CN102268653A - Preparation method of hard alloy tool diamond interlayer - Google Patents
Preparation method of hard alloy tool diamond interlayer Download PDFInfo
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- CN102268653A CN102268653A CN 201110172966 CN201110172966A CN102268653A CN 102268653 A CN102268653 A CN 102268653A CN 201110172966 CN201110172966 CN 201110172966 CN 201110172966 A CN201110172966 A CN 201110172966A CN 102268653 A CN102268653 A CN 102268653A
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Abstract
The invention belongs to the technical field of diamond coating and particularly relates to a preparation method of a hard alloy tool diamond interlayer. The method comprises the following steps: installing a hard alloy substrate which is subjected to a simple surface treatment in a plasma chemical vapor deposition device, introducing mixed gas, exciting and decomposing the mixed gas of H2, siloxane and hydrocarbon at 0.5-8kPa under the action of the plasma generated through low temperature discharging while heating the hard alloy substrate to 600-850 DEG C, and depositing for 1-10 hours to obtain the SiC-based interlayer on the surface of the substrate. The mixed gas comprises the following components by volume: 94-98% of H2, 1-3% of siloxane and 1-3% of hydrocarbon gas. The invention has the following advantages: the adhesive force of the diamond coating can be effectively increased, the reduction of the mechanical strength of the hard alloy substrate, caused by the conventional treatment, can be avoided; and the interlayer is prepared by using non-toxic and cheap raw materials such as siloxane and has high safety and economy.
Description
Technical field
The invention belongs to the diamond coatings technical field, a kind of diamond coatings and its transition layer that is applied to various carbamide tool surface applied are had high adhesive force particularly is provided, thereby can be used to make method corresponding diamond coatings tool manufacture, that on carbamide tool, prepare the transition layer of diamond coatings.
Background technology
The carbamide tool of diamond coatings not only has the advantage of adamantine high rigidity, high-wearing feature, low-friction coefficient, and have Wimet good toughness, cost is low, the shape handiness is strong characteristics, thereby in modern industrial technology, have a wide range of applications.
But the problem of poor adhesive force is restricting the application of Wimet diamond coatings tool technique for a long time between diamond coatings and the carbamide tool matrix.This mainly be because, utilizing the chemical vapor deposition (CVD) method when with Co being the WC-Co series hard alloy tool surfaces deposition of diamond coatings of binding agent, bonding phase Co in the Wimet can cause carbon dissolving, suppress the diamond phase forming core, promote the generation of graphite phase, and this can make diamond coatings at the carbamide tool surface deposition because the coating adhesion deficiency influences its use properties.
Have high sticking power between diamond coatings and the hard alloy substrate in order to make, the measure that can take comprises usually:
(1) roughening treatment is carried out on the surface of hard alloy substrate;
(2) remove the Co on Wimet top layer with different etching means.
In order further to improve aforesaid method in the validity aspect the raising diamond coatings sticking power, people often combine use together to above-mentioned two kinds of methods.But then, even after having adopted aforesaid method, formed also mostly between diamond coatings and the carbamide tool matrix is that the lower mechanical type of sticking power adheres to, thereby its sticking power is generally lower.This is because aforesaid method can not guarantee that strong chemical bonding generation is arranged between institute sedimentary diamond and the Wimet as coated substrate.On the contrary, the diamond coatings that is deposited usually just simply physical attachment on the Wimet substrate.Moreover above-mentioned measure also can cause the damage on Wimet top layer, reduces the physical strength of Wimet substrate self greatly.Above-mentioned two kinds of situations all cause is comparatively disliking under the instrument working conditions slightly, perhaps the sticking power deficiency of diamond coatings, cause disbonding, the perhaps undercapacity of carbamide tool and whole fracture, the failure mode of these two kinds of diamond coatings instruments has perplexed the development of technology.
At this situation, having the scholar to propose to adopt at carbamide tool surface preparation one deck in recent years is the method for the transition layer of base with SiC.Because Si is a kind of chemical property and the very similar element of the adamantine C of composition.Thereby, between diamond coatings and Wimet substrate, introduce Si, to help to form chemical bonding strong between the Si-C element, thereby change the sticking power character between diamond coatings and hard alloy substrate, the change physical attachment is chemical attachment, improves the sticking power of diamond coatings to the Wimet substrate.Simultaneously, this use is that the method for the transition layer of base has been avoided the damage of traditional method to the Wimet top layer with SiC, thereby can not cause the reduction of Wimet base material mechanical property.
