CN109207960A - A kind of carbonization titanium nanocrystals coating and its preparation method and application being compound in M42 steel surface - Google Patents
A kind of carbonization titanium nanocrystals coating and its preparation method and application being compound in M42 steel surface Download PDFInfo
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- CN109207960A CN109207960A CN201710539215.4A CN201710539215A CN109207960A CN 109207960 A CN109207960 A CN 109207960A CN 201710539215 A CN201710539215 A CN 201710539215A CN 109207960 A CN109207960 A CN 109207960A
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- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/32—Carbides
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- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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Abstract
The present invention relates to a kind of carbonization titanium nanocrystals coatings and its preparation method and application for being compound in M42 steel surface.Specifically, the invention discloses a kind of preparation method of carbonization titanium nanocrystals coating, the method prepares the carbonization titanium nanocrystals coating in M42 steel surface with Low Pressure Chemical Vapor Deposition.The invention also discloses the carbonization titanium nanocrystals coatings to be compound in M42 steel surface made from the preparation method.The preparation method has many advantages, such as simple process, at low cost, safety and environmental protection.The coating has the characteristics that coefficient of friction is moderate, strong with matrix M42 steel binding force.
Description
Technical field
The present invention relates to Material Fields to be compound in more particularly to ceramic base coating preparation field more particularly, to one kind
Carbonization titanium nanocrystals coating of M42 steel surface and its preparation method and application.
Background technique
M42 high-speed steel is widely used as a kind of wear-resisting, impact-resistant steel in screw industry and forging industry, especially in spiral shell
Silk manufacturing industry is widely used.
As important industrial spare and accessory parts, screw is in electronic product, engineering goods, digital product, power equipment, electromechanical machine
There is a large amount of application in the industrial products such as tool product.However, different equipment is often in different use environments, for example,
Marine ship travels in ocean throughout the year, and internal environment inevitably contains a large amount of steam and salts substances.This requires all kinds of
Screw in equipment can adapt to its unique use environment.It is well known that M42 steel mechanical performance is no doubt outstanding, but as iron
Sill can not be effective against all kinds of chemical attacks or moisture attacks.
In order to solve the problems, such as that M42 steel screw is anticorrosive or corrosion, people have attempted the method for many surfacecti proteons, wrap
Include plating protective layer, brushed with organic coating etc..The protective coating advantage and disadvantage of all kinds of means of defence preparations are had nothing in common with each other: some coating energy
Enough make screw anticorrosion, is but restricted the screw thread mechanical property of screw, such as: the coefficient of friction of common steel screw is general
Within the scope of 0.1-0.2, coating coefficient of friction is excessive or too small, and will lead to screw can not normally load and unload with nut；Some coatings
It is not strong with screw surface binding force, the charge and discharge operations of screw and nut can not be adapted to and fallen off easily；Some coating productions
Economic cost is high, such as prepares protective coating using physical vaporous deposition；The preparation process of some coating productions can generate
Environmental pollution, such as galvanoplastic, electroless plating method.
The antiacid caustic corrosion and salt resistance of ceramic material divide corrosive power to be better than general ferrous metals material, thus, exploitation
A kind of M42 steel surface ceramic base protective coating haveing excellent performance and preparation method thereof has highly important application value.
Summary of the invention
The purpose of the present invention is to provide the outstanding M42 steel surface protective coatings of a kind of excellent in mechanical performance, protective performance
And its preparation method and application.
The first aspect of the present invention provides a kind of preparation of carbonization titanium nanocrystals coating for being compound in M42 steel surface
Method, described method includes following steps:
1) M42 high-speed steel, carbon source, titanium source and auxiliary gas are provided；
2) the M42 high-speed steel is placed in CVD furnace, under the auxiliary gas atmosphere, heating CVD furnace to deposit heat preservation
Temperature；
3) carbon source and the titanium source are passed through in the heated CVD furnace, keep the temperature first time period；
4) the CVD furnace is cooled to second temperature with the first rate of temperature fall, is simultaneously stopped and is passed through the carbon source and described
Titanium source；
5) after the CVD furnace is cooled to second temperature, stopping is passed through the auxiliary gas, obtains described being compound in M42
The carbonization titanium nanocrystals coating of steel surface.
