Pt coating and Ti substrate interface bonding strengthening structure and method

Abstract

The invention discloses an interface bonding strengthening structure and method of a Pt coating and a Ti substrate, and belongs to the technical field of heterogeneous metal material bonding. The method comprises the following steps: putting a Ti substrate on which a Pt plating layer is prefabricated or a Pt foil sheet is stacked into heat treatment equipment; setting a heat treatment atmosphere in the heat treatment equipment, heating the sample to a preset temperature at a heating speed of 1-100 DEG C / min, carrying out heat preservation for 1-200 minutes, and then cooling the sample to room temperature at a speed of 1-100 DEG C / min so as to realize interface bonding strengthening of the Pt coating or the Pt foil and the Ti substrate; and carrying out XRD (X-Ray Diffraction) analysis on the Pt-plated titanium substrate obtained after heat treatment so as to observe whether a Pt-Ti intermetallic compound and / or a (Ti, Pt) ss solid solution is formed on a contact interface between the Pt plating layer or the Pt foil and the Ti substrate, and if so, determining that the production is qualified. According to the method for strengthening the combination of the Pt plating layer and the Ti substrate interface, heat treatment process parameters are adjusted in a specific range, strengthening treatment on the combination of the Pt / Ti interface is achieved, reliable combination of the Pt plating layer and the Ti substrate is guaranteed, the process is simple, and remarkable technical advantages and high application value are achieved.

Description

Technical Field

[0001] The present application relates to the technical field of heterogeneous metal material bonding, and specifically to an interface bonding strengthening structure and method between a Pt coating and a Ti substrate. Background Art

[0002] As an ideal form of energy, hydrogen energy can accelerate the adjustment of energy structure and promote the realization of the two carbon goals. Proton exchange membrane water electrolysis (PEMWE) hydrogen production has the advantages of high current density, high hydrogen purity and fast start-stop speed, and is one of the most important mainstream hydrogen production technologies at present. The PEMWE hydrogen production system mainly includes bipolar plates (BPs), membrane electrodes (MEA) and porous transport layers (PTLs). The bipolar plates and transport layers on the anode side need to serve for a long time in a high potential and acidic environment, so these components must have excellent corrosion resistance. At present, Ti with good corrosion resistance is widely used as a material for preparing bipolar plates and transport layers. However, since Ti with high reactivity is very easy to combine with O to form TiO2, its contact resistance increases and the efficiency of water electrolysis is seriously reduced. It is usually necessary to prepare a layer of Pt coating on the surface of the Ti substrate. At the same time, the easy oxidation property of Ti also makes it almost impossible to completely remove the oxide layer on its surface. Therefore, the interface bonding strength between the Pt coating prepared by electroplating, brush plating and magnetron sputtering and the Ti substrate is not high enough. During the operation of the electrolytic cell, the premature detachment of the Pt coating will seriously damage the electrolytic performance and thus restrict the durability of the electrolytic cell. Obviously, strengthening the interface bonding between the Pt coating and the Ti substrate is crucial to promoting the development and application of PEMWE.

[0003] At present, there are many related fields involving similar technical research, such as the patent document with patent number KR102389921B1, which discloses a method for manufacturing an electrode for an ion generator, which records: preparing an electrode plate made of titanium (Ti) coated with platinum (Pt); an immersion step of immersing the electrode plate in a graphene oxide solution; a drying step of taking out the electrode plate for drying; a heat treatment step of heat-treating the electrode plate at 300-400°C. This electrode plate is a mesh electrode plate made of titanium material plated with platinum, and typically, the thickness of platinum is preferably 0.2-0.3 μm. However, after being treated by this method, the bonding strength between Pt and Ti is not good.

[0004] At present, there is no technical means reported that can effectively enhance the interface bonding between the Pt coating and the Ti substrate. Therefore, it is urgent to develop a method that can effectively enhance the interface bonding between the Pt coating and the Ti substrate to achieve reliable bonding between the Pt coating and the Ti substrate. Summary of the invention

[0005] The present application aims to solve at least one of the technical problems in the relevant field to a certain extent. To this end, the present application provides a structure and method for strengthening the interface bonding between a Pt coating and a Ti substrate, which achieves strengthening treatment of the Pt / Ti interface bonding by adjusting the heat treatment process parameters within a specific range, ensures reliable bonding between the Pt coating and the Ti substrate, has a simple process, and has significant technical advantages and high application value.

[0006] To achieve the above objectives, in a first aspect, the present application provides an interface bonding strengthening structure between a Pt coating and a Ti substrate, wherein the interface bonding structure comprises a Pt-Ti intermetallic compound and / or (Ti, Pt) formed at the interface bonding between the Pt coating and the Ti substrate. ss Solid solution.

[0007] Preferably, the Ti matrix is ​​made of Ti-based metal and alloy.

[0008] In a second aspect, the present application provides a method for strengthening the interface bonding between a Pt coating and a Ti substrate, comprising the following steps:

[0009] Set the heat treatment atmosphere and heat treatment parameters;

[0010] The Ti substrate prefabricated with a Pt coating or stacked with a Pt foil is heat treated to 300-1200°C and kept warm for 1-200 minutes to form a Pt-Ti intermetallic compound and / or a (Ti, Pt)ss solid solution at the interface between the Pt coating and the Ti substrate, so as to achieve interface strengthening between the Pt coating or the Pt foil and the Ti substrate.

[0011] Preferably, the heat treatment is carried out by one or more of the following methods: heating by heat treatment equipment, electromagnetic induction heating, microwave heating, direct application of current heating or laser heating.

[0012] Preferably, when the Ti substrate stacked with the Pt foil is subjected to heat treatment, a certain axial pressure is applied to the stacked member consisting of the Pt foil and the Ti substrate to make the Pt foil closely attached to the Ti substrate.

[0013] Preferably, the method of prefabricating the Pt coating comprises one or a combination of several methods selected from electroplating, brush plating, magnetron sputtering, plasma spraying, thermal spraying, cold spraying, chemical vapor deposition, physical vapor deposition, hot dip plating and powder metallurgy.

[0014] Preferably, the step of setting the heat treatment atmosphere includes setting the heat treatment atmosphere to a high vacuum, a low vacuum, a reducing gas or an inert gas atmosphere, wherein the high vacuum atmosphere is 10 -2 ~10 -6 Pa, low vacuum atmosphere is 0.1~100Pa.

[0015] Preferably, the reducing gas includes hydrogen, argon-hydrogen mixed gas or nitrogen-hydrogen mixed gas; the inert gas atmosphere adopts one or a combination of argon, nitrogen, neon and xenon.

[0016] Preferably, the method further comprises: placing the Pt-plated titanium substrate obtained after the heat treatment in deionized water for ultrasonic treatment for a certain period of time or treating the Pt coating by a bonding-peeling method or a scribing or chemical lattice method, and then using a SEM electron microscope to detect whether the Pt coating falls off or warps. If there is no falling off or warping, the production is qualified.

[0017] Preferably, the method further comprises: performing XRD analysis on the Pt-plated titanium substrate obtained after the heat treatment to observe whether Pt-Ti intermetallic compounds and / or (Ti, Pt) are formed at the contact interface between the Pt coating or the Pt foil and the Ti substrate. ss Solid solution, if present, the production is qualified.

[0018] Preferably, the step of heat treating the Ti substrate prefabricated with a Pt coating or stacked with Pt foil also includes: heating the sample to a preset temperature at a heating rate of 1 to 100°C / min and keeping it at that temperature for 1 to 200 minutes, and then cooling it to room temperature at a rate of 1 to 100°C / min.

[0019] Based on the above technical solution, it can be seen that the interface bonding strengthening structure and method of a Pt coating and a Ti substrate of the present application have the following beneficial effects compared with the prior art:

[0020] The method for strengthening the interface bonding between the Pt coating and the Ti substrate of the present application achieves the strengthening treatment of the Pt / Ti interface bonding by adjusting the heat treatment process parameters within a specific range, thereby ensuring the reliable bonding between the Pt coating and the Ti substrate. Under the heat treatment conditions of the present application, Pt atoms and Ti atoms diffuse with each other and react chemically to form Pt-Ti intermetallic compounds and / or (Ti, Pt)ss solid solutions at the Pt / Ti interface, thereby achieving interface metallurgical bonding. The interface bonding strength is substantially improved, and the contact resistance of the sample does not increase significantly.

[0021] Other features and advantages of the present application will be described in the subsequent description, and in part will become apparent from the description, or it may be understood through the implementation of the present application that the objects and other advantages of the present application can be realized and obtained through the structures particularly pointed out in the written description, claims, and drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 A connection block diagram of a second embodiment of a method for strengthening the interface bonding between a Pt coating and a Ti substrate of the present application;

[0023] Figure 2 A connection block diagram of a third embodiment of a method for strengthening the interface bonding between a Pt coating and a Ti substrate of the present application;

[0024] Figure 3 This is the BSE microscopic morphology of the Pt-plated titanium felt after heat treatment in this application;

[0025] Figure 4 This is the XRD analysis result diagram of the Pt-plated titanium felt after heat treatment in this application;

[0026] Figure 5 This is the BSE microscopic morphology of the Pt-plated porous titanium sheet after heat treatment in this application;

[0027] Figure 6 This is the XRD analysis result diagram of the Pt-plated porous titanium sheet after heat treatment in this application;

[0028] Figure 7 This is the BSE microscopic morphology of the Pt-plated TC4 alloy after heat treatment in this application;

[0029] Figure 8 This is the XRD analysis result diagram of the Pt-plated TC4 alloy after heat treatment in this application;

[0030] Fig. 9 This is a comparison chart of the performance of a single cell tested by magnetron sputtering Pt titanium plate before and after heat treatment in this application;

[0031] Fig.10 This is a comparison chart of the single-cell test performance of electroplated Pt titanium felt before and after heat treatment for this application. DETAILED DESCRIPTION

[0032] In order to make the objectives, technical solutions and advantages of the present application more clearly understood, the present application is further described in detail below in combination with specific embodiments and with reference to the accompanying drawings.

[0033] The terms used in the embodiments of the present invention are only for the purpose of describing specific embodiments, and are not intended to limit the embodiments of the present invention. The singular forms "a", "said" and "the" used in the embodiments of the present invention and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings.

[0034] In view of the deficiencies in the prior art, the object of the present invention is to provide an interface bonding strengthening structure and method for a Pt coating and a Ti substrate, so as to achieve a substantial improvement in the Pt / Ti interface bonding strength without a significant increase in the contact resistance of the sample.

[0035] The basic idea of ​​the present invention is to adjust the heat treatment process parameters within a specific range, so that the temperature of the heat treatment equipment is heated to a preset temperature at a predetermined heating rate and kept at that temperature for a certain period of time, and then cooled to room temperature at a predetermined cooling rate, so as to form a Pt-Ti intermetallic compound and / or (Ti, Pt) at the interface between the Pt coating and the Ti substrate. ss Solid solution is used to achieve the interface bonding strengthening between Pt coating and Ti substrate.

[0036] The method specifically comprises:

[0037] Set the heat treatment atmosphere and heat treatment parameters;

[0038] The Ti substrate prefabricated with a Pt coating or stacked with a Pt foil is heat treated to 300-1200°C and kept warm for 1-200 minutes to form a Pt-Ti intermetallic compound and / or a (Ti, Pt)ss solid solution at the interface between the Pt coating and the Ti substrate, so as to achieve interface strengthening between the Pt coating or the Pt foil and the Ti substrate.

[0039] Therefore, by adjusting the heat treatment process parameters within a specific range, the Pt / Ti interface bonding is strengthened, ensuring the reliable bonding of the Pt coating and the Ti substrate. Under the heat treatment conditions of the present application, Pt atoms and Ti atoms diffuse with each other and react chemically to form Pt-Ti intermetallic compounds and / or (Ti, Pt) at the Pt / Ti interface. ss Solid solution, thereby achieving a substantial improvement in the interface bonding strength without a significant increase in the contact resistance of the sample.

[0040] Embodiment 1

[0041] In order to develop a method that can effectively improve the Pt / Ti interface bonding strength, the inventors have conducted in-depth research on heat treatment technology, an interface bonding strengthening structure between a Pt coating and a Ti substrate, the interface bonding structure includes a Pt-Ti intermetallic compound and / or (Ti, Pt) formed at the interface bonding between the Pt coating and the Ti substrate. ss Wherein, the Ti matrix is ​​made of Ti-based metal and alloy.

[0042] Specifically, XRD analysis can be used to verify whether Pt-Ti intermetallic compounds and / or (Ti, Pt) are formed at the contact interface between the Pt coating or Pt foil and the Ti substrate. ss Solid solution, if formed with Pt-Ti intermetallic compounds and / or (Ti,Pt) ss Solid solution, Pt / Ti interface bonding strength is high.

[0043] Embodiment 2

[0044] In order to develop a method that can effectively improve the bonding strength of the Pt / Ti interface, the inventors conducted in-depth research on heat treatment technology and proposed a method for strengthening the interface bonding between the Pt coating and the Ti substrate.