But, in preparation above-mentioned with SiC be the transition layer of base in, unstripped gas or great toxicity silane (SiH that people use
4), or very expensive tetramethylsilane (Si (CH
3)
4), this has limited greatly is the use of transition layer in carbamide tool diamond coatings technology of base with SiC.
By contrast, a large amount of siloxanes that use have cheap, two characteristics of nontoxicity in the industrial technology, can be used to replace silane, tetramethylsilane with the SiC transition layer in the substrate of preparation Wimet.But, use siloxanes to substitute silane, tetramethylsilane and prepare that needed SiC transition layer has two difficult points in the Wimet substrate.
First, contain a large amount of oxygen elements in the siloxane molecule, and if oxygen element will slacken the ability that forms chemical bonding between transition layer and the diamond coatings, because the chemical property difference between two kinds of materials of oxygenatedchemicals and diamond is bigger when being contained in the transition layer.
The second, the structure of siloxane molecule is very stable, and under the temperature that adopts usually, pressure condition, the molecule of siloxanes steam is difficult for decomposing, thereby is the silicon oxide compound that normally is rich in silicon, oxygen of feedstock production with the siloxanes.As mentioned above, above-mentioned silicon oxide compound can not be used as the transition layer between Wimet substrate and the diamond coatings.
Summary of the invention
In order to address the above problem, the invention provides the very cheap and avirulent unstripped gas of a kind of use, both can overcome diamond coatings to the low problem of Wimet substrate sticking power, can avoid the silane that uses toxicity very big or comparatively expensive, the preparation in the carbamide tool substrate of tetramethylsilane raw material again is the novel method of the transition layer of base with SiC.
The raw material that the present invention is used for preparing the SiC transition layer is that a large amount of chemical formulas that use are the siloxanes of (R-SiO) x in the Chemical Manufacture, and wherein, R represents various functional hydrocarbon group, and x represents that its chemical ingredients is transformable.Siloxanes is very cheap as a kind of industrial chemicals commonly used, is nontoxic, colourless liquid under normal temperature, normal pressure, but when being heated, and it will change into can be easy to the siloxanes steam that is used, thereby can be used to the preparation of SiC class material.
In order to solve the above-mentioned difficult point of using siloxanes to prepare the transition layer of Wimet substrate surface diamond coatings, the present invention will be used in combination two kinds of methods:
First, comparatively stable at the siloxane molecule structure, it is not labile characteristics under typical temperature and pressure condition, we will use the method that forms plasma body under low temperature and elevated pressures, utilize the characteristics that contain high-energy electron in the plasma body under low temperature, the elevated pressures, allow high-energy electron and siloxane molecule that collision mutually takes place, thereby promote the decomposition of siloxane molecule:
(R-SiO)x?+?e
=> R?+?SiO
In following formula, e represents the high-energy electron in the plasma body, and R, SiO are the products that decomposes.The decomposition of siloxane molecule is for preparation is that basic transition layer has been created condition with SiC.
Second, at the characteristics that contain a large amount of oxygen elements in the siloxane molecule, we will adopt the siloxanes vapor dilution in the stronger gas of a large amount of reductibilities and form the way of the plasma body of low temperature, elevated pressures, utilize the strong reducing property of plasma body, the siloxane gas molecule that has been decomposed further is reduced, captures the oxygen in its degradation production.For example, utilizing CH
4During as the main ingredient in the reducing gas, its reduction reaction can schematically be expressed as:
SiO?+?CH
4=> SiC?+?H
2O
This shows that in reducing atmosphere, siloxane gas will be reduced, and then reaches the purpose that preparation is the transition layer of base with SiC.