In another preferred example, the carbon source is selected from the group: methane, ethane, propane, ethylene, propylene, acetylene or its group
It closes；And/or
The titanium source includes titanium tetrachloride.
In another preferred example, the carbon source is gaseous state.
In another preferred example, the titanium source is liquid.
In another preferred example, when the titanium source is liquid, before being passed through CVD furnace, the titanium source is through vaporization process.
In another preferred example, the auxiliary gas is non-oxidizing gas.
In another preferred example, the auxiliary gas is selected from the group: hydrogen, argon gas, or combinations thereof.
In another preferred example, the auxiliary gas has effect selected from the group below:
1) it is used as carrier, the titanium source through vaporizing is loaded into CVD furnace；
2) it is used as anti-oxidant gas, is aoxidized during the deposition process to avoid the titanium carbide.
In another preferred example, the deposition holding temperature be 1000-1020 DEG C, preferably 1005-1020 DEG C, more preferably
1010-1020℃。
In another preferred example, step 3) carries out the deposition process of the coating, and in step 3), the auxiliary gas with
The flow-rate ratio of the carbon source is 3-10, preferably 4-9.
In another preferred example, in step 3), the flow of the carbon source is 300-1100sccm, preferably 400-
1000sccm, more preferably 500-900sccm.
In another preferred example, in step 3), the flow of the auxiliary gas is 2500-5000sccm, preferably 3000-
4500sccm。
In another preferred example, in step 3), the first time period is 20-100min, preferably 30-80min, more preferably
Ground 40-70min.
In another preferred example, in step 4), first rate of temperature fall be 4-10 DEG C/min, preferably 4-9 DEG C/
Min, more preferably 5-9 DEG C/min.
In another preferred example, the second temperature is room temperature, such as 25-40 DEG C, preferably 30-35 DEG C.
The second aspect of the present invention provides a kind of composite material, and the composite material includes:
Substrate；With
It is compound in the coating of the substrate surface, the coating is carbonization titanium nanocrystals coating；
And the composite material is using made from preparation method described in first aspect present invention.
In another preferred example, the substrate is M42 steel.
In another preferred example, described to be complex as being chemically bonded.
In another preferred example, the coefficient of friction of the carbonization titanium nanocrystals coating is 0.1-0.3, preferably
0.12-0.28, more preferably 0.15-0.25；And/or
It is described carbonization titanium nanocrystals coating and substrate bond strength be >=30N, preferably >=40N, more preferably >=
50N。
In another preferred example, the composite material has one or more features selected from the group below:
1) partial size for forming the crystal grain of the carbonization titanium nanocrystals coating is less than 200nm, preferably less than 150nm, more
It is less than 100nm goodly；
2) it is described carbonization titanium nanocrystals coating with a thickness of 0.5-3 μm, preferably 0.8-2 μm, more preferably 1-1.5 μm；
3) in the carbonization titanium nanocrystals coating, the content of the titanium elements is 70-80wt%, and the carbon contains
Amount is 20-30wt%.
The third aspect of the present invention, provides a kind of product, and the product includes compound described in second aspect of the present invention
Material or the composite material described in second aspect of the present invention are made.
In another preferred example, the product is selected from the group: corrosion-resistant fastener, corrosion-resistant finishes material.
It should be understood that above-mentioned each technical characteristic of the invention and having in below (eg embodiment) within the scope of the present invention
It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, exist
This no longer tires out one by one states.
Detailed description of the invention
Fig. 1 is the SEM test chart for the carbonization titanium nanocrystals coating 1 for being compound in M42 steel surface that embodiment 1 obtains.
Fig. 2 is the SEM test in carbonization 1 section of titanium nanocrystals coating for being compound in M42 steel surface that embodiment 1 obtains
Figure.
