CN1583354A - Method for connecting diamond thick film with hard base firmly - Google Patents
Method for connecting diamond thick film with hard base firmly Download PDFInfo
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- CN1583354A CN1583354A CN 200410010895 CN200410010895A CN1583354A CN 1583354 A CN1583354 A CN 1583354A CN 200410010895 CN200410010895 CN 200410010895 CN 200410010895 A CN200410010895 A CN 200410010895A CN 1583354 A CN1583354 A CN 1583354A
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- film
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- diamond
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Abstract
A technology for firmly joining thick film of diamond with hard substrate includes such steps as pretreating, sequentially stacking the subsrate, Ag.Cu alloy sheet, Ti foil or TiH2 (or Ti) powder, and thick film of diamond and table in vacuum furnace, vacuumizing, heating to 870 degc, holding the temp for 40-60 min, cooling to 500 deg.C at 8-12 deg.C/min and natural cooling.
Description
Technical field
The invention belongs to the welding field of superhard material, particularly the method for attachment of diamond film and matrix.
Background technology
Diamond is difficult to not affinity of it and other material firmly be connected with other material because the characteristic of itself makes.The CVD diamond film is a kind of new material, it is to be the synthetic a kind of flaky material that is made of diamond fully of raw material with the hydrocarbon gas with chemical gaseous phase depositing process, wherein do not contain other impurity, have the various excellent properties identical, utilize diamond thick-film to make various machining tools and have broad application prospects with natural diamond.But, make it and other material form and firmly be connected to become difficulty just because of diamond film has the character identical with natural diamond.Reach diamond and other object forms firm purpose of connecting, address the problem 1, will form one deck carburization zone, make diamond film and be connected object and form metallurgical binding as transition by carburization zone on the diamond film surface; 2, since diamond and the thermal coefficient of expansion that is connected between the object (matrix of carbide alloy or steel material) differ greatly, and welding all is at high temperature to carry out, therefore the internal stress that in welding process, produces must be eliminated, otherwise firm the connection can not be formed between diamond and the matrix.
With the close prior art of the present invention is the article that is published in " welding journal " the 20th volume the 1st phase (1999.3) P43～47, and exercise question is " diamond thick-film is connected with carbide alloy ".The disclosed technology contents of this paper is, between CVD diamond thick-film (thickness 30 μ m) and carbide alloy (YG8), " intermediate layer material of interpolation is made up of pure Ti paper tinsel and Ag-Cu Alloy Foil "; Arrange in proper order by carbide alloy, Ag-Cu Alloy Foil, Ti paper tinsel, diamond film, on vacuum radiation heating diffusion welding machine, connect, impose certain pressure thereon, the insulation that increases temperature and pass through certain hour under vacuum environment links together diamond film and carbide alloy (WC)." concrete parameter is as follows: vacuum B=2.5 * 10
-3Pa; Heating-up temperature T=880 ℃; Heating-cooling speed v=30 ℃/min; Temperature retention time t=30min; P=10Pa exerts pressure "." result has formed more firm metallurgy and has connected.”
This paper is also pointed out " thickness of film is big more, and thermal stress is also big more, and easy more and matrix breaks away from "." active element Ti is the necessary condition that realizes that metal is connected with diamond with the chemical reaction of forming between the adamantine C element.According to diffusion law and kinetics, only under the situation of certain temperature and temperature retention time, this reaction just can be carried out.But if temperature is too high, the time is oversize, and causing generating excessive carbide also can influence strength of joint.Therefore, must preferred optimal processing parameter.This part work awaits further research." in addition; though the Ti paper tinsel at high temperature can form skim TiC with the carbon of diamond surface; the thickness of this layer TiC generally has only several microns; thereby be that the Ti paper tinsel of 30 μ m can not melt fully by the Ag-Cu alloy and dilutes; still have one deck Ti to exist and the Ag-Cu alloy flow after the fusing formed and hinder, can not make liquid Ag-Cu alloy contact the formation metallurgical binding with the TiC layer as adding material thickness; At this moment cross section actual distribution is hard substrate from bottom to top, Ag-Cu alloy, Ti layer, TiC layer, diamond film.The existence of Ti layer has also increased the fragility of solder side, makes weld interface produce very big internal stress simultaneously, and these all can influence diamond film and be connected high base strength.
Summary of the invention
The technical problem to be solved in the present invention is to overcome disadvantages of background technology, and technical process and process conditions that preferred diamond thick-film is connected with carbide alloy or steel matrix reach the purpose that technology is simple, be suitable for practicality, firm welding.