[0045] Specifically, Figure 1 As shown, a method for strengthening the interface bonding between a Pt coating and a Ti substrate comprises the following steps:

[0046] S1. Setting heat treatment atmosphere and heat treatment parameters;

[0047] S2. Heat-treating the Ti substrate prefabricated with a Pt coating or stacked with a Pt foil, heating to 300-1200° C. and keeping the temperature for 1-200 min, so that a Pt-Ti intermetallic compound and / or a (Ti, Pt)ss solid solution is formed at the interface between the Pt coating and the Ti substrate, so as to strengthen the interface between the Pt coating or the Pt foil and the Ti substrate;

[0048] S3. Place the Pt-plated titanium substrate obtained after heat treatment in deionized water for ultrasonic treatment for a certain period of time or use the bonding-peeling method or the scribing and chemical grid method to treat the Pt coating. Then use a SEM electron microscope to detect whether the Pt coating falls off or warps. If there is no falling off or warping, the production is qualified.

[0049] The heat treatment method can be carried out by one or more of the following methods: heating with heat treatment equipment (such as a heat treatment furnace), electromagnetic induction heating, microwave heating, direct current heating or laser heating. However, it is not necessarily limited to the above methods, and other methods that can heat the sample can also be used. When a heat treatment furnace is used for heating, the Ti substrate prefabricated with a Pt coating or stacked with a Pt foil can be first placed in the heat treatment furnace; then the heat treatment atmosphere in the heat treatment furnace is set, and the temperature in the furnace is heated to a preset temperature at a heating rate of 1 to 100°C / min and kept warm for 1 to 200 minutes, and then cooled to room temperature at a rate of 1 to 100°C / min to achieve interface bonding strengthening between the Pt coating or Pt foil and the Ti substrate.

[0050] Further preferably, the temperature in the above furnace can be heated to a preset temperature at a heating rate of 50 to 100° C. / min and kept warm for 100 to 200 minutes, and then cooled to room temperature at a rate of 60 to 100° C. / min.

[0051] Preferably, in order to further enhance the interface bonding effect between the Pt coating or Pt foil and the Ti substrate, when setting the heat treatment atmosphere in the heat treatment furnace, the temperature in the furnace can be selected to be heated to a preset temperature at a heating rate of 5 to 30°C / min and kept warm for 5 to 120 minutes, and then cooled to room temperature at a rate of 1 to 20°C / min to enhance the interface bonding strengthening effect.

[0052] Preferably, when the Ti substrate stacked with the Pt foil is placed in a heat treatment furnace, a certain axial pressure is applied to the stacked member consisting of the Pt foil and the Ti substrate to make the Pt foil close to the Ti substrate, so as to ensure good contact between the Pt foil and the surface of the Ti substrate. After the heat treatment is completed, the excess Pt foil on the substrate surface is torn off.

[0053] Preferably, the method of prefabricating the Pt coating is one or a combination of electroplating, brush plating, magnetron sputtering, plasma spraying, thermal spraying, cold spraying, chemical vapor deposition, physical vapor deposition, hot dip plating and powder metallurgy. Each of the above methods has its specific application scenarios and advantages. The choice of coating preparation method depends on factors such as the required coating performance, substrate type, cost-effectiveness and production efficiency.

[0054] Preferably, the step of setting the heat treatment atmosphere in the heat treatment equipment furnace includes setting the heat treatment atmosphere in the furnace to a high vacuum, a low vacuum, a reducing gas or an inert gas atmosphere, wherein the high vacuum atmosphere is 10 -2 ~10 -5 Pa, low vacuum atmosphere is 0.1~100Pa.

[0055] The reducing gas includes hydrogen, argon-hydrogen mixed gas or nitrogen-hydrogen mixed gas; the inert gas atmosphere adopts one or a combination of argon, nitrogen, neon and xenon.

[0056] Inert gas atmosphere is mainly used to prevent materials from reacting with oxygen or other active gases in the atmosphere at high temperatures, thereby protecting the surface of the material from oxidation or other chemical reactions. Because when heat treated in an oxygen-rich environment (such as air), Ti atoms will preferentially combine with O to form TiO2, causing the Pt coating to peel and fall off, and the contact resistance of the sample will increase sharply. When selecting the atmosphere, it is necessary to consider the chemical properties of the material, the expected reactivity, cost-effectiveness, availability, and the requirements of the specific process. For example, argon has become one of the most commonly used protective gases due to its chemical inertness, cost-effectiveness, and wide availability. However, in some specific cases, other gases or gas mixtures may need to be used to meet specific process or performance requirements.

