CN108660431A - A kind of preparation method of high-densit diamond thin - Google Patents
A kind of preparation method of high-densit diamond thin Download PDFInfo
- Publication number
- CN108660431A CN108660431A CN201710193644.0A CN201710193644A CN108660431A CN 108660431 A CN108660431 A CN 108660431A CN 201710193644 A CN201710193644 A CN 201710193644A CN 108660431 A CN108660431 A CN 108660431A
- Authority
- CN
- China
- Prior art keywords
- diamond
- matrix
- pretreatment fluid
- preparation
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- 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
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/271—Diamond only using hot filaments
-
- 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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
-
- 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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
-
- 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
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/274—Diamond only using microwave discharges
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Carbon And Carbon Compounds (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The present invention provides a kind of preparation methods of high-densit diamond thin, including：To hard alloy substrate, surface charge processing is carried out, keeps its positively charged or negative electricity；Organic acid or amine-containing based compound is added in Xiang Shuizhong, and diamond original powder is added and is uniformly dispersed to obtain Nano diamond suspension；Matrix is placed in the suspension of the Nano diamond opposite with its surface electrical behavior and carries out ultrasonic vibration, the Nano diamond is made to be adsorbed on described matrix surface；Growth on the matrix of chemical vapor depsotition equipment after the treatment is finally used to obtain high-densit diamond thin.Low, diamond thin compactness difference problem that this method solve Nano diamond Enhancing Nucleation Densities in the prior art, it is easy to operate, it is suitble to large-scale production.
Description
Technical field
The invention belongs to Nano diamond technical fields, and in particular to a kind of preparation method of high-densit diamond thin.
Background technology
Diamond material most hard in the world as known to, and there is the low coefficient of sliding friction and highest elasticity
Can, thus it is considered to be cutting element and the desired coating material of other mechanical organs, in hard alloy (WC-Co), titanium alloy
Growth diamond can greatly improve the wearability of tool and component, processing efficiency etc. on equal matrixes.
However, in deposition growing diamond thin on hard alloy substrate, it is commonly present that diamond nucleation density is low, film
It is not fine and close and lead to the interface of film and matrix there are holes, to the problem of combination force difference between film and matrix occur.
In addition, when film is not fine and close, the cobalt in hard alloy can be diffused into from matrix in diamond thin, the generation of catalytic graphite,
Make the degradation of diamond thin.Therefore, the Enhancing Nucleation Density for how improving diamond thin one of is a problem to be solved.
The method for improving diamond nucleation density includes applying middle layer, blanket ion injection, is biased and uses
Bortz powder plants crystalline substance etc., wherein most efficient method is that power supply is biased on pedestal so far, highest in this way
Enhancing Nucleation Density is up to 0.9 × 1010cm-2, but be biased method and be not used to complicated shape matrix, such as sharp blade, complex die
Tool etc., industrial applicibility is poor；And the diamond nucleation density of other methods is relatively low, often 107cm-2Left and right.
Invention content
In view of this, low and to be not suitable for the depositing diamond on complex-shaped workpieces thin for prior art Enhancing Nucleation Density
The shortcomings that film, the present invention provides a kind of preparation method of high-densit diamond thin, this method is suitable for the work of any shape
Depositing diamond film on part can make Enhancing Nucleation Density of the diamond thin on matrix reach 1010cm-2Left and right, to grow
High-densit diamond thin.
In a first aspect, the present invention provides a kind of preparation method of high-densit diamond thin, include the following steps：
(1) hard alloy substrate is taken, its surface is subjected to surface charge processing, the surface chargeization processing includes just
Electrification or negative electricityization processing；
(2) diamond suspension is prepared：Organic acid or amine-containing based compound is added in Xiang Shuizhong, obtains pretreatment fluid；And it will
Diamond original powder is added in the pretreatment fluid, evenly dispersed, obtains Nano diamond suspension；Wherein, organic acid includes
One or more in oxalic acid and citric acid, the amine-containing based compound is selected from glutamic acid and aspartic acid and carbon atom number
It is one or more in the fatty amine of 2-5；
(3) by surface electrification, treated that matrix is placed in the Nano diamond suspension carries out ultrasonic vibration,
The Nano diamond is set to be adsorbed on described matrix surface, wherein the electrical and described matrix of the Nano diamond suspension
It is electrical opposite；
(4) chemical vapor depsotition equipment, the growing diamond membrane on the matrix that step (3) obtains are used.
In the present invention, diamond original powder is added in the preprocessing solution of aqueous and organic acid or amine-containing based compound,
Obtain Nano diamond suspension.Under the action of organic acid or amine-containing based compound, obtained Nano diamond can be molten
Evenly dispersed in liquid, stable suspersion, and grain size is hydrated in smaller range, solve reunion, the settlement issues of diamond original powder, and
And obtained Nano diamond surface can be with different electrical.Wherein, when the organic acid is added into water, obtained nanometer
The surface of diamond is negatively charged；When the amine-containing based compound is added into water, the surface band of obtained Nano diamond is just
Electricity.
The present invention provides a kind of method that electrostatic attraction is implanted into diamond seeds, by surface electrification treated matrix with
The suspension of the opposite Nano diamond of its surface electrical behavior carries out sonic oscillation together, and the pre- shape of diamond is carried out in matrix surface
Core, it may be possible to which the Enhancing Nucleation Density for effectively improving diamond thin makes Enhancing Nucleation Density up to 1010cm-2More than, it is to report at this stage
20-1000 times, under so high Enhancing Nucleation Density, can grow to obtain high-densit diamond thin, improve film and base
Binding ability between body.
Further, when containing the organic acid in the pretreatment fluid, positive electrification processing is carried out to described matrix.
Wherein, the positive electrification processing is that surface hydriding is handled, and is specifically included：Matrix is placed in the vacuum chamber of filming equipment
It is interior, it is passed through high-purity hydrogen, the control indoor air pressure of vacuum is 0.5~20kPa, and substrate temperature is 900~1100 DEG C.Higher temperature
Under hydrogenation treatment under (900~1100 DEG C), on the one hand cemented carbide substrate surfaces is made to hydrogenate, surface is positively charged；On the other hand
The cobalt that cemented carbide substrate surfaces can be removed reduces the diffusion of follow-up cobalt.
Preferably, the hydrotreated time is 0.5~1h.Hydrogen forms hydroperoxyl radical in the plasma, with matrix table
Face interacts, and matrix surface outermost layer atomic layer is made to be connected with hydrogen atom, after the matrix of this surface hydriding is placed in water, base
Body surface face is positively charged.
Further, when containing the amine-containing based compound in the pretreatment fluid, negative electricity is carried out to described matrix
Processing.
Wherein, the negative electricityization processing includes any one of the following manners：The hard is closed using Caro mixed acid
Auri body carries out oxide etch；It is cleaned alternatively, hard alloy substrate is placed in oxygen plasma cleaning machine.
Further, the time of the oxide etch is 0.5~1min.The time of the oxygen plasma cleaning can be 2-
15min。
Specifically, using Caro mixed acid (H2SO4：H2O2=1：10) oxide etch hard alloy substrate can remove portion
Divide Co, and matrix surface is aoxidized, keeps matrix surface negatively charged；Oxygen plasma cleaning is carried out, matrix surface can be made
Take the groups such as-OH.
In Nano diamond suspension the grain size (grain size be less than 50nm) of Nano diamond compared to diamond original powder have compared with
It is big to reduce.In the application, the diamond original powder is commercial product, and (alternatively referred to as Nano diamond aggregation is obtained with explosion method
Object), do not carry out any processing, for particle size from hundreds of nanometers to more than ten micron, average grain diameter is other in the micron-scale.
Preferably, in the Nano diamond suspension, the grain size of Nano diamond is 5-35nm.
Preferably, in the Nano diamond suspension, the grain size of Nano diamond is 5-15nm.Further preferably 5-
10nm。
Preferably, in the Nano diamond suspension, the grain size of Nano diamond is 10-35nm.Further preferably
10-30nm or 10-25nm.
Preferably, the quality of the diamond original powder is the diamond original powder and the quality sum of the treatment fluid
0.005%~0.5%.
In an embodiment of the present invention, when the organic acid or amine-containing based compound are added into water, further include：Using
PH adjusting agent adjusts pH value, and it is 2-10 to make the pH of the pretreatment fluid.PH adjusting agent can be sodium hydroxide or hydrochloric acid.
