CN105239026B - One-dimensional diamond reinforced aluminum matrix composite material and preparing method thereof - Google Patents
One-dimensional diamond reinforced aluminum matrix composite material and preparing method thereof Download PDFInfo
- Publication number
- CN105239026B CN105239026B CN201510659346.7A CN201510659346A CN105239026B CN 105239026 B CN105239026 B CN 105239026B CN 201510659346 A CN201510659346 A CN 201510659346A CN 105239026 B CN105239026 B CN 105239026B
- Authority
- CN
- China
- Prior art keywords
- diamond
- dimensional
- aluminum
- aluminum matrix
- film
- 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.)
- Active
Links
Abstract
The invention discloses a one-dimensional-diamond-reinforced aluminum matrix composite material and a preparing method. The composite material is characterized in that a diamond array composed of a plurality of one-dimensional diamond wires is distributed in an aluminum matrix, and the one-dimensional diamond wires are surface-modified diamond wires and are combined with the aluminum matrix in a metallurgical manner. The preparing method of the composite material includes the steps that after the surface-modified diamond wires are distributed in an array manner, the aluminum matrix or the aluminum matrix containing surface-modified diamond particles is compounded with the diamond wire array through one of a casting technology, an infiltration technology, a cold pressing sