dm between ^2; wherein the temperature of the plating temperature is set within ± 3 ℃ is. The method for producing a hydrophobic conductive tool coated with a chromium carbide-based cermet plating layer according to claim 6, wherein the linear conductive corrosion of the hydrophobic conductive tool coated with the chromium carbide-based cermet plating layer The current is 1 × 10 ^-5 amps or less.