Preferably, when the organic acid is added into water, the pH of the pretreatment fluid is 2-9.The pretreatment fluid
PH value needs to control in a certain range, in case organic acid is caused suspension unstable and is made diamond particles by more dissociation
Sedimentation.At this point, the surface of Nano diamond is negatively charged in obtained Nano diamond suspension, this is mainly due to organic acids
Carboxyl in (oxalic acid, citric acid) can be adsorbed on diamond original powder particle, keep entire diamond particles negatively charged.
Further, when the organic acid being added into water is citric acid, the pH value of the pretreatment fluid is 3.5-9；When
When the organic acid that Xiang Shuizhong is added is specially oxalic acid, the pH value of the pretreatment fluid is 2-8.
Further, the organic acid in pretreatment fluid a concentration of 10-5~10-3mol/L.Organic acid is described pre-
Suitable concentration in treatment fluid can ensure organic acid all covering diamond particles；The concentration of organic acid cannot be excessive, otherwise
The ionic strength in pretreatment fluid can be improved and then shorten the Debye length (Debye length) of diamond particles in water, and
Diamond particles are caused to attract together and cause to reunite and precipitate under the action of Coulomb force.
In the present invention, when the amine-containing based compound is added into water, obtained Nano diamond suspension is positively charged.
When the amine-containing based compound is while containing carboxyl and amino-NH2Glutamic acid or aspartic acid when, the carboxyl in their molecules
Preferentially can mutually it attract with diamond particle surfaces, and amino obtains proton in water, makes the outermost layer in water in diamond particles
Charge is positively charged.And when the amine-containing based compound is fatty amine, fatty amine forms positively charged NH in water3+, it can be with gold
Hard rock particle surface mutually attracts, and diamond particles is made to be dispersed.
Preferably, the fatty amine is at least one of ethylenediamine and n-propylamine.
Further, the amine-containing based compound in pretreatment fluid a concentration of 10-5~10-3mol/L。
Further, when containing the fatty amine in the pretreatment fluid, the pH of the pretreatment fluid is 3-10.
Further, when containing glutamic acid in the pretreatment fluid, the pH of the pretreatment fluid is 3-10.It is further excellent
It is selected as 3-5.Concentration of the glutamic acid in pretreatment fluid is preferably 10-5~10-4mol/L。
Further, when containing aspartic acid in the pretreatment fluid, the pH of the pretreatment fluid is 5-10.
In step (3) of the present invention, the time of the ultrasonic vibration is 10min-2h, power 200-500W.
Preferably, after the ultrasonic vibration of step (3), further include：Described matrix is taken out, is sequentially placed into water, ethyl alcohol
It is cleaned by ultrasonic, nitrogen is used in combination to dry up.
In step (4) of the present invention, the mode of growing diamond membrane can be heated filament vapor deposition, and microwave plasma increases
Extensive chemical is vapor-deposited, and can also be obtained by the way of other chemical vapor depositions.Diamond crystals in diamond thin
It can be nanometer or micron level, reality can be carried out by the content and gas pressure in vacuum, substrate temperature etc. for controlling reaction gas
It is existing.
In an embodiment of the present invention, diamond thin is prepared by the way of heated filament vapor deposition, sedimentary condition is：
Using hydrogen and methane as reaction gas, methane accounts for total gas volume ranging from 0.6%-2%, gas pressure in vacuum 2-
10kPa；Filament temperature is 1800-2800 DEG C, and the temperature range of matrix is 700-800 DEG C when deposition；Sedimentation time is 1-4h, system
It is standby to obtain diamond thin.The diamond crystals of the diamond film layer are micron level at this time.
Optionally, the thickness of the diamond thin is 0.2~5 μm.
In high-densit thin diamond membrane preparation method provided by the invention, by being connect on surface electrification treated matrix
The kind small particle Nano diamond electrically opposite with it, can greatly improve the Enhancing Nucleation Density of diamond thin, make Enhancing Nucleation Density
Up to 1010cm-2More than, be 20-1000 times reported at this stage, can be made high-densit diamond thin, while with current forming core
The best bias method of density is compared, and technique is simpler, does not need grid bias power supply, especially in workpiece surface in irregular shape
Uniform coated, and bias method can not accomplish the uniform coated on sharp blade due to point discharge effect.This method solve
Nano diamond Enhancing Nucleation Density is low in the prior art, problem of diamond thin compactness difference, easy to operate, is suitble to scale metaplasia
Production.
Advantages of the present invention will be illustrated partly in the following description, and a part is apparent according to specification
, or can be through the embodiment of the present invention implementation and know.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Obtain other attached drawings according to these attached drawings.