The technical process that diamond thick-film of the present invention is connected with matrix is pre-treatment process, charging process, welding process in order.Still selecting Ag-Cu alloy and Ti paper tinsel is solder; Said charging process is, presses the order of matrix, Ag-Cu alloy, Ti paper tinsel, diamond thick-film, is placed on the loading platform of vacuum drying oven, and applies the pressure of 10Mpa magnitude thereon.Said pre-treatment process is that diamond thick-film boils the clear water flushing again in the mixed solution of sulfuric acid, nitric acid, remove the surface film oxide that matrix is connected face, with acetone or carbon tetrachloride diamond thick-film, solder, matrix surface is carried out oil removal treatment.Said welding process is that vacuum drying oven is evacuated to 1 * 10
-3～2 * 10
-3Pa is warming up to 860～890 ℃ with 10～20 ℃/min heating rate, constant temperature 40～60min, and the rate of temperature fall with 8～12 ℃/min is cooled to 600～400 ℃ afterwards, is cooled to room temperature more naturally.Said Ag-Cu alloy be sheet or sheet netted, the Ti paper tinsel is that sheet is netted.
Selected Ag-Cu alloy can be the 72Ag-28Cu alloy, and thickness can be 200～300 μ m; The thickness of Ti paper tinsel can be 20～40 μ m.The Ag-Cu alloy that sheet is netted or the netted aperture of Ti paper tinsel can be 0.2～0.8mm, and the interval of Kong Yukong can be 0.4～0.7mm.
Said solder Ti can use TiH
2The pasty mixture of powder or Ti powder and ethanol, when filling with substance are filled in the mesh of the netted Ag-Cu alloy of sheet, place between diamond thick-film and the matrix again and weld.
When the thickness of diamond thick-film is bigger, such as greater than 150 μ m, aufwuchsplate does not have through milled processed, for guaranteeing bond strength, can select smoother substrate surface as joint face.
The said hard substrate of the present invention mainly is meant carbide alloy WC-6%Co or WC-8%Co and 40Cr or 45
#Steel.
Diamond thick-film of the present invention forms the firm method that is connected with hard substrate, owing to make the Ti paper tinsel netted or use TiH
2Or the Ti powder, comparing with background technology has had basic variation, can avoid Ti to have the obstruction that the Ag-Cu alloy flow after the fusing is formed with the form of layer, and at high temperature Ye Tai Ag-Cu alloy can arrive each position of faying face; Again because the strong osmosis of Ti metal, along with flowing of the Ag-Cu alloy of liquid state, part Ti and Ag-Cu alloy form liquid Ag-Cu-Ti alloy and arrive whole solder side, with the TiC formation metallurgical binding on diamond film surface.Simultaneously, the speed of intensification and cooling is low in the process conditions, and temperature retention time is longer, helps eliminating the internal stress that produces in welding process.Thereby make diamond film and be connected object and firmly be connected.Product with method welding of the present invention is checked through tensile testing machine, shear strength is all greater than 160MPa, maximum has reached 209MPa, product draws back the back and all leave solder on the solder side of diamond thick-film and matrix, diamond film does not break away from solder layer, illustrates that solder is all very firm with being connected of diamond thick-film and matrix.
The specific embodiment
Embodiment 1
The pre-treatment process:
A. diamond thick-film places sulfuric acid: the mixed solution of nitric acid=3: 1 boiled 20 minutes, removed the impurity such as graphite on diamond film surface, with clear water well-done diamond film was rinsed well.
B. with the face that is connected of processing carbide alloy such as emery wheel or grinding machine or sand paper or steel, remove surface film oxide.
C. prepare the suitable 72Ag-28Cu alloy of size according to actual needs, general thickness is 0.2～0.3mm.Prepare size and the essentially identical netted Ti paper tinsel of Ag-Cu alloy, general thickness is 20～40 μ m.
D. with acetone or carbon tetrachloride to diamond thick-film, solder, be connected matrix surface and carry out oil removal treatment.
The charging process:
By order from bottom to top carbide alloy or steel, Ag-Cu alloy, netted Ti paper tinsel, diamond thick-film are stacked sample, lie on the loading platform in the vacuum drying oven, press weight in the above, pressure is about 10MPa.
Be preferably between sample and the weight and separate, prevent that a sample and weight briquetting are welded together with graphite flake.
