CN116593259B - Copper-titanium diffusion couple and preparation method thereof - Google Patents
Copper-titanium diffusion couple and preparation method thereof Download PDFInfo
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- CN116593259B CN116593259B CN202310869707.5A CN202310869707A CN116593259B CN 116593259 B CN116593259 B CN 116593259B CN 202310869707 A CN202310869707 A CN 202310869707A CN 116593259 B CN116593259 B CN 116593259B
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- 238000009792 diffusion process Methods 0.000 title claims abstract description 212
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000010936 titanium Substances 0.000 claims abstract description 51
- 239000010949 copper Substances 0.000 claims abstract description 43
- 238000010438 heat treatment Methods 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 20
- 239000010935 stainless steel Substances 0.000 claims abstract description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000005272 metallurgy Methods 0.000 abstract description 2
- YADHPPSCECSOLO-UHFFFAOYSA-N [Sn]=O.[Zn].[Cu] Chemical compound [Sn]=O.[Zn].[Cu] YADHPPSCECSOLO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 238000001878 scanning electron micrograph Methods 0.000 description 16
- 229910017945 Cu—Ti Inorganic materials 0.000 description 10
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000010963 304 stainless steel Substances 0.000 description 4
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 4
- 230000008646 thermal stress Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 210000001503 joint Anatomy 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/225—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion
- G01N23/2251—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion using incident electron beams, e.g. scanning electron microscopy [SEM]
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- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of metallurgy, in particular to a copper-titanium diffusion pair and a preparation method thereof. The interface layer of the copper-titanium diffusion couple comprises Cu 4 Ti diffusion layer, cu 4 Ti 3 Diffusion layer, cuTi diffusion layer and CuTi 2 A diffusion layer; cuTi (copper zinc tin oxide) 2 The thickness of the diffusion layer is more than or equal to 1 mu m; the hardness of the copper-titanium diffusion couple is more than or equal to 160HV. The copper-titanium diffusion couple has high overall hardness and CuTi 2 The thickness of the diffusion layer is large. The preparation method of the copper-titanium diffusion couple comprises the following steps: the method comprises the steps that one surface of metallic copper is attached to one surface of metallic titanium by utilizing a molybdenum sheet, and a stainless steel fastener is used for locking and fixing the molybdenum sheet to obtain a connecting piece; heating the connecting piece to 740-890 ℃ at a heating rate of less than or equal to 10 ℃/min, preserving heat for 2-6 h, and cooling to obtain the copper-titanium diffusion couple. The copper-titanium diffusion couple prepared by the method has higher hardness and CuTi 2 The diffusion layer has a large thickness.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a copper-titanium diffusion pair and a preparation method thereof.
Background
Copper is a metal with conductivity inferior to silver and is cheaper, but pure copper has poor mechanical properties. Titanium has excellent properties such as high specific strength, good heat resistance and corrosion resistance, and is used as an indispensable structural material in the modern aerospace industry. The effective joint of copper and titanium not only can meet the requirements of heat conduction, wear resistance and corrosion resistance, but also can meet the requirements of light weight and high strength, and has wide application prospect in the fields of aerospace, ships, instruments and meters and the like. The application of the dissimilar metal joint in aerospace, instruments and meters, electronic equipment and heat exchanger parts, especially the wide application of the copper-titanium joint, needs to be deeply understood about the adhesion and connection of the copper-titanium joint, and the adoption of the method for preparing the copper-titanium diffusion pair can directly study the performance of the copper-titanium joint, so that the method is a main method for researching the tissue performance of the copper-titanium joint at present.
CuTi is present in copper-titanium diffusion couple 2 、CuTi、Cu 4 Ti 3 、Cu 4 Ti and solid solutions. Due to the low diffusion rate, each diffusion layer has a thickness of only a few microns even if the diffusion time is long enough, which makes it difficult to study each diffusion layer in a copper-titanium diffusion couple. It is therefore desirable to produce copper-titanium diffusion couples with thicker diffusion layers. The interface region structure strongly influences the hardness of the copper-titanium diffusion couple, so that the diffusion couple is required to have higher hardness as a whole, whereas CuTi 2 Has the highest hardness in copper-titanium diffusion couple four phases, but the thickness is often less than 1 micron for CuTi 2 Is difficult to study and regulate.