Fig. 3 is the XRD test chart for the carbonization titanium nanocrystals coating 1 for being compound in M42 steel surface that embodiment 1 obtains.
Fig. 4 is the SEM test chart for the carbonization titanium nanocrystals coating 2 for being compound in M42 steel surface that embodiment 2 obtains.
Fig. 5 is the SEM figure for the carbonization titanium crystal coating C1 for being compound in M42 steel surface that comparative example 1 obtains.
Fig. 6 is the XRD diagram for the carbonization titanium crystal coating C1 for being compound in M42 steel surface that comparative example 1 obtains.
Fig. 7 is the SEM figure for the carbonization titanium crystal coating C2 for being compound in M42 steel surface that comparative example 2 obtains.
Fig. 8 is the SEM figure for the carbonization titanium crystal coating C4 for being compound in M42 steel surface that comparative example 4 obtains.
Specific embodiment
The present inventor's in-depth study by long-term, by regulating and controlling the preparation process of the coating (such as deposition heat preservation temperature
Rate of temperature fall, raw material gas flow etc. in deposition process after degree, deposition) a kind of mechanics unexpectedly is prepared in M42 steel surface
It has excellent performance and carbonization titanium nanocrystals coating that protective performance is outstanding.The preparation method has simple process, at low cost, peace
The advantages that loopful is protected.The coating has the characteristics that coefficient of friction is moderate, strong with matrix M42 steel binding force.On this basis, it sends out
Bright people completes the present invention.
Preparation method
The present invention provides a kind of preparation method of carbonization titanium nanocrystals coating for being compound in M42 steel surface, the sides
Method includes the following steps:
1) M42 high-speed steel, carbon source, titanium source and auxiliary gas are provided；
2) the M42 high-speed steel is placed in CVD furnace, under the auxiliary gas atmosphere, heating CVD furnace to deposit heat preservation
Temperature；
3) carbon source and the titanium source are passed through in the heated CVD furnace, keep the temperature first time period；
4) the CVD furnace is cooled to second temperature with the first rate of temperature fall, is simultaneously stopped and is passed through the carbon source and described
Titanium source；
5) after the CVD furnace is cooled to second temperature, stopping is passed through the auxiliary gas, obtains described being compound in M42
The carbonization titanium nanocrystals coating of steel surface.
It should be understood that in the present invention, the deposition holding temperature should be maintained between 1000-1030 DEG C.When the deposition
When holding temperature is lower than 1000 DEG C (such as comparative example 2), there are cotton-shaped titanium carbides to receive for the carbonization titanium nanocrystals coating surface of acquisition
Rice wall, influences the structure and frictional behaviour of coating；When the deposition holding temperature is higher than 1020 DEG C (such as comparative example 1), obtain
Carbonization titanium crystal crystal grain it is excessive, coefficient of friction be greater than common fastener material, be unfavorable for as machanical fastener coating
It uses.
It should be understood that in the present invention, the flow-rate ratio of the auxiliary gas and the carbon source should be maintained between 3-10, when
When flow-rate ratio < 3, the crystal grain for depositing the titanium carbide coating surface of acquisition is in the form of a column, and crystallite dimension is coarse.
It should be understood that in the present invention, first rate of temperature fall should be maintained at 4-10 DEG C/min.When first cooling
10 DEG C/min of rate >, the titanium carbide coating for depositing acquisition, which is usually present, to fall off or the problem not strong with M42 steel matrix binding force；
As 4 DEG C/min of the first rate of temperature fall <, the unnecessary waste of gas resource can be produced electricl energy and assisted.