Welding process:
Vacuum drying oven is evacuated to 1.5 * 10
-3～1.8 * 10
-3Begin during Pa to heat, programming rate is 15 ℃/min, begins insulation when temperature is raised to 870 ℃, constant temperature time 50min, and 10 ℃/min of rate of temperature fall, cooling naturally when reducing to 500 ℃ is opened vacuum chamber and is taken out sample when temperature is reduced to room temperature.
By above-mentioned pre-treatment, charging, welding procedure, all very firm until the diamond thick-film of 1.6mm to thickness with being connected of carbide alloy or steel at 90,160,400,900 μ m, shear strength is all greater than 160MPa, and the 209MPa of shear strength maximum obtains when the 1.6mm thickness is tested.
Embodiment 2
Use netted 72Ag-28Cu alloy and TiH
2Powder is that its body way of additive is exemplified as: it is netted that thickness is that the 72Ag-28Cu alloy sheet of 0.3mm is made, and the aperture is about 0.5mm, and Kong Yukong is spaced apart 0.5-0.6mm; With ethanol and TiH
2Powder mixes and stirs in the hole that pasty state is filled into the Ag-Cu alloy sheet, and is placed on diamond film and is connected between the object.Other technical process is identical with embodiment 1.TiH
2The granularity of powder is 50 μ m with carefully, and present embodiment uses the TiH of 30 μ m
2Powder.
The Ag-Cu alloy is liquid under the high temperature, TiH
2Be reduced into Ti, it is wandering to arriving a solder side that part Ti and liquid Ag-Cu alloy form the Ag-Cu-Ti alloy, Ti forms TiC to the diamond thick-film diffusion into the surface and on the diamond thick-film surface and the Ag-Cu-Ti alloy forms metallurgical binding, and diamond thick-film and connected matrix are firmly linked together.This method stacks this procedure of Ti paper tinsel owing to having reduced in the charging process, simplified technical process, especially makes charging become easy when the welding small sample.
Substitute TiH with granularity 50 μ m with thin Ti powder
2Powder, effect and use TiH
2Powder is the same substantially.
Embodiment 3
72Ag-28Cu alloy among the embodiment 1 and Ti paper tinsel are all made netted in flakes, also can be realized the effect of embodiment 1.
Embodiment 4
In the charging process, the substrate surface of diamond thick-film is followed solder Ti contact, remaining process by embodiment 1, condition are welded, and the result connects also very firm, is suitable for practical application.
Select smoother substrate surface as joint face for guaranteeing bond strength.Because our used diamond film all is to adopt chemical gaseous phase depositing process synthetic, when diamond film synthetic, backing material generally all is the material that can form carbide with carbon, the atom of substrate material surface will form carbide (MoC, Mo to the carbon atom on diamond film diffusion into the surface and diamond film surface under the effect of high temperature bar in the diamond film building-up process
2C, WC, W
2C, SiC etc. specifically are which kind of carbide is relevant with backing material) this layer carbide help being connected of diamond thick-film and matrix.For the connection of thickness greater than the diamond thick-film of 150 μ m, selecting substrate surface for use is very suitable as joint face.
Embodiment 5
Use diamond thick-film, matrix, the solder of embodiment 1, press the processing step of embodiment 1 and implement welding, just welding temperature uprises, and is 900 ℃; Temperature retention time shortens, and is 25min; Rate of temperature fall accelerates, and is 25 ℃/min.Because it is not enough to alleviate the internal stress degree, though welding result also relatively firmly, shear strength does not reach the effect of embodiment 1.Explanation is in lower welding temperature, such as 860～870 ℃; Long temperature retention time is such as 40～60min; Lower rate of temperature fall such as 8～10 ℃/min, does not cause generating excessive carbide, helps the release of internal stress, has reached the purpose of firm welding.
Claims (5)
1, a kind of diamond thick-film forms the firm method that is connected with hard substrate, and technical process is pre-treatment process, charging process, welding process in order; Selecting Ag-Cu alloy and Ti paper tinsel is solder; Said charging process is, presses the order of matrix, Ag-Cu alloy, Ti paper tinsel, diamond thick-film, is placed on the loading platform of vacuum drying oven, and applies the pressure of 10Mpa magnitude thereon; It is characterized in that, said pre-treatment process is, diamond thick-film boils the clear water flushing again in the mixed solution of sulfuric acid, nitric acid, remove the surface film oxide that matrix is connected face, with acetone or carbon tetrachloride diamond thick-film, solder, matrix surface is carried out oil removal treatment; Said welding process is that vacuum drying oven is evacuated to 1 * 10
-3～2 * 10
-3Pa is warming up to 860～890 ℃ with 10～20 ℃/min heating rate, constant temperature 40～60min, and the rate of temperature fall with 8～12 ℃/min is cooled to 600～400 ℃ afterwards, is cooled to room temperature more naturally; Said Ag-Cu alloy be sheet or sheet netted, the Ti paper tinsel is that sheet is netted.