At above-mentioned use siloxanes is in the process of transition layer of base with SiC as unstripped gas preparation, needs to use the plasma body of low temperature, elevated pressures as media, in order to decompose the comparatively stable siloxanes vapour molecule of common structure.The method that can be utilized to produce this plasma body comprises various geseous discharge technology, as DC arc plasma, rf (discharge) plasma and microwave-assisted plasma body etc.But, because siloxanes has certain oxidation capacity, thereby be not suitable for being used in parts and be easy in the oxidized plasma generation technology, be heated to the heated filament auxiliary plasma technology of red-hot wire as use as the plasma excitation mode.
At above-mentioned use siloxanes is in the process of transition layer of base with SiC as unstripped gas preparation, needs to use higher gaseous tension.This is because under lower gaseous tension, the collision of high-energy electron will be frequent inadequately in siloxanes vapour molecule and the plasma body, thereby the decomposition of siloxanes vapour molecule will be abundant inadequately.Simultaneously, siloxanes itself has very strong polymerization and deposition tendency, i.e. the siloxanes atmosphere of part decomposition will cause a large amount of siloxane molecule to be deposited, thereby does not reach the purpose that deposition is the transition layer of base with SiC.
At above-mentioned use siloxanes is in the process of transition layer of base with SiC as unstripped gas preparation, also needs to use the atmosphere than strong reducing property.Among this, the atmosphere that has than strong reducing property mainly should comprise various hydrocarbon gas, and often is diluted in H
2In, promptly above-mentioned reducing gas is often with H
2As the main ingredient of gas, and hydrocarbon polymer such as CH
4Then for gas provides stronger reductibility, and the C that contains in latter's molecule will further to help to form with SiC be the transition layer of base.
Technical scheme of the present invention is:
A kind of preparation method of carbamide tool diamond transition layer specifically may further comprise the steps:
Wimet substrate after the simple process is packed in the plasma CVD device, feed by H
2Account for cumulative volume and account for cumulative volume than 94-98%, siloxanes and account for the mixed gas that cumulative volume is formed than 1-3% than 1-3%, hydrocarbon gas, under the pressure of 0.5～8kPa, under the effect of the plasma body that low temperature discharge produces, H
2, siloxanes and hydrocarbon polymer will be excited and decompose, and simultaneously the Wimet substrate is heated to 600-850 ° of C, depositing time is 1-10 hour, can obtain with SiC on the surface of Wimet substrate is the transition layer of base.
Further, described siloxanes comprises the various Si of containing, O, H element, constitutes backbone structure, the chemical formula organic silicide for (R-SiO) x with the Si-O-Si key, and wherein, R represents functional hydrocarbon group, and the value of X is 1-10.
Further, described hydrocarbon gas is CH
4Or C
2H
2
Described low temperature discharge plasma body is DC arc plasma, rf (discharge) plasma or microwave-assisted plasma body etc.
Wherein,
Requirement to siloxanes is that it will have certain equilibrium vapor pressure near room temperature, thereby can be applied to the chemical vapor deposition processes of SiC for the transition layer of base.
The requirement of hydrocarbon gas is that it can play strong reductive action in the chemical vapor deposition processes of SiC for the transition layer of base
The common feature of various method of generating plasma is that it can make used gas raw material be excited, thereby can make each decomposing gas become the transition layer required constituent element of deposition SiC for base.But then, because siloxanes has certain oxidisability, thereby described low temperature discharge plasma body does not comprise the heated filament auxiliary plasma of the red-hot wire of use as plasma exciting method.
The invention has the advantages that:
1. use with SiC is that basic transition layer can significantly improve the sticking power of diamond coatings for carbamide tool.This be because, the Si element has the character similar to the C in the diamond, thereby transition layer will form stronger chemical bonding with diamond coatings and Wimet both, change many sticking power mechanism based on physical attachment between diamond coatings and the hard alloy substrate.Simultaneously, use with SiC be that the transition layer of base can also avoid that conventional surface coarsening to hard alloy substrate is handled, the damage of carbamide tool surface mechanical property that the etching means go Co to handle to cause;
2. above-mentioned preparation is that the method for the transition layer of base only need be used nontoxic, cheap siloxanes and H with SiC
2, hydrocarbon polymer is as raw material, its security, good economy performance, and can have a better effect.
Description of drawings
Fig. 1 be utilize the application method preparation be the surface topography map of the transition layer of base with SiC.