Typically, the preparation method includes the following steps:
(1) a kind of M42 high-speed steel, carbon source, titanium source and auxiliary gas are provided, the titanium source is the liquid that purity is 99.99%
State titanium tetrachloride, the carbon source are the gaseous methane that purity is 99.99%, and the auxiliary gas is the hydrogen that purity is 99.99%
Gas；
(2) step (1) the M42 stainless steel is placed in CVD furnace, is evacuated to vacuum degree less than 1Pa, is passed through hydrogen, institute
Stating hydrogen flowing quantity is 50-150sccm；
(3) it is heated to 800-900 DEG C with the rate of 5-20 DEG C/min, opens titanium tetrachloride preheating, preheating temperature 30-80
℃；Continue to be heated to 1000-1020 DEG C with the rate of 5-20 DEG C/min, is passed through four chlorinations of carbon-source gas and preheated vaporization
Titanium keeps the temperature 20-110min, and the methane flow is 300-1100sccm, and is carrier gas by the four of vaporization using the auxiliary gas
Titanium chloride is loaded into the CVD furnace, carrier gas flux 300-11000sccm.Cooling stops ventilation, is compound in M42 steel described in acquisition
The carbonization titanium nanocrystals coating on surface.
In another preferred example, it derusted, washed, be dried to the M42 high-speed steel before being placed in CVD furnace.
Composite material and its application
The present invention also provides a kind of composite material, the composite material includes:
Substrate；With
It is compound in the coating of the substrate surface, the coating is carbonization titanium nanocrystals coating；
And the composite material is using made from the preparation method.
In the present invention, the range scale for forming the crystal grain of the carbonization titanium nanocrystals coating is less than 200nm, preferably
Less than 150nm, more preferably less than 100nm.
The present invention also provides a kind of product, the product is comprising the composite material or by the composite material system
At.
In another preferred example, the product includes (but being not limited to) the following group: corrosion-resistant fastener, corrosion-resistant finishes material
Material.
It should be understood that when the composite material is applied to the machine industries such as screw, mold, it can be in many complicated rings
The effect of anticorrosion, anti-corrosion is effectively acted as in border.
Compared with prior art, the present invention has following major advantage:
(1) preparation method has many advantages, such as simple process, at low cost, safety and environmental protection.
(2) preparation method does not mix foreign gas during the preparation process, and preparation process is easily controllable, and it is high to be suitable for preparation
Purity silicon carbide titanium nanocrystals coating.
(3) coating has the characteristics that coefficient of friction is moderate, strong with matrix M42 steel binding force.
(4) the coating constituent purity is high, no undesired impurities, dimensional structure are uniform.
(5) friction coefficient of composite material is moderate, is suitable for all kinds of machanical fasteners.
(6) the composite material acid/alkali-corrosion-resistant and brine corrosion are had excellent performance, suitable in the sea of high salt, high humility
The various ship being on active service in foreign environment.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are calculated by weight.
Unless otherwise defined, it anticipates known to all professional and scientific terms as used herein and one skilled in the art
Justice is identical.In addition, any method similar to or equal to what is recorded and material can be applied to the method for the present invention.Wen Zhong
The preferred implement methods and materials are for illustrative purposes only.
Experimental raw
1, " M42 high-speed steel " is the steel that U.S.'s AISI standard brand is M42, the corresponding China's GB standard brand of the trade mark steel
W2Mo9Cr4VCo8, the german standard din trade mark S2-10-1-8, Japanese JIS standard brand SKH55." M42 steel " and " M42 high speed
Steel " is used interchangeably.
2, methane refers to that purity is 99.99% methane gas.
3, titanium tetrachloride refers to that purity is 99.99% liquid.
4, auxiliary gas refers to that purity is 99.99% gas.
1 composite material 1 (the carbonization titanium nanocrystals coating 1 for being compound in M42 steel surface) of embodiment
M42 high-speed steel having a size of 10mm*10mm*5mm is subjected to surface polishing derusting, with alcohol rinse, drying, is placed in
In CVD furnace.CVD stove evacuation is to 10-1Pa is filled with hydrogen, gas flow 100cssm.CVD furnace starts heating mode, heating
990 DEG C of target temperature, 15 DEG C/min of the rate of heat addition.CVD stove heating opens the preheating of titanium tetrachloride pipeline, preheating temperature to 900 DEG C
It is 50 DEG C.CVD stove heating is passed through methane and titanium tetrachloride to 1010 DEG C into holding mode, soaking time 40min, first
Alkane flow is 500sccm, and titanium tetrachloride is loaded into CVD furnace, carrier gas flux 4000sccm by carrier gas of hydrogen.CVD furnace terminates to protect
Cooled down after warm mode with the rate of temperature fall of 5 DEG C/min, is simultaneously stopped and is passed through methane and titanium tetrachloride.After being cooled to room temperature, stop
It is passed through hydrogen, obtains the carbonization titanium nanocrystals coating 1 (i.e. composite material 1) for being compound in M42 steel surface.