2, form the firm method that is connected according to described diamond thick-film of claim 1 and hard substrate, it is characterized in that, selected Ag-Cu alloy is the 72Ag-28Cu alloy, and thickness is 200～300 μ m; The thickness of Ti paper tinsel is 20～40 μ m; The Ag-Cu alloy that sheet is netted or the netted aperture of Ti paper tinsel are 0.2～0.8mm, and that Kong Yukong is 0.4～0.7mm at interval.
3, form the firm method that is connected according to claim 1 or 2 described diamond thick-films with hard substrate, it is characterized in that, said solder Ti uses TiH
2The pasty mixture of powder or Ti powder and ethanol, when filling with substance are filled in the mesh of the netted Ag-Cu alloy of sheet, place between diamond thick-film and the matrix again and weld.
4, form the firm method that is connected according to claim 1 or 2 described diamond thick-films with hard substrate, it is characterized in that, said diamond thick-film selects level and smooth substrate surface as joint face.
5, form the firm method that is connected according to described diamond thick-film of claim 3 and hard substrate, it is characterized in that, said diamond thick-film selects level and smooth substrate surface as joint face.
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|---|---|---|---|
| CNB2004100108953A CN100368140C (en) | 2004-06-03 | 2004-06-03 | Method for connecting diamond thick film with hard base firmly |
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|---|---|---|---|
| CNB2004100108953A CN100368140C (en) | 2004-06-03 | 2004-06-03 | Method for connecting diamond thick film with hard base firmly |
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| CN1583354A true CN1583354A (en) | 2005-02-23 |
| CN100368140C CN100368140C (en) | 2008-02-13 |
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| CNB2004100108953A Expired - Fee Related CN100368140C (en) | 2004-06-03 | 2004-06-03 | Method for connecting diamond thick film with hard base firmly |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012129B (en) * | 2006-11-08 | 2010-04-14 | 吉林大学 | Method of modifying diamond film or natural diamond surface |
| CN103894695A (en) * | 2014-04-22 | 2014-07-02 | 太原理工大学 | Method for welding CVD diamond thick film and hard alloy |
| CN106645265A (en) * | 2016-11-01 | 2017-05-10 | 山西太钢不锈钢股份有限公司 | Method for judging and eliminating expansibility of auxiliary material for steelmaking |
| CN107350664A (en) * | 2017-09-04 | 2017-11-17 | 湖北汽车工业学院 | A kind of copper silver brazing masterbatch and its soldering processes |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1313762C (en) * | 1985-11-19 | 1993-02-23 | Sumitomo Electric Industries, Ltd. | Hard sintered compact for a tool |
| CN1006613B (en) * | 1987-11-28 | 1990-01-31 | 国家建筑材料工业局人工晶体研究所 | Welding-type polycrystal composite with synthetic diamond and its manufacturing method |
| US5523158A (en) * | 1994-07-29 | 1996-06-04 | Saint Gobain/Norton Industrial Ceramics Corp. | Brazing of diamond film to tungsten carbide |
| CN1094810C (en) * | 1999-12-27 | 2002-11-27 | 华南理工大学 | Active solder and its preparation |
-
2004
- 2004-06-03 CN CNB2004100108953A patent/CN100368140C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012129B (en) * | 2006-11-08 | 2010-04-14 | 吉林大学 | Method of modifying diamond film or natural diamond surface |
| CN103894695A (en) * | 2014-04-22 | 2014-07-02 | 太原理工大学 | Method for welding CVD diamond thick film and hard alloy |
| CN103894695B (en) * | 2014-04-22 | 2015-12-09 | 太原理工大学 | The welding method of a kind of cvd diamond thick film and carbide alloy |
| CN106645265A (en) * | 2016-11-01 | 2017-05-10 | 山西太钢不锈钢股份有限公司 | Method for judging and eliminating expansibility of auxiliary material for steelmaking |
| CN107350664A (en) * | 2017-09-04 | 2017-11-17 | 湖北汽车工业学院 | A kind of copper silver brazing masterbatch and its soldering processes |
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| Publication number | Publication date |
|---|---|
| CN100368140C (en) | 2008-02-13 |
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