Fig. 1 is scanning electron microscope (SEM) figure in diamond thin nucleation process in the embodiment of the present invention 1；
Fig. 2 dissipates for the surface (a) SEM secondary electron images of diamond thin, the section (b) SEM back ofs the body in the embodiment of the present invention 1
Penetrate image, (c) Raman spectrogram.
Specific implementation mode
Technical scheme of the present invention will be clearly and completely described below.Obviously, described embodiment is only
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
The every other embodiment obtained without creative efforts, shall fall within the protection scope of the present invention.Below
Described is the preferred embodiment of the embodiment of the present invention, it is noted that for those skilled in the art,
Under the premise of not departing from principle of the embodiment of the present invention, several improvements and modifications can also be made, these improvements and modifications are also considered as
The protection domain of the embodiment of the present invention.
Embodiment 1
A kind of preparation method of high-densit diamond thin, including：
Step 1, the processing of matrix surface negative electricityization：
Using YG6X (WC-6%Co) carbide chips sold on domestic market as matrix, by it successively in acetone
It is cleaned by ultrasonic 10 minutes in alcohol, then it is KOH to be immersed in proportioning：K3[Fe(CN)6]：H2O=1：1：10 (mass ratioes) it is molten
10 minutes in liquid, to enhance the contact area and mechanical snap (this step can also be omitted) of matrix and follow-up diamond thin,
Then it is H matrix to be immersed in proportioning2SO4：H2O2=1：Oxide etch 30 is carried out in the Caro mixed acid solutions of 10 (volume ratios)
Second, keep matrix surface negatively charged.
Step 2 prepares the suspension of positively charged diamond nano-particles：
Glutamic acid is added in Xiang Shuizhong, and it is 4 to adjust its pH, obtains pretreatment fluid, wherein pretreatment fluid Glutamic Acid is dense
Degree is 7 × 10-5mol/L；Then commercially available Nano diamond original powder is added in above-mentioned pretreatment fluid, it is evenly dispersed, it is received
Rice diamond suspension；Wherein, mass concentration of the Nano diamond in Nano diamond suspension is 0.005wt.%.
Step 3, by step 1, treated that hard alloy substrate is put into that the Nano diamond suspension in step 2 carries out
Sonic oscillation 30 minutes, ultrasonic power 250W make Nano diamond granular absorption in cemented carbide substrate surfaces, wherein adsorbing
It is less than 50nm (being specially 35-45nm) in the grain size of the Nano diamond of cemented carbide substrate surfaces.
Step 4 takes out hard alloy substrate, is sequentially placed into water, alcohol and is cleaned by ultrasonic, is finally dried with nitrogen.
Step 5, by treated, sample is placed in the vacuum chamber of hot-filament chemical vapor deposition equipment, using following ginseng
Number growing diamond membrane 2.5h, obtains high-densit diamond thin：Using hydrogen and methane as reaction gas, hydrogen and first are controlled
The flow of alkane is respectively 800sccm and 16sccm, and deposition pressure 4kPa, filament temperature is 2400 DEG C, 850 DEG C of substrate temperature.
Wherein, the surface topography of first 10 minutes progress diamond nucleations is grown as shown in Figure 1, being computed, this Enhancing Nucleation Density
Up to 1.1 × 1010cm-2.Continue after depositing 1.5h, surface topography, Cross Section Morphology and the Raman spectrum of this film are shown in such as Fig. 2 institutes
Show, the thickness of obtained diamond thin is 2 μm, 1 μm of the crystallite dimension of diamond.It can be seen that from (a) and (b) in Fig. 2
Diamond thin even compact, the 1338cm in Raman spectrum ((c) in Fig. 2)-1Place shows the peak of sharp diamond,
1400cm-1To 1600cm-1The peak value of the graphite-phase broad peak at place is very low, this illustrates that diamond quality is higher.
Embodiment 2
A kind of preparation method of high-densit diamond thin, including：
Step 1, matrix surface carry out hydrogenation treatment：
Using YG8 (WC-8%Co) carbide chips sold on domestic market as matrix, by it successively in acetone
It is cleaned by ultrasonic 10 minutes in alcohol, then matrix is put into the vacuum chamber of microwave plasma enhanced chemical vapor depsotition equipment
It is interior, to vacuum chamber in be only passed through high-purity hydrogen, control deposition pressure ranging from 3kPa, substrate temperature is 1000 DEG C, microwave power
1000W keeps matrix surface positively charged.