As a result
SEM, EDS, XRD etc. are carried out to the carbonization titanium nanocrystals coating 1 for being compound in M42 steel surface that embodiment 1 obtains
Test.
Fig. 1 is the SEM test chart for the carbonization titanium nanocrystals coating 1 for being compound in M42 steel surface that embodiment 1 obtains.
Fig. 1 is shown: 1 surface compact of carbonization titanium nanocrystals coating for being compound in M42 steel surface that embodiment 1 obtains, brilliant
Grain is in Nano grade (being less than 100nm).
Fig. 2 is the SEM test in carbonization 1 section of titanium nanocrystals coating for being compound in M42 steel surface that embodiment 1 obtains
Figure.
Fig. 2 is shown: 1 surface compact of carbonization titanium nanocrystals coating for being compound in M42 steel surface that embodiment 1 obtains, thick
Degree is about 1um.
Fig. 3 is the XRD test chart for the carbonization titanium nanocrystals coating 1 for being compound in M42 steel surface that embodiment 1 obtains.
Fig. 3 is shown: what embodiment 1 obtained is compound in the ingredient of the carbonization titanium nanocrystals coating 1 of M42 steel surface to be carbonized
Titanium.
Through calculating, what embodiment 1 obtained is compound in the element of the carbonization titanium nanocrystals coating 1 of M42 steel surface as titanium member
Element and carbon, it is about 76.32% that the titanium elements content, which accounts for weight ratio, and the carbon element content accounts for weight ratio and is about
23.68% (as shown in table 1).
Table 1
| Element | Weight content % | Constituent content % |
| C | 23.68 | 55.31 |
| Ti | 76.32 | 44.69 |
| It is total | 100.00 |
After tested, the binding force of carbonization titanium nanocrystals coating and M42 steel matrix is 52N in composite material 1；Titanium carbide is received
The coefficient of friction of meter Jing Ti coating is between 0.1-0.2.
2 composite material 2 (the carbonization titanium nanocrystals coating 2 for being compound in M42 steel surface) of embodiment
M42 high-speed steel having a size of 10mm*10mm*5mm is subjected to surface polishing derusting, with alcohol rinse, drying, is placed in
In CVD furnace.CVD stove evacuation is to 10-1Pa is filled with hydrogen, gas flow 100cssm.CVD furnace starts heating mode, heating
1010 DEG C of target temperature, 5 DEG C/min of the rate of heat addition.CVD stove heating opens the preheating of titanium tetrachloride pipeline, preheating temperature to 910 DEG C
It is 50 DEG C.CVD stove heating is passed through methane and titanium tetrachloride to 1020 DEG C into holding mode, soaking time 60min, first
Alkane flow is 750sccm, and titanium tetrachloride is loaded into CVD furnace, carrier gas flux 3500sccm by carrier gas of hydrogen.CVD furnace terminates to protect
Cooled down after warm mode with the rate of temperature fall of 9 DEG C/min, is simultaneously stopped and is passed through methane and titanium tetrachloride.After being cooled to room temperature, stop
It is passed through hydrogen, obtains the carbonization titanium nanocrystals coating 2 (i.e. composite material 2) for being compound in M42 steel surface.
As a result
The test such as SEM, EDS is carried out to the carbonization titanium nanocrystals coating 2 for being compound in M42 steel surface that embodiment 2 obtains.
Fig. 4 is the SEM test chart for the carbonization titanium nanocrystals coating 2 for being compound in M42 steel surface that embodiment 2 obtains.