The surface topography map of the diamond coatings that Fig. 2 is after utilizing the application's method to prepare with SiC to be the transition layer of base, prepare on this transition layer again.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further.
Embodiment 1
Carried out following simple process to desiring by the carbamide tool matrix of diamond coatings:
1. its surface is polished with mechanical means.For this purpose, can use conventional abrasion wheel grinding method, also can use the method for hand lapping.The purpose of grinding is to obtain a comparatively smooth matrix surface and lower surfaceness.
2. with scavenging solutions commonly used such as alcohol hard alloy substrate is cleaned.
Thereafter, utilizing the DC electric arc plasma chemical vapor deposition method to prepare required is the transition layer of base with SiC.Among this process, unstripped gas comprises H
2, CH
4(as reducing gas) and octamethylcyclotetrasiloxane (it is a kind of as siloxanes, is the main raw material gas of deposition transition layer).Because octamethylcyclotetrasiloxane at room temperature is a liquefied compound, thereby need to adopt H
2Bring the steam of its generation into sediment chamber.
The Wimet substrate is packed in the DC electric arc plasma chemical vapor deposition apparatus, feed by H
2, CH
4With the mixed gas of octamethylcyclotetrasiloxane composition, and with CH in the mixed gas
4Be adjusted to 1% and 1.5% with the ratio of octamethylcyclotetrasiloxane, and the pressure of gas is adjusted to 2kPa.Under the effect of the plasma body that direct current arc produces, H
2, CH
4To be excited and decompose with octamethylcyclotetrasiloxane, and be heated to deposit with SiC in 800 ° of Wimet substrates about C be the base transition layer.Keep above-mentioned mode of deposition 6 hours constant, until the deposition of finishing transition layer.Thus, can obtain as shown in Figure 1 with SiC be the base transition layer.
After having deposited transition layer, use same DC electric arc plasma chemical vapor deposition apparatus, but only feed by H
2, CH
4The mixed gas of forming can continue to finish the deposition of diamond coatings, and the diamond coatings that obtains as shown in Figure 2
Embodiment 2
Undertaken as after the identical surface of embodiment 1 by the carbamide tool matrix of diamond coatings desiring, utilizing microwave-assisted plasma activated chemical vapour deposition method to prepare required is the transition layer of base with SiC.Among this process, unstripped gas comprises H
2, C
2H
2(as reducing gas) and hexamethyldisiloxane (as the main raw material gas of deposition transition layer).Hexamethyldisiloxane at room temperature also is liquid, thereby also needs to adopt H
2Bring the steam of its generation into sediment chamber.
The Wimet substrate is packed in the microwave-assisted plasma CVD device, feed by H
2, C
2H
2With the mixed gas of hexamethyldisiloxane composition, and with C in the mixed gas
2H
2Be adjusted to 2.5% and 3% with the ratio of hexamethyldisiloxane, and the pressure of gas is adjusted to 6kPa.Under the effect of microwave-assisted plasma body, H
2, C
2H
2To be excited and decompose with hexamethyldisiloxane, and be heated to deposit with SiC in 820 ° of Wimet substrates about C be the base transition layer.Keep above-mentioned mode of deposition 10 hours constant, until the deposition of finishing transition layer.Thus, can obtain with SiC is the transition layer of base.After this, use same microwave-assisted plasma CVD device, but only feed by H
2, C
2H
2The mixed gas of forming can continue to finish the deposition of diamond coatings.
Embodiment 3
Undertaken as after the identical surface of embodiment 1 by the carbamide tool matrix of diamond coatings desiring, utilizing the rf (discharge) plasma chemical gaseous phase depositing process to prepare required is the transition layer of base with SiC.Among this process, unstripped gas comprises H
2, CH
4(as reducing gas) and hexamethyl cyclotrisiloxane (as the main raw material gas of deposition transition layer).Because hexamethyl cyclotrisiloxane at room temperature also is a liquefied compound, thereby need to adopt H
2Bring the steam of its generation into sediment chamber.