Step 2 prepares the suspension of electronegative diamond nano-particles：
Oxalic acid is added in Xiang Shuizhong, and it is 6 to adjust its pH, obtains pretreatment fluid, the wherein concentration of pretreatment fluid Glutamic Acid
It is 10-4mol/L；Then commercially available Nano diamond original powder is added in above-mentioned pretreatment fluid, it is evenly dispersed, obtain a nanometer Buddha's warrior attendant
Stone suspension；Wherein, mass concentration of the Nano diamond in Nano diamond suspension is 0.5wt.%.
Step 3, by step 1, treated that hard alloy substrate is put into that the Nano diamond suspension in step 2 carries out
Sonic oscillation 15 minutes, ultrasonic power 300W make Nano diamond granular absorption in cemented carbide substrate surfaces, wherein adsorbing
It is less than 50nm (being specially 20-25nm) in the grain size of the Nano diamond of cemented carbide substrate surfaces.
Step 4 takes out hard alloy substrate, is sequentially placed into water, alcohol and is cleaned by ultrasonic, is finally dried with nitrogen.
Step 5, by the vacuum chamber of treated sample is placed on microwave plasma enhanced chemical vapor depsotition equipment
In, using following parameter growing diamond membrane 2h：Using hydrogen and methane as reaction gas, to control the flow of hydrogen and methane
Respectively 500sccm and 20sccm, deposition pressure 3kPa, 800 DEG C of substrate temperature.
In the present embodiment 2, the thickness of the diamond thin formed after deposition is 3 μm, the crystalline substance of diamond in diamond thin
Particle size is 80nm, and the Enhancing Nucleation Density in 20 minutes forming core stages is up to 1.3 × 10 before deposition growing10cm-2。
Embodiment 3
A kind of preparation method of high-densit diamond thin, including：
Step 1, the processing of matrix surface negative electricityization：
Using YT15 (WC-15%TiC) the hard alloy transposition blades sold on domestic market as matrix, successively by it
It is cleaned by ultrasonic 10 minutes in acetone and alcohol, nitrogen is used in combination to dry up；Then matrix oxygen plasma machine is placed in clean
4min keeps matrix surface negatively charged；
Step 2 prepares the suspension of positively charged diamond nano-particles：
Aspartic acid is added in Xiang Shuizhong, and it is 7 to adjust its pH, obtains pretreatment fluid, wherein aspartic acid in pretreatment fluid
A concentration of 7 × 10-5mol/L；Then commercially available Nano diamond original powder is added in above-mentioned pretreatment fluid, it is evenly dispersed, it obtains
To Nano diamond suspension；Wherein, mass concentration of the Nano diamond in Nano diamond suspension is 0.01wt.%.
Step 3, by step 1, treated that hard alloy substrate is put into that the Nano diamond suspension in step 2 carries out
Sonic oscillation 40 minutes, ultrasonic power 280W make Nano diamond granular absorption in cemented carbide substrate surfaces, wherein adsorbing
It (is specially (being specially 10-20nm) to be less than 50nm in the grain size of the Nano diamond of cemented carbide substrate surfaces.
Step 4 takes out hard alloy substrate, is sequentially placed into water, alcohol and is cleaned by ultrasonic, is finally dried with nitrogen.
Step 5, by treated, sample is placed in the vacuum chamber of hot-filament chemical vapor deposition equipment, with hydrogen and first
Alkane is reaction gas, using following parameter growing diamond membrane 2h：Control methane accounts for the 1% of total gas volume, deposition process
Middle gas pressure in vacuum ranging from 6kPa, 2800 DEG C of filament temperature, 880 DEG C of substrate temperature obtain the diamond that thickness is 3 μm and apply
Layer, in diamond coatings, diamond grain size is 2 μm.
Embodiment 4
A kind of preparation method of high-densit diamond thin, including：
Step 1, the processing of matrix surface negative electricityization：
Using YG6X (WC-6%Co) carbide chips sold on domestic market as matrix, by it successively in acetone
It is cleaned by ultrasonic 10 minutes in alcohol, then it is KOH to be immersed in proportioning：K3[Fe(CN)6]：H2O=1：1：10 (mass ratioes) it is molten
30 minutes in liquid, to enhance the contact area and mechanical snap (this step can also be omitted) of matrix and follow-up diamond thin,
Then it is H matrix to be immersed in proportioning2SO4：H2O2=1：Oxide etch 25 is carried out in the Caro mixed acid solutions of 10 (volume ratios)
Second, keep matrix surface negatively charged.