Fig. 4 is shown: 2 surface compact of carbonization titanium nanocrystals coating for being compound in M42 steel surface that embodiment 2 obtains,
Particle size is in Nano grade.
Calculate through EDS, the element of the carbonization titanium nanocrystals coating 2 for being compound in M42 steel surface of the acquisition of embodiment 2 is titanium
Element and carbon, it is about 75.72% that the titanium elements content, which accounts for weight ratio, and the carbon element content accounts for weight ratio and is about
24.28% (as shown in table 2).
Table 2
After tested, the binding force of carbonization titanium nanocrystals coating and M42 steel matrix is 57N in composite material 2；Titanium carbide is received
The coefficient of friction of meter Jing Ti coating is between 0.1-0.2.
1 composite material C1 of comparative example (the carbonization titanium crystal coating C1 for being compound in M42 steel surface)
With embodiment 1, difference is: the holding temperature of CVD furnace is 1030 DEG C.
As a result
SEM, EDS, XRD etc. is carried out to the carbonization titanium crystal coating C1 for being compound in M42 steel surface that comparative example 1 obtains to survey
Examination.
Fig. 5 is the SEM figure for the carbonization titanium crystal coating C1 for being compound in M42 steel surface that comparative example 1 obtains.
From fig. 5, it can be seen that the carbonization titanium crystal coating C1 crystal grain for being compound in M42 steel surface that comparative example 1 obtains is in cone
Shape, particle size are about 0.5um, hence it is evident that the carbonization titanium nanocrystals coating for being compound in M42 steel surface obtained greater than embodiment 1
The size of crystal grain in 1.
Fig. 6 is the XRD diagram for the carbonization titanium crystal coating C1 for being compound in M42 steel surface that comparative example 1 obtains.
From fig. 6, it can be seen that the ingredient for the carbonization titanium crystal coating C1 for being compound in M42 steel surface that comparative example 1 obtains is
Titanium carbide.
Through calculating, comparative example 1 obtain be compound in M42 steel surface carbonization titanium crystal coating C1 element be titanium elements and
Carbon, it is about 66.36% that the titanium elements content, which accounts for weight ratio, and it is about 33.64% (such as that the carbon element content, which accounts for weight ratio,
Shown in table 3).
Table 3
| Element | Weight content % |
| C | 33.64 |
| Ti | 66.36 |
| It is total | 100.00 |
After tested, in composite material C1 be carbonized titanium nanocrystals coating and M42 steel matrix binding force and Examples 1 and 2
The composite material 1 and 2 obtained respectively is not much different, but wherein the coefficient of friction of carbonization titanium crystal coating is between 0.4-0.5,
It is much bigger compared with composite material 1 and 2 and common fastener material.
2 composite material C2 of comparative example (the carbonization titanium crystal coating C2 for being compound in M42 steel surface)
With embodiment 1, difference is: the holding temperature of CVD furnace is 990 DEG C.
As a result
The test such as SEM and EDS is carried out to the carbonization titanium crystal coating C2 for being compound in M42 steel surface that comparative example 2 obtains.
Fig. 7 is the SEM figure for the carbonization titanium crystal coating C2 for being compound in M42 steel surface that comparative example 2 obtains.
From figure 7 it can be seen that there are cotton-shaped impurity substances for titanium carbide nanocrystal surface, and after measured, the impurity substances
For titanium carbide nm wall.
3 composite material C3 of comparative example (the carbonization titanium crystal coating C3 for being compound in M42 steel surface)
With embodiment 1, difference is: rate of temperature fall is 12 DEG C/min after deposition.
There is local shedding in the titanium crystal coating that is carbonized in composite material C3, and M42 steel matrix surface can not be protected to make it comprehensively
Do not corroded by soda acid and salinity.
Also, after tested, the binding force of carbonization titanium nanocrystals coating and M42 steel matrix is less than 10N.
4 composite material C4 of comparative example (the carbonization titanium crystal coating C4 for being compound in M42 steel surface)
With embodiment 2, difference is: methane flow 1200sccm.