Thus, a thick CuTi is provided 2 The copper-titanium diffusion couple with high hardness has important significance.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a copper-titanium diffusion couple, cuTi in which 2 The thickness of the diffusion layer is large, and the copper-titanium diffusion couple is high in overall hardness.
The second aim of the invention is to provide a preparation method of the copper-titanium diffusion couple, which has higher hardness and CuTi 2 The diffusion layer has a large thickness.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a copper-titanium diffusion couple, the interface layer of which comprises Cu 4 Diffusion of TiLayer, cu 4 Ti 3 Diffusion layer, cuTi diffusion layer and CuTi 2 A diffusion layer; wherein the CuTi 2 The thickness of the diffusion layer is more than or equal to 1 mu m; the hardness of the copper-titanium diffusion couple is more than or equal to 160HV.
The invention also provides a preparation method of the copper-titanium diffusion couple, which comprises the following steps:
a molybdenum sheet is utilized to enable one surface of metallic copper to be attached to one surface of metallic titanium, and a stainless steel fastener is utilized to lock and fix the molybdenum sheet, so that a connecting piece is obtained;
heating the connecting piece to 740-890 ℃ at a heating rate of less than or equal to 10 ℃/min, preserving heat for 2-6 hours, and cooling to obtain the copper-titanium diffusion couple;
wherein the heating is performed under vacuum of 1×10 -3 Pa~5×10 -3 Under vacuum conditions of Pa.
Compared with the prior art, the invention has the beneficial effects that:
(1) The copper-titanium diffusion couple provided by the invention has uniform tissue components and CuTi 2 The diffusion layer has a large thickness. In addition, the copper-titanium diffusion couple has excellent comprehensive performance, in particular to excellent room temperature hardness.
(2) The preparation method of the copper-titanium diffusion couple provided by the invention can improve the room temperature hardness of the copper-titanium diffusion couple and improve the CuTi 2 Thickness of the diffusion layer.
(3) The copper-titanium diffusion couple prepared by the preparation method provided by the invention has uniform concentration gradient, and the uniformity of material performance is ensured.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a copper-titanium diffusion pair provided in example 1 of the present invention;
FIG. 2 is an SEM image of a copper-titanium diffusion pair according to example 2 of the present invention;
FIG. 3 is an SEM image of a copper-titanium diffusion pair provided in example 3 of the present invention;
FIG. 4 is an SEM image of a copper-titanium diffusion pair provided in example 4 of the present invention;
FIG. 5 is an SEM image of a copper-titanium diffusion pair provided in example 5 of the present invention;
FIG. 6 is an SEM image of a copper-titanium diffusion pair provided in comparative example 1 of the present invention;
FIG. 7 is an SEM image of a copper-titanium diffusion pair provided in comparative example 2 of the present invention;
FIG. 8 is an SEM image of a copper-titanium diffusion pair provided in comparative example 3 of the present invention;
FIG. 9 is a scan of copper-titanium diffusion even lines provided in example 1 of the present invention;
FIG. 10 is a scan of copper-titanium diffusion even lines provided in example 2 of the present invention;
FIG. 11 is a scan of copper-titanium diffusion even lines provided in example 3 of the present invention;
fig. 12 is a scan of copper-titanium diffusion even lines provided in example 4 of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In a first aspect, the present invention provides a copper-titanium diffusion couple consisting essentially of metallic copper and metallic titanium which undergo atomic diffusion upon heating, the copper-titanium diffusion couple comprisingThe interface layer of the copper-titanium diffusion couple comprises Cu 4 Ti diffusion layer, cu 4 Ti 3 Diffusion layer, cuTi diffusion layer and CuTi 2 And a diffusion layer.
Wherein the CuTi 2 The thickness of the diffusion layer is more than or equal to 1 mu m; including but not limited to a dot value of any one of 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2 μm, or a range value between any two.
The hardness of the copper-titanium diffusion couple is more than or equal to 160HV, including but not limited to a point value of any one of 170HV, 180HV, 190HV, 200HV, 210HV, 220HV, 230HV, 240HV, 250HV, 260HV, 270HV, 280HV, 290HV or a range value between any two. The hardness refers to room temperature hardness.
The copper-titanium diffusion couple provided by the invention has uniform tissue components and four uniform diffusion layers, wherein the uniformity refers to the uniformity of the thickness of each diffusion layer, and the element content of each diffusion layer is uniform (the element content uniformity result can be confirmed by a line scanning detection result). The uniform thickness of each diffusion layer can obtain more accurate diffusion kinetics results. While the elemental content of each diffusion layer is uniform so that the properties of the characterized diffusion layer are consistent with the properties of the corresponding compound.