Step 2 prepares the suspension of positively charged diamond nano-particles：
N-propylamine is added in Xiang Shuizhong, and it is 6 to adjust its pH, obtains pretreatment fluid, wherein pretreatment fluid Glutamic Acid is dense
Degree is 6 × 10-5mol/L；Then commercially available Nano diamond original powder is added in above-mentioned pretreatment fluid, it is evenly dispersed, it is received
Rice diamond suspension；Wherein, mass concentration of the Nano diamond in Nano diamond suspension is 0.05wt.%.
Step 3, by step 1, treated that hard alloy substrate is put into that the Nano diamond suspension in step 2 carries out
Sonic oscillation 30 minutes, ultrasonic power 300W.
Step 4 takes out hard alloy substrate, is sequentially placed into water, alcohol and is cleaned by ultrasonic, is finally dried with nitrogen.
Step 5, by treated, sample is placed in the vacuum chamber of hot-filament chemical vapor deposition equipment, first hydrogen and
The flow of methane is respectively 500sccm and 10sccm, continues 0.5h；Then methane flow is reduced to 5sccm, and hydrogen flowing quantity is kept
It is constant, continue 2.5h.Obtain high-densit diamond thin：Using hydrogen and methane as reaction gas, the stream of hydrogen and methane is controlled
Amount is respectively 800sccm and 16sccm.Gas pressure in vacuum ranging from 3kPa in deposition process, 2500 DEG C of filament temperature, matrix temperature
850 DEG C of degree obtains thickness as 4 μm of diamond coatings, and in diamond coatings, diamond grain size is 3 μm.
For prominent beneficial effects of the present invention, the present invention also provides following comparative examples：
Comparative example 1：On the basis of embodiment 1, using the aqueous suspension of commercially available diamond original powder directly to acetone, alcohol
Matrix after ultrasonic cleaning carries out implantation diamond seeds, by same thin film growth process growing diamond membrane, after testing,
The Enhancing Nucleation Density of the preceding 10 minutes diamonds of growth is only 107cm-2.And there are porous structures in diamond thin, it is less fine and close.
When this explanation does not carry out chargeization processing to matrix, the Nano diamond suspension obtained using present invention preparation is connect
Kind, and Enhancing Nucleation Density when growing diamond membrane is still relatively low.
Comparative example 2：On the basis of embodiment 1, using suspension (the paddy ammonia for preparing positively charged diamond nano-particles
Acid, water, pH=7) implantation diamond seeds directly are carried out to the matrix after acetone, alcohol ultrasonic cleaning, it is given birth to by same film
Long technique growing diamond membrane, after testing, the Enhancing Nucleation Density for growing preceding 10 minutes diamonds are 108cm-2.The above comparison is said
Bright, the parameters such as pH of the pretreatment fluid containing glutamic acid have a major impact the Enhancing Nucleation Density of final diamond coatings, need to control
In protection scope of the present invention.
It should be noted that according to the above description the announcement of book and with illustrate, those skilled in the art in the invention also
The above embodiment can be changed and be changed.Therefore, the invention is not limited in specific realities disclosed and described above
Mode is applied, some equivalent modifications and change to the present invention should also be as within the scope of the claims of the present invention.This
Outside, although having used some specific terms in this specification, these terms are merely for convenience of description, not to the present invention
Constitute any restrictions.
Claims (10)
1. a kind of preparation method of high-densit diamond thin, which is characterized in that include the following steps：
(1) hard alloy substrate is taken, its surface is subjected to surface charge processing, the surface chargeization processing includes positive electrification
Or negative electricityization processing；
(2) diamond suspension is prepared：Organic acid or amine-containing based compound is added in Xiang Shuizhong, obtains pretreatment fluid；And by Buddha's warrior attendant
Stone original powder is added in the pretreatment fluid, evenly dispersed, obtains Nano diamond suspension；Wherein, organic acid includes oxalic acid
With it is one or more in citric acid, the amine-containing based compound is selected from glutamic acid and aspartic acid and carbon atom number is 2-5
Fatty amine in it is one or more；
(3) by the surface chargeization, treated that matrix is placed in the Nano diamond suspension carries out ultrasonic vibration, makes
The Nano diamond is adsorbed on described matrix surface, wherein the electrical and described matrix of the Nano diamond suspension
It is electrically opposite；
(4) chemical vapor depsotition equipment, the growing diamond membrane on the matrix that step (3) obtains are used.