[0057] Preferably, the Ti matrix is ​​made of TA1, TA2 or TC4 titanium alloy, or other Ti-based metals or alloys. Each titanium alloy has its own specific product characteristics, and the choice of alloy depends on the required application scenario and performance requirements.

[0058] Preferably, the interface bonding strengthening between the Pt coating or Pt foil and the Ti substrate is achieved by forming a Pt-Ti intermetallic compound and / or (Ti, Pt) at the contact interface between the Pt coating or Pt foil and the Ti substrate. ss Solid solution. The contact interface forms Pt-Ti intermetallic compounds and / or (Ti, Pt) ss The solid solution indicates that Pt atoms and Ti atoms diffuse with each other and react chemically, and the interface bonding strength will be substantially improved.

[0059] Preferably, the preset temperature is 300-1200°C, and specifically 1000-1200°C.

[0060] Embodiment 3

[0061] like Figure 2 As shown, it is a connection block diagram of a third embodiment of a method for strengthening the interface bonding between a Pt coating and a Ti substrate of the present application, which is different from the first embodiment in that, in this embodiment, it also includes:

[0062] S4. Perform XRD (i.e., X-ray diffraction) analysis on the Pt-plated titanium substrate obtained after heat treatment to observe whether Pt-Ti intermetallic compounds and / or (Ti, Pt) are formed at the contact interface between the Pt coating or Pt foil and the Ti substrate. ss Solid solution, if present, the production is qualified.

[0063] XRD analysis, or X-ray diffraction, is an important technique for analyzing the crystal structure of materials. By measuring the diffraction pattern of X-rays in a material, the crystal structure, phase composition, grain size, stress state and other properties of the material can be determined. XRD is a non-destructive analysis method that is widely used in the fields of materials science, earth science, chemistry, physics and engineering. Through XRD analysis, important information about the crystal structure and properties of a material can be obtained. In this embodiment, by performing XRD analysis on the Pt-plated titanium substrate obtained after heat treatment, it can be verified whether Pt-Ti intermetallic compounds and / or (Ti, Pt) are formed at the contact interface between the Pt coating or the Pt foil and the Ti substrate. ss Solid solution, if formed with Pt-Ti intermetallic compounds and / or (Ti,Pt) ss Solid solution, Pt / Ti interface bonding strength is high.

[0064] Embodiment 4

[0065] The heat-treated sample of a method for strengthening the interface bonding between a Pt coating and a Ti substrate provided in this embodiment is a Pt-plated titanium felt, and the method is carried out according to the following steps:

[0066] 1. The Pt-plated titanium felt prepared by electroplating is cleaned and dried by ultrasonic cleaning with anhydrous ethanol, and then placed in a heat treatment device;

[0067] 2. Vacuum the heat treatment equipment to 5×10 -3 Pa, heating to 400°C at a rate of 0-20°C / min, preferably 20°C / min, and keeping the temperature for 120 min;

[0068] 3. Cool the furnace to room temperature at a rate of 0-20°C / min, preferably 10°C / min, to achieve interface strengthening between the Pt coating and the Ti substrate.

[0069] 4. The Pt-plated titanium substrate obtained after heat treatment was subjected to XRD analysis.

[0070] 5. Place the heat-treated Pt-plated titanium felt in deionized water and use an ultrasonic cleaner (800W) for 60 minutes to perform ultrasonic treatment. Use a SEM electron microscope to detect whether the Pt coating has fallen off.

[0071] like Figure 3 As shown, this is a backscattering (BSE) microscopic morphology image of the Pt-plated titanium felt after heat treatment in this embodiment. It can be seen that there are a large number of bright white phases and a small amount of dark gray phases on the surface of the titanium felt, indicating that Pt atoms and Ti atoms diffuse with each other and undergo chemical reactions.

[0072] like Figure 4 As shown in FIG. 1 , the XRD analysis result of the Pt-plated titanium felt after heat treatment in this embodiment is shown. The XRD analysis results show that the titanium felt forms a Pt-Ti intermetallic compound phase and (Ti, Pt) ss Solid solution. Pt-Ti intermetallic compound and (Ti,Pt) ss The formation of solid solution indicates that metallurgical bonding has been formed between the Pt coating and the Ti substrate, which will substantially enhance the Pt / Ti interface bonding. After ultrasonic treatment, there is no sign of Pt coating falling off.