The copper-titanium diffusion couple provided by the invention has enough thickness of each diffusion layer, especially CuTi 2 The thickness of the diffusion layer is more than or equal to 1 mu m, and the processing detection is convenient. In addition, the copper-titanium diffusion couple Kendall hole and other defects are few, the comprehensive performance is excellent, and particularly the copper-titanium diffusion couple has excellent hardness, and the room temperature hardness of the copper-titanium diffusion couple is more than or equal to 160HV.
In a preferred embodiment, the Cu 4 The thickness of the Ti diffusion layer is 3 μm or more, including but not limited to a dot value of any one of 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm or a range value between any two.
In a preferred embodiment, the Cu 4 Ti 3 The thickness of the diffusion layer is ≡4 μm, including but not limited to a dot value of any one of 4.5 μm, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm, 10 μm or a range between any two.
In a preferred embodiment, the thickness of the CuTi diffusion layer is 10 μm or more, including but not limited to a dot value of any one of 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm or a range value between any two.
In a preferred embodiment, the total thickness of the interfacial layer of the copper-titanium diffusion couple is 15 μm to 35 μm, including but not limited to a point value of any one of 16 μm, 18 μm, 19 μm, 20 μm, 23 μm, 25 μm, 28 μm, 30 μm, 33 μm, or a range value between any two.
In a preferred embodiment, the copper-titanium diffusion couple is mainly obtained by heating metallic copper and metallic titanium at 740-890 ℃ at a heating rate of less than or equal to 10 ℃/min. The CuTi with high hardness can be obtained by adopting the heating temperature and the heating rate 2 Copper-titanium diffusion couple with large diffusion layer thickness.
In a second aspect, the invention provides a method for preparing a copper-titanium diffusion couple, comprising the following steps:
and (3) attaching one surface of the metallic copper to one surface of the metallic titanium by utilizing the molybdenum sheet, and locking and fixing the molybdenum sheet by adopting a stainless steel fastener to obtain the connecting piece.
Heating the connecting piece to 740-890 ℃ at the heating rate of less than or equal to 10 ℃/min, preserving heat for 2-6 h, and cooling to obtain the copper-titanium diffusion couple.
Wherein the heating is performed under vacuum of 1×10 -3 Pa~5×10 -3 Under vacuum conditions of Pa.
It will be appreciated that the molybdenum sheet has through holes through which stainless steel fasteners can pass. In the preparation process, two molybdenum sheets are adopted to clamp metallic copper and metallic titanium, so that one surface of the metallic copper is attached to one surface of the metallic titanium, and then a stainless steel fastener is penetrated into the through holes of the two molybdenum sheets to realize locking and fixing, thus obtaining the connecting piece.
The metal molybdenum is adopted, and does not react with metal copper or metal titanium at high temperature, namely, does not participate in the reaction of diffusion couple; and the adhesive has certain dimensional stability at high temperature and certain strength, and can play a role in fixation.
The stainless steel fastener is adopted, and the stainless steel can meet the strength condition, so that the firm matrix after connection is ensured. Because diffusion couples occur with increasing temperature of the heat, the fastener is required to have sufficient strength to ensure that it is not affected by high temperature expansion. In addition, the stainless steel has a heat conduction coefficient and a thermal expansion coefficient matched with those of the matrix material, and if the heat conduction coefficient is lower, the heating condition of the matrix metal can be influenced, the diffusion efficiency is reduced, and the thickness of the diffusion layer is further influenced; if the coefficients of thermal expansion are not matched, stresses occur at the contact of the fastener and the base material when the temperature increases, which can affect the overall performance of the diffusion couple.
The preparation method adopts specific heating rate and heating temperature, and the four diffusion layers of the prepared copper-titanium diffusion couple have larger thickness, especially CuTi 2 The thickness of the diffusion layer is more than or equal to 1 mu m. In addition, the copper-titanium diffusion couple has higher room temperature hardness and excellent comprehensive performance.
Specifically, because the thermal expansion coefficients of Cu and Ti are different, if the temperature rising and falling rate is too high in the diffusion process, residual thermal stress is easily generated at the interface, so that the mechanical property of the diffusion couple is reduced, even the diffusion couple is broken, and the preparation is failed. The residual thermal stress can be reduced by adopting the temperature rising rate, so that the influence on the diffusion couple mechanical property is reduced.