2. preparation method as described in claim 1, which is characterized in that when containing the organic acid in the pretreatment fluid,
Positive electrification processing is carried out to described matrix；When in the pretreatment fluid contain the amine-containing based compound when, to described matrix into
The processing of row negative electricityization.
3. preparation method as claimed in claim 1 or 2, which is characterized in that the positive electrification processing is that surface hydriding is handled, tool
Body includes：Matrix is placed in the vacuum chamber of filming equipment, is passed through high-purity hydrogen, the control indoor air pressure of vacuum is 0.5~
20kPa, substrate temperature are 900~1100 DEG C.
4. preparation method as claimed in claim 1 or 2, which is characterized in that the negative electricityization processing includes in following manner
It is any：
Oxide etch is carried out to the hard alloy substrate using Caro mixed acid；
It is cleaned alternatively, hard alloy substrate is placed in oxygen plasma cleaning machine.
5. preparation method as described in claim 1, which is characterized in that when the organic acid or amino-contained chemical combination are added into water
When object, further include：PH value is adjusted using pH adjusting agent, it is 2-10 to make the pH of the pretreatment fluid.
6. processing method as claimed in claim 5, which is characterized in that when the organic acid being added into water is citric acid
When, the pH value of the pretreatment fluid is 3.5-9；
When the organic acid being added into water is oxalic acid, the pH value of the pretreatment fluid is 2-8.
7. preparation method as claimed in claim 5, which is characterized in that when the amine-containing based compound being added into water is paddy
When propylhomoserin or fatty amine, the pH of the pretreatment fluid is 3-10；
When the amine-containing based compound being added into water is aspartic acid, the pH of the pretreatment fluid is 5-10.
8. preparation method as described in claim 1, which is characterized in that the organic acid or amine-containing based compound are in pretreatment fluid
In a concentration of 10-5~10-3mol/L。
9. preparation method as described in claim 1, which is characterized in that the quality of the diamond original powder is that the diamond is former
Powder and the 0.005%~0.5% of the quality sum of the treatment fluid.
10. preparation method as described in claim 1, which is characterized in that Nano diamond in the Nano diamond suspension
Grain size be less than 50nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710193644.0A CN108660431A (en) | 2017-03-28 | 2017-03-28 | A kind of preparation method of high-densit diamond thin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710193644.0A CN108660431A (en) | 2017-03-28 | 2017-03-28 | A kind of preparation method of high-densit diamond thin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108660431A true CN108660431A (en) | 2018-10-16 |
Family
ID=63786703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710193644.0A Pending CN108660431A (en) | 2017-03-28 | 2017-03-28 | A kind of preparation method of high-densit diamond thin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108660431A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109853003A (en) * | 2019-03-06 | 2019-06-07 | 江西科技师范大学 | A kind of micro channel type boride of resistance to fused salt corrosion/diamond composite and preparation method thereof |
| CN110699689A (en) * | 2019-09-11 | 2020-01-17 | 深圳先进技术研究院 | Diamond film and preparation method and application thereof |
| CN113445024A (en) * | 2021-06-28 | 2021-09-28 | 浙江劳伦斯机床有限公司 | Preparation method of diamond coating, diamond coating and cutter |
| DE102021115887A1 (en) | 2021-06-18 | 2022-12-22 | Oerlikon Surface Solutions Ag, Pfäffikon | Process for improving the adhesion of diamond coatings |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5485804A (en) * | 1994-05-17 | 1996-01-23 | University Of Florida | Enhanced chemical vapor deposition of diamond and related materials |
| CN104746030A (en) * | 2015-04-23 | 2015-07-01 | 太原理工大学 | Method for improving bonding strength of hard alloy and diamond coating |
| WO2015185555A1 (en) * | 2014-06-02 | 2015-12-10 | Gühring KG | Diamond-coated machining tool and method for production thereof |
| CN105256278A (en) * | 2015-11-13 | 2016-01-20 | 浙江工业大学 | Method for preparing diamond film on stainless steel surface |