The Wimet substrate is packed in the rf (discharge) plasma chemical vapor deposition unit, feed by H
2, CH
4With the mixed gas of hexamethyl cyclotrisiloxane composition, and with CH in the mixed gas
4Be adjusted to 1.5% and 2% with the ratio of hexamethyl cyclotrisiloxane, and the pressure of gas is adjusted to 0.8kPa.Under the effect of rf (discharge) plasma, H
2, CH
4To be excited and decompose with hexamethyl cyclotrisiloxane, and be heated to deposit with SiC in 780 ° of Wimet substrates about C be the base transition layer.After this, use DC electric arc plasma chemical vapor deposition apparatus instead, but only feed by H
2, CH
4The mixed gas of forming can continue to finish the deposition of diamond coatings.
Claims (4)
1. the preparation method of a carbamide tool diamond transition layer is characterized in that it specifically may further comprise the steps:
Will the Wimet substrate after simple surfaces is handled pack in the plasma CVD device, feed by H
2Accounting for cumulative volume and account for cumulative volume than 94-98%, siloxanes and account for the mixed gas that cumulative volume is formed than 1-3% than 1-3%, hydrocarbon gas, is under 0.5～8kPa at pressure, under the effect of the plasma body that low temperature discharge produces, and H
2, siloxanes and hydrocarbon polymer will be excited and decompose, and simultaneously the Wimet substrate is heated to 600-850 ° of C, depositing time is 1-10 hour, can obtain with SiC on its surface be the transition layer of base.
2. preparation method according to claim 1, it is characterized in that described siloxanes comprises the various Si of containing, O, H element, constitutes backbone structure, the chemical formula organic silicide for (R-SiO) x with the Si-O-Si key, wherein, R represents functional hydrocarbon group, and the value of X is 1-10.
3. preparation method according to claim 1 is characterized in that, described hydrocarbon gas is CH
4Or C
2H
2
4. preparation method according to claim 1 is characterized in that, described low temperature discharge plasma body is DC arc plasma, rf (discharge) plasma or microwave-assisted plasma body.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105274489A (en) * | 2014-07-21 | 2016-01-27 | 奈尔公司 | Preparation method for forming nano sheet structure network on substrate and substrate |
| CN106835064A (en) * | 2016-12-16 | 2017-06-13 | 中国科学院深圳先进技术研究院 | A kind of instrument with diamond/silicon carbide composite coating and preparation method thereof |
| CN112981205A (en) * | 2021-02-05 | 2021-06-18 | 哈尔滨工业大学 | Low-cost preparation method of high-thermal-conductivity diamond-reinforced metal-based composite material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1632165A (en) * | 2004-12-28 | 2005-06-29 | 北京科技大学 | Process for preparing diamond covering on sintered-carbide tool |
-
2011
- 2011-06-24 CN CN 201110172966 patent/CN102268653A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1632165A (en) * | 2004-12-28 | 2005-06-29 | 北京科技大学 | Process for preparing diamond covering on sintered-carbide tool |
Non-Patent Citations (2)
| Title |
|---|
| 《北京科技大学学报》 20070430 刘素田等 含Si金刚石涂层的工艺研究 第408-412页 1-4 第29卷, 第4期 * |
| 《金刚石与磨料磨具工程》 20050228 樊凤玲等 化学气相沉积过程中Si的引入对硬质合金金刚石涂层附着力的影响 第31-35页 1-4 , 第1期 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105274489A (en) * | 2014-07-21 | 2016-01-27 | 奈尔公司 | Preparation method for forming nano sheet structure network on substrate and substrate |
| CN105274489B (en) * | 2014-07-21 | 2018-06-19 | 奈尔公司 | Preparation method for forming nano sheet structure network on substrate and substrate |
| CN106835064A (en) * | 2016-12-16 | 2017-06-13 | 中国科学院深圳先进技术研究院 | A kind of instrument with diamond/silicon carbide composite coating and preparation method thereof |
| CN106835064B (en) * | 2016-12-16 | 2019-06-25 | 中国科学院深圳先进技术研究院 | A kind of tool and preparation method thereof with diamond/silicon carbide composite coating |
| CN112981205A (en) * | 2021-02-05 | 2021-06-18 | 哈尔滨工业大学 | Low-cost preparation method of high-thermal-conductivity diamond-reinforced metal-based composite material |
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Application publication date: 20111207 |