Further, the copper-titanium diffusion couple prepared by adopting the heating temperature has a uniform concentration gradient, wherein uniform refers to uniform thickness of each diffusion layer and uniform element content of each diffusion layer, the uniform thickness of each diffusion layer can more accurately obtain dynamic behaviors of diffusion, the uniform element content of each diffusion layer can ensure that the diffusion layer is better matched with a corresponding compound, and then the performance characterization of the diffusion layer can represent the performance of the compound, exclude other influences and ensure that the material has uniform properties; the gradient is that Cu content of each diffusion layer is sequentially reduced and Ti content is sequentially increased from Cu layer to Ti layer in the copper-titanium diffusion couple.
In addition, the preparation method is simple to operate, short in process flow and low in cost.
In the heating process, the temperature rising rate comprises but notA point value limited to any one of 9 ℃/min, 8 ℃/min, 7 ℃/min, 6 ℃/min, 5 ℃/min, or a range value between any two; the temperature of heating includes, but is not limited to, any one of a point value or a range value between any two of 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃, 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃; the heat preservation time of the heating comprises, but is not limited to, any one point value or range value between any two of 3h, 4h and 5 h; vacuum level includes, but is not limited to, 2X 10 -3 Pa、3×10 -3 Pa、4×10 -3 A point value of any one of Pa or a range value between any two.
Ti element is easily oxidized at high temperature, and if Ti element is oxidized in the diffusion process, ti oxide is formed on the surface, so that diffusion of the Cu matrix and the Ti matrix is blocked, and a diffusion reaction cannot be performed, therefore, in order to ensure that Ti is not oxidized and diffusion reaction with Cu occurs, the diffusion process needs to be performed under the vacuum condition.
By adopting the preparation parameters, the mutual diffusion between the metallic copper and the metallic titanium can be fully completed; and the prepared copper-titanium diffusion couple has more uniform concentration gradient.
In a preferred embodiment, the temperature rise rate is 8 ℃/min to 10 ℃/min, including but not limited to a point value of any one of 8.5 ℃/min, 9 ℃/min, 9.5 ℃/min, or a range value between any two.
In a preferred embodiment, the cooling rate in the cooling process is 8 ℃/min to 10 ℃/min, including but not limited to any one of 8.5 ℃/min, 9 ℃/min, 9.5 ℃/min, or a range between any two. By adopting the cooling rate, the residual thermal stress can be further reduced, so that the excellent mechanical property of the diffusion couple is ensured.
In a preferred embodiment, the shapes of the metallic copper and the metallic titanium are blocky, and the purities of the metallic copper and the metallic titanium are more than or equal to 99.9 percent; the metallic molybdenum having the through-holes has a sheet shape.
In a preferred embodiment, the stainless steel fastener comprises at least one of a stainless steel screw, a stainless steel bolt, a stainless steel stud, and a stainless steel pin.
In a preferred embodiment, the stainless steel fastener material comprises 304 stainless steel.
In a preferred embodiment, the heating is performed in a vacuum and protective atmosphere.
In a preferred embodiment, the heating is performed in a high temperature vacuum oven.
In a preferred embodiment, the metallic copper and metallic titanium are pretreated prior to fixing to remove the oxide layer on the metallic copper and metallic titanium surfaces. The pretreatment method comprises grinding, polishing, cleaning and drying.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The purity of the copper metal block and the titanium metal block used in each of the following examples of the present invention was 99.9%, and the sizes of the copper metal block and the titanium metal block were 10mm×10mm×5mm (length×width×height).
The molybdenum metal sheets used in the following examples of the present invention were 40mm by 25mm by 1mm (length by width by height).
The dimensions of the 304 stainless steel screws used in the following examples of the invention are: the diameter of the thread is 5mm, and the length of the thread is 30mm.
Example 1
The preparation method of the copper-titanium diffusion couple provided by the embodiment comprises the following steps:
step (1), sample processing: sequentially polishing the copper metal block and the titanium metal block by using 400-mesh, 800-mesh, 1500-mesh and 2000-mesh metallographic sand paper, removing the surface oxide layer by polishing, respectively cleaning by using absolute ethyl alcohol and acetone, and drying by using hot air of a blower. And round holes with diameter phi=8mm are drilled at the positions 7mm away from the boundary at the four corners of the molybdenum sheet.