-
2017
- 2017-03-28 CN CN201710193644.0A patent/CN108660431A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5485804A (en) * | 1994-05-17 | 1996-01-23 | University Of Florida | Enhanced chemical vapor deposition of diamond and related materials |
| WO2015185555A1 (en) * | 2014-06-02 | 2015-12-10 | Gühring KG | Diamond-coated machining tool and method for production thereof |
| CN104746030A (en) * | 2015-04-23 | 2015-07-01 | 太原理工大学 | Method for improving bonding strength of hard alloy and diamond coating |
| CN105256278A (en) * | 2015-11-13 | 2016-01-20 | 浙江工业大学 | Method for preparing diamond film on stainless steel surface |
Non-Patent Citations (1)
| Title |
|---|
| TAO WANG ET AL.: "Enhancing the colloidal stability of detonation synthesized diamond particles in aqueous solutions by adsorbing organic mono-, bi- and tridentate molecules", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109853003A (en) * | 2019-03-06 | 2019-06-07 | 江西科技师范大学 | A kind of micro channel type boride of resistance to fused salt corrosion/diamond composite and preparation method thereof |
| CN110699689A (en) * | 2019-09-11 | 2020-01-17 | 深圳先进技术研究院 | Diamond film and preparation method and application thereof |
| DE102021115887A1 (en) | 2021-06-18 | 2022-12-22 | Oerlikon Surface Solutions Ag, Pfäffikon | Process for improving the adhesion of diamond coatings |
| CN113445024A (en) * | 2021-06-28 | 2021-09-28 | 浙江劳伦斯机床有限公司 | Preparation method of diamond coating, diamond coating and cutter |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108660431A (en) | A kind of preparation method of high-densit diamond thin | |
| EP1964812B1 (en) | Carbon nano tube electrode formed by directly growing carbon nano tube on surface of carbon paper and supporting platinum-based nano catalyst on carbon nano tube using cvd method and manufacturing method thereof | |
| US11603594B2 (en) | Boron doped diamond electrode and preparation method and applications thereof | |
| CN109422262B (en) | Super-dispersed nano-diamond dispersion liquid and preparation method and application thereof | |
| CN108149219B (en) | Diamond composite coating cutter and preparation method thereof | |
| CN111334779B (en) | Boron-doped diamond film and preparation method thereof, oil-water separation element, water treatment electrode and preparation method thereof, and water treatment device | |
| CN109097754A (en) | A kind of surface have high density nano diamond thin workpiece and a kind of preparation method of high density nano diamond thin | |
| CN1528947A (en) | Hard alloy matix complex shape cutter diamond coating preparation method | |
| CN105755448A (en) | Nano diamond thin film and preparation method thereof | |
| CN111058011A (en) | Nano-diamond-graphene composite film electrode and preparation method thereof | |
| CN110885968B (en) | Preparation method of diamond coating, diamond coating prepared by preparation method and cutting tool | |
| CN113445024B (en) | Preparation method of diamond coating, diamond coating and cutter | |
| Mahajan et al. | Carbon nanotube–nanocrystal heterostructures fabricated by electrophoretic deposition | |
| CN105779965B (en) | A method of porous doped diamond film is prepared using particle beams control technique | |
| CN109518160B (en) | Surface treatment process | |
| CN110496616B (en) | Photoelectrocatalysis metal-loaded boron-doped diamond, preparation method and application | |
| KR20150004664A (en) | Pre-processes for diamond film coating and diamond film coating method using the same | |
| WO2018176217A1 (en) | Method of preparing high-density diamond thin film | |
| CN116377575A (en) | Method for growing diamond on laser crystal | |
| CN113410062B (en) | Carbon nanocoil accumulation body/nickel-cobalt compound supercapacitor composite electrode material and preparation method thereof | |
| CN109248684A (en) | A kind of MWCNT@Cu composite catalyst and its preparation method and application | |
| CN108441825A (en) | Doping metals diamond-like coating preparation method and its product | |
| CN111155071B (en) | Sulfur ion injection nano diamond-graphene composite film electrode and preparation method thereof | |
| CN1316274A (en) | Electrochemical process for modifying surface of biologic metal/Ca-P ceramic material | |
| CN111607816A (en) | Method for pulse electrodeposition of Ni-SiC composite coating on surface of aluminum alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181016 |