[0073] Embodiment 5

[0074] The difference between this embodiment and the fourth embodiment is that the embodiment is heated to 1200°C at a rate of 0-40°C / min, preferably 40°C / min, the holding time is 5 minutes, and the furnace is cooled to room temperature at a rate of 0-40°C / min, preferably 40°C / min. The other parameters and steps are the same as those of the fourth embodiment. XRD analysis detected that Pt-Ti intermetallic compounds and / or (Ti, Pt) were formed on the surface of the sample after heat treatment. ss After ultrasonic treatment, the Pt coating showed no signs of falling off, indicating that the Pt coating and the Ti substrate have been reliably combined.

[0075] Embodiment 6

[0076] The difference between this embodiment and the fourth embodiment is that the heat treatment equipment is in a low vacuum atmosphere, the vacuum degree is about 50Pa, and the other parameters and steps are the same as those of the fourth embodiment. XRD analysis detected that Pt-Ti intermetallic compounds and / or (Ti, Pt)ss solid solutions were formed on the surface of the sample after heat treatment. And after ultrasonic treatment, there was no sign of the Pt coating falling off, indicating that the Pt coating and the Ti substrate have been reliably combined.

[0077] Embodiment 7

[0078] The difference between this embodiment and the fourth embodiment is that the heat treatment equipment is inert gas atmosphere, the atmosphere is circulating or closed high-purity Ar atmosphere, and the other parameters and steps are the same as those of the third embodiment. XRD analysis detected that Pt-Ti intermetallic compounds and / or (Ti, Pt)ss solid solutions were formed on the surface of the sample after heat treatment. And after ultrasonic treatment, there is no sign of Pt coating falling off, indicating that the Pt coating has been reliably combined with the Ti substrate.

[0079] Embodiment 8

[0080] This embodiment is different from the fourth embodiment in that the heat-treated sample of this embodiment is a porous titanium sheet plated with Pt by brush plating. This embodiment is heated to 1100°C at a speed of 0 to 60°C / min, preferably 60°C / min, and the heat preservation time is 30 minutes. The furnace body is cooled to room temperature at a speed of 0 to 60°C / min, preferably 60°C / min. Other parameters and steps are the same as those of the fourth embodiment.

[0081] like Figure 5 and Figure 6 As shown, Figure 5 This is the BSE microscopic morphology of the Pt-plated porous titanium sheet after heat treatment in this embodiment. Figure 6 The XRD analysis result of the Pt-plated porous titanium sheet after heat treatment in this embodiment is shown in Figure 2. It can be seen that Pt-Ti intermetallic compounds and (Ti, Pt)ss solid solutions are formed on the surface of the Pt-plated porous titanium sheet after heat treatment. And after ultrasonic treatment, there is no sign of the Pt coating falling off, indicating that the Pt coating has been reliably combined with the Ti substrate.

[0082] Embodiment 9

[0083] The difference between this embodiment and the fourth embodiment is that the heat-treated sample is a porous titanium sheet plated with Pt by electroplating. This embodiment is heated to 700°C at a rate of 0-80°C / min, preferably 80°C / min, and the holding time is 30 minutes. The furnace body is cooled to room temperature at a rate of 20-80°C / min, preferably 80°C / min. The other parameters and steps are the same as those of the fourth embodiment. Pt-Ti intermetallic compounds and / or (Ti, Pt)ss solid solutions are formed on the surface of the Pt-plated porous titanium sheet after heat treatment. And after ultrasonic treatment, there is no sign of Pt coating falling off, indicating that the Pt coating has been reliably combined with the Ti substrate.

[0084] Embodiment 10

[0085] This embodiment is different from the fourth embodiment in that the heat-treated sample of this embodiment is a magnetron sputtered TC4 alloy. This embodiment is heated to 1000°C at a speed of 0 to 90°C / min, preferably 90°C / min, and the holding time is 20 minutes. The furnace body is cooled to room temperature at a speed of 50 to 90°C / min, preferably 90°C / min. Other parameters and steps are the same as those of the fourth embodiment.