Step (2), assembling a clamp: and (3) butt-jointing the polished surfaces of the copper metal block and the titanium metal block, then adopting two molybdenum sheets to be respectively stuck to the upper surface of the copper metal block and the lower surface of the titanium metal block (namely, the surface of the metal block which is not in butt joint is stuck with the molybdenum sheets), and connecting the two molybdenum sheets by utilizing 304 stainless steel screws to obtain the connecting piece.
Step (3), heating: heating the connecting piece prepared in the step (2) in a high-temperature vacuum furnace under the protection of nitrogen, and keeping the vacuum degree at 1.0x10 -3 Pa; heating from room temperature to 890 ℃ at a heating rate of 9 ℃/min, preserving heat for 4 hours, cooling to room temperature at a cooling rate of 9 ℃/min, and taking out and removing the molybdenum sheet and the 304 stainless steel screw to obtain the copper-titanium diffusion couple.
As shown in FIG. 1, which is an SEM image of the Cu-Ti diffusion couple, the interfacial layer of the Cu-Ti diffusion couple comprises Cu 4 Ti diffusion layer, cu 4 Ti 3 Diffusion layer, cuTi diffusion layer and CuTi 2 Diffusion layers, and the thicknesses of the four phase layer diffusion layers were 5.39 μm, 7.11 μm, 14.6 μm, and 1.78 μm, respectively.
Example 2
The preparation method of the copper-titanium diffusion couple provided in this example is basically the same as that of example 1, except that in step (3), the heating temperature is replaced with 840 ℃.
As shown in FIG. 2, which is an SEM image of the Cu-Ti diffusion couple, the interfacial layer of the Cu-Ti diffusion couple comprises Cu 4 Ti diffusion layer, cu 4 Ti 3 Diffusion layer, cuTi diffusion layer and CuTi 2 Diffusion layers, and the thicknesses of the four phase layer diffusion layers were 4.43 μm, 5.97 μm, 13.40 μm, and 1.31 μm, respectively.
Example 3
The preparation method of the copper-titanium diffusion couple provided in this example is basically the same as that of example 1, except that in step (3), the heating temperature is replaced with 790 ℃.
As shown in FIG. 3, which is an SEM image of the Cu-Ti diffusion couple, the interfacial layer of the Cu-Ti diffusion couple comprises Cu 4 Ti diffusion layer, cu 4 Ti 3 Diffusion layer, cuTi diffusion layer and CuTi 2 Diffusion layers, and the thicknesses of the four phase layer diffusion layers were 3.40 μm, 4.42 μm, 10.70 μm, and 1.16 μm, respectively.
Example 4
The preparation method of the copper-titanium diffusion couple provided in this embodiment is basically the same as that in embodiment 3, except that in step (3), the heat preservation time is replaced by 5h.
As shown in FIG. 4, which is an SEM image of the Cu-Ti diffusion couple, the interfacial layer of the Cu-Ti diffusion couple comprises Cu 4 Ti diffusion layer, cu 4 Ti 3 Diffusion layer, cuTi diffusion layer and CuTi 2 Diffusion layers, and the thicknesses of the four phase layer diffusion layers were 4.07 μm, 4.29 μm, 10.60 μm, and 1.15 μm, respectively.
Example 5
The preparation method of the copper-titanium diffusion couple provided in this example is basically the same as that of example 3, except that in step (3), the heating rate is replaced by 8 ℃/min.
As shown in FIG. 5, which is an SEM image of the Cu-Ti diffusion couple, the interfacial layer of the Cu-Ti diffusion couple comprises Cu 4 Ti diffusion layer, cu 4 Ti 3 Diffusion layer, cuTi diffusion layer and CuTi 2 Diffusion layers, and the thicknesses of the four phase layer diffusion layers were 4.15 μm, 4.46 μm, 13.6 μm, and 1.18 μm, respectively.
From the above results, it is understood that the temperature rise rate is reduced in example 5 compared with example 3, and the thickness of each of the four diffusion layers is increased.
Furthermore, as can be seen from fig. 1, 2, 3, 4 and 5, the thickness of each diffusion layer is substantially uniform and the boundaries are clear. This shows that the thickness of each diffusion layer of the copper-titanium diffusion pair provided by the invention is uniform.