SEM and EDS test is carried out to the carbonization titanium crystal coating C4 for being compound in M42 steel surface that comparative example 4 obtains.
Fig. 8 is the SEM figure for the carbonization titanium crystal coating C4 for being compound in M42 steel surface that comparative example 4 obtains.
Fig. 8 shows that the crystal grain on titanium carbide coating surface in composite material C4 is in the form of a column, and crystallite dimension is 150-500nm.
Through calculating, comparative example 4 obtain be compound in M42 steel surface carbonization titanium crystal coating C4 element be titanium elements and
Carbon, it is about 66.36% that the titanium elements content, which accounts for weight ratio, and it is about 33.64% (such as that the carbon element content, which accounts for weight ratio,
Shown in table 4).
Table 4
| Element | Weight content % |
| C | 38.61 |
| Ti | 61.39 |
| Total amount: | 100.00 |
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To make various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (10)
1. a kind of preparation method for the carbonization titanium nanocrystals coating for being compound in M42 steel surface, which is characterized in that the method packet
Include following steps:
1) M42 high-speed steel, carbon source, titanium source and auxiliary gas are provided；
2) the M42 high-speed steel is placed in CVD furnace, under the auxiliary gas atmosphere, heating CVD furnace to deposition heat preservation temperature
Degree；
3) carbon source and the titanium source are passed through in the heated CVD furnace, keep the temperature first time period；
4) the CVD furnace is cooled to second temperature with the first rate of temperature fall, is simultaneously stopped and is passed through the carbon source and the titanium source；
5) after the CVD furnace is cooled to second temperature, stopping is passed through the auxiliary gas, obtains described being compound in M42 steel table
The carbonization titanium nanocrystals coating in face.
2. the method as described in claim 1, which is characterized in that the carbon source is selected from the group: methane, ethane, propane, ethylene,
Propylene, acetylene, or combinations thereof；And/or
The titanium source includes titanium tetrachloride.
3. the method as described in claim 1, which is characterized in that the deposition holding temperature is 1000-1020 DEG C.
4. the method as described in claim 1, which is characterized in that step 3) carries out the deposition process of the coating, and step 3)
In, the flow-rate ratio of the auxiliary gas and the carbon source is 3-10.
5. the method as described in claim 1, which is characterized in that in step 3), the first time period is 20-100min.
6. the method as described in claim 1, which is characterized in that in step 4), first rate of temperature fall be 4-10 DEG C/
min。
7. a kind of composite material, which is characterized in that the composite material includes:
Substrate；With
It is compound in the coating of the substrate surface, the coating is carbonization titanium nanocrystals coating；
And the composite material is using made from preparation method described in claim 1.
8. composite material as claimed in claim 7, which is characterized in that it is described carbonization titanium nanocrystals coating coefficient of friction be
0.1-0.3；And/or
The bond strength of the carbonization titanium nanocrystals coating and substrate is >=30N.
9. composite material as claimed in claim 7, which is characterized in that the composite material has one selected from the group below or more
A feature:
1) partial size for forming the crystal grain of the carbonization titanium nanocrystals coating is less than 200nm；
2) it is described carbonization titanium nanocrystals coating with a thickness of 0.5-3 μm；
3) in the carbonization titanium nanocrystals coating, the content of the titanium elements is 70-80wt%, and the content of the carbon is
20-30wt%.
10. a kind of product, which is characterized in that the product is comprising composite material as claimed in claim 7 or by claim 7 institute
The composite material stated is made.
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| CN113235069A (en) * | 2021-05-11 | 2021-08-10 | 中国石油天然气集团有限公司 | Corrosion-resistant titanium nitride wear-resistant coating, preparation method thereof and product comprising coating |
| CN115704090A (en) * | 2021-08-10 | 2023-02-17 | 中国石油天然气集团有限公司 | Hydrogen-resistant composite coating and preparation method thereof |
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| CN109207960B (en) | 2021-02-02 |
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