[0086] like Figure 7 and Figure 8 As shown, Figure 7 This is the BSE microscopic morphology of the magnetron sputtering Pt TC4 alloy after heat treatment in this embodiment. Figure 8 The XRD analysis result of the magnetron sputtering Pt TC4 alloy after heat treatment in this embodiment is shown. It can be seen that Pt-Ti intermetallic compounds and (Ti, Pt)ss solid solutions are formed on the surface of the magnetron sputtering TC4 alloy after heat treatment. Due to the solid solution of Pt element in (Ti, Pt)ss solid solution, its lattice constant changes, and the diffraction angle in the corresponding XRD spectrum shifts relative to pure Ti. After heat treatment, the Pt coating is treated by bonding-peeling method and scribing and lattice method respectively, and then the Pt coating is detected by SEM electron microscope without falling off or warping, indicating that the Pt coating and the Ti substrate have been reliably combined.

[0087] Embodiment 11

[0088] This embodiment provides a Pt coating and Ti substrate bonding structure, the Pt coating and Ti substrate bonding structure is processed by the above method, and the Pt coating and Ti substrate bonding structure forms a Pt-Ti intermetallic compound and / or (Ti, Pt) at the contact interface between the two. ss Solid solution.

[0089] The combined structure of Pt (platinum) coating and Ti (titanium) substrate has a wide range of applications in many fields due to its unique physical and chemical properties.

[0090] For example, in the PEMWE hydrogen production system, the bipolar plate and transport layer on the anode side need to serve for a long time in a high potential and acidic environment, so Ti with good corrosion resistance is widely used as a material for preparing bipolar plates and transport layers. However, since Ti with high reactivity can easily combine with O to form TiO2, its contact resistance increases and seriously reduces the efficiency of water electrolysis, and a Pt coating is usually required on the surface of the Ti substrate.

[0091] For example, titanium alloys are widely used in medical devices such as artificial joints and dental implants due to their biocompatibility. Pt coating can provide additional wear resistance and corrosion resistance, extending the service life of the equipment.

[0092] It should be noted that other products produced by the above-mentioned method of strengthening the interface bonding between the Pt coating and the Ti substrate are also within the scope of protection of the present application, including but not limited to the Pt-plated titanium mesh used in the gas diffusion layer in the fuel cell; the Pt-plated titanium felt and Pt-plated porous titanium used in the transmission layer in the electrolytic hydrogen production electrolyzer; the Pt-plated titanium plate used for the bipolar plate in the electrolytic hydrogen production electrolyzer; and the Pt-plated titanium electrode used for the electrode in the electrolysis field.

[0093] Embodiment 12

[0094] This example provides the performance changes of magnetron sputtering Pt titanium plate in single cell test before and after heat treatment. The heat treatment conditions of Pt titanium plate are: heating to 800℃ at a rate of 95℃ / min, and keeping warm for 30min, high-purity Ar gas environment; the single cell test conditions are: the test active area is 5×5cm 2 , commercial membrane electrode, commercial transport layer, commercial carbon paper, test water temperature is 60oC, and assembly pressure is 2MPa.

[0095] Depend on Fig. 9 It can be seen that the performance of the single cell of the Pt-plated titanium plate after heat treatment is very close to that before heat treatment. 2 The corresponding voltage under the electric density is about 1.890 V. It can be seen that this heat treatment process not only enhances the bonding strength between the Pt coating and the Ti substrate, but also does not damage its electrochemical performance in the single cell, showing great practical application advantages.

[0096] Embodiment 13

[0097] This embodiment is different from the twelfth embodiment in that the heat-treated sample of this embodiment is electroplated Pt-plated titanium felt, this embodiment is heated to 900°C at a rate of 75°C / min, and the holding time is 20 minutes. The bipolar plate used in the single-cell test of this embodiment is an unheat-treated Pt-plated titanium plate, and the other parameters and steps are the same as those of the twelfth embodiment.

[0098] Depend on Fig.10It can be seen that the single cell performance of the Pt titanium felt after heat treatment is slightly better than that of the Pt titanium felt before heat treatment. 2 The corresponding voltages under electrical density are 1.890 V and 1.884 V. Similarly, while the heat treatment enhances the interfacial bonding strength between the Pt coating and the Ti felt, it does not damage its electrochemical performance in the single cell, showing great practical application advantages.

[0099] The above describes specific embodiments of the present invention. Other embodiments are within the scope of the appended claims. In some cases, the actions or steps recorded in the claims can be performed in an order different from that in the embodiments and still achieve the desired results. In addition, the processes depicted in the accompanying drawings do not necessarily require the specific order or continuous order shown to achieve the desired results. In some embodiments, multitasking and parallel processing are also possible or may be advantageous.