Comparative example 1
The preparation method of the copper-titanium diffusion couple provided in this comparative example is substantially the same as in example 3, except that in step (3), the heating temperature is replaced with 700 ℃.
An SEM image of the copper-titanium diffusion couple produced in this comparative example is shown in fig. 6.
Comparative example 2
The preparation method of the copper-titanium diffusion couple provided in this comparative example was substantially the same as in example 3, except that in step (3), the heating temperature was replaced with 950 ℃.
An SEM image of the copper-titanium diffusion couple produced in this comparative example is shown in fig. 7.
Comparative example 3
The preparation method of the copper-titanium diffusion couple provided in this comparative example is basically the same as that of example 3, except that in step (3), the temperature rising rate is replaced with 20 ℃/min.
An SEM image of the copper-titanium diffusion couple produced in this comparative example is shown in fig. 8.
Experimental example 1
The room temperature hardness (25 ℃) of the copper-titanium diffusion couple obtained in each of the above examples and each of the comparative examples was measured, and the results are shown in Table 1.
Table 1 Room temperature hardness results for copper-titanium diffusion couples
As can be seen from Table 1, the copper-titanium diffusion couple prepared in each example has a relatively high room temperature hardness. In particular, the room temperature hardness of example 1 is as high as 241HV.
Comparative example 1, however, does not have uniform CuTi due to the use of too low a heating temperature 2 A diffusion layer is present; comparative example 2 caused melting of the diffusion couple due to the excessively high heating temperature, without an obvious diffusion layer; comparative example 3 has residual thermal stress at the interface of the diffusion couple due to the excessively high temperature rising rate, resulting in cracking of the diffusion couple.
Experimental example 2
In order to verify that the element content of each diffusion layer of the copper-titanium diffusion couple prepared by the method is uniform, the concentration content test (line scanning) of copper element and titanium element is carried out on the copper-titanium diffusion couples prepared by the examples 1-4 respectively, and the results are shown in fig. 9-12. Wherein, FIG. 9 is a scanning graph of copper-titanium diffusion even lines prepared in example 1; FIG. 10 is a scan of copper-titanium diffusion even lines obtained in example 2; FIG. 11 is a scan of copper-titanium diffusion even lines obtained in example 3; FIG. 12 is a scan of copper-titanium diffusion even lines obtained in example 4. The ordinate unit at.% in fig. 9 to 12 represents the atomic percentage (mole fraction).
As can be seen from fig. 9 to 12, the atomic percentage of each diffusion layer is approximately in a straight line state, i.e., the element contents are substantially uniform, which means that each diffusion layer has a uniform concentration.
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.
Claims (5)
1. A copper-titanium diffusion couple, which is characterized in that an interfacial layer of the copper-titanium diffusion couple comprises Cu 4 Ti diffusion layer, cu 4 Ti 3 Diffusion layer, cuTi diffusion layer and CuTi 2 A diffusion layer;
wherein the CuTi 2 The thickness of the diffusion layer is more than or equal to 1 mu m;
the hardness of the copper-titanium diffusion couple is more than or equal to 160HV;
the preparation method of the copper-titanium diffusion couple comprises the following steps: a molybdenum sheet is utilized to enable one surface of metallic copper to be attached to one surface of metallic titanium, and a stainless steel fastener is utilized to lock and fix the molybdenum sheet, so that a connecting piece is obtained; heating the connecting piece to 790-890 ℃ at a heating rate of 8-10 ℃/min, preserving heat for 4-6 hours, and cooling to obtain the copper-titanium diffusion couple; the heating is performed under vacuum degree of 1×10 -3 Pa~5×10 -3 Under vacuum conditions of Pa;
the cooling rate in the cooling process is 8-10 ℃/min.
2. The copper-titanium diffusion pair of claim 1, wherein the Cu 4 The thickness of the Ti diffusion layer is more than or equal to 3 mu m.
3. The copper-titanium diffusion pair of claim 1, wherein the Cu 4 Ti 3 The thickness of the diffusion layer is more than or equal to 4 mu m.
4. The copper-titanium diffusion pair according to claim 1, wherein the thickness of the CuTi diffusion layer is not less than 10 μm.
5. The copper-titanium diffusion pair of claim 1, wherein the stainless steel fastener comprises at least one of a stainless steel screw, a stainless steel bolt, a stainless steel stud, and a stainless steel pin.
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