[0100] In the description of the embodiments of the present invention, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the embodiments of the present invention. In the embodiments of the present invention, the schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in the embodiments of the present invention and the features of the different embodiments or examples, without contradiction.

[0101] In addition, the terms "first" and "second" are used for descriptive purposes only and are not to be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features, and do not include any ordering. Thus, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features and are used to distinguish each other. In the description of the embodiments of the present invention, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0102] Any process or method description in a flowchart or otherwise described herein may be understood to represent a module, fragment or portion of code comprising one or more executable instructions for implementing the steps of a custom logical function or process, and the scope of the preferred implementation of the embodiments of the present invention includes alternative implementations in which functions may not be performed in the order shown or discussed, including performing functions in a substantially simultaneous manner or in reverse order depending on the functions involved, which should be understood by technicians in the technical field to which the embodiments of the present invention belong.

[0103] The above description is only a preferred embodiment of the embodiment of the present invention and is not intended to limit the embodiment of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the embodiment of the present invention should be included in the scope of protection of the embodiment of the present invention.

Claims

1. An interface bonding strengthening structure between a Pt coating and a Ti substrate, characterized in that: The interface bonding structure includes a Pt-Ti intermetallic compound and / or (Ti, Pt) formed at the interface bonding between the Pt coating and the Ti substrate. ss Solid solution.

2. The interface bonding structure according to claim 1, characterized in that: The Ti matrix is ​​made of Ti-based metal and alloy.

3. A method for strengthening the interface bonding between a Pt coating and a Ti substrate, characterized in that: The following steps are involved: Set the heat treatment atmosphere and heat treatment parameters; The Ti substrate prefabricated with a Pt coating or stacked with a Pt foil is heat treated to 300-1200°C and kept warm for 1-200 minutes to form a Pt-Ti intermetallic compound and / or a (Ti, Pt)ss solid solution at the interface between the Pt coating and the Ti substrate, so as to achieve interface strengthening between the Pt coating or the Pt foil and the Ti substrate.

4. The method according to claim 3, characterized in that The heat treatment is carried out by one or more of the following methods: heating by heat treatment equipment, electromagnetic induction heating, microwave heating, direct current application heating or laser heating.

5. The method according to claim 3, characterized in that: When the Ti substrate stacked with the Pt foil is subjected to heat treatment, a certain axial pressure is applied to the stacked member consisting of the Pt foil and the Ti substrate to make the Pt foil closely adhere to the Ti substrate.

6. The method according to claim 3, characterized in that: The method of prefabricating the Pt coating includes one or a combination of several methods selected from electroplating, brush plating, magnetron sputtering, plasma spraying, thermal spraying, cold spraying, chemical vapor deposition, physical vapor deposition, hot dip plating and powder metallurgy.

7. The method according to claim 3, characterized in that The step of setting the heat treatment atmosphere includes setting the heat treatment atmosphere to a high vacuum, a low vacuum, a reducing gas or an inert gas atmosphere, wherein the high vacuum atmosphere is 10 -2 ~10 -6 Pa, low vacuum atmosphere is 0.1~100Pa.

8. The method according to claim 7, characterized in that The reducing gas includes hydrogen, argon-hydrogen mixed gas or nitrogen-hydrogen mixed gas; the inert gas atmosphere adopts one or a combination of argon, nitrogen, neon and xenon.

9. The method according to claim 3, characterized in that: The method further comprises: placing the Pt-plated titanium substrate obtained after the heat treatment in deionized water for ultrasonic treatment for a certain period of time or treating the Pt coating by a bonding-peeling method or a scribing or chemical grid method, and then using a SEM electron microscope to detect whether the Pt coating falls off or warps, and if there is no falling off or warping, the production is qualified.

10. The method according to claim 3, characterized in that: The method further comprises: performing XRD analysis on the Pt-plated titanium substrate obtained after the heat treatment to observe whether Pt-Ti intermetallic compounds and / or (Ti, Pt) are formed at the contact interface between the Pt coating or the Pt foil and the Ti substrate. ss Solid solution, if present, the production is qualified.

11. The method according to claim 3, characterized in that The step of heat treating the Ti substrate prefabricated with a Pt coating or stacked with Pt foil also includes: heating the sample to a preset temperature at a heating rate of 1 to 100°C / min and keeping the temperature for 1 to 200 minutes, and then cooling to room temperature at a rate of 1 to 100°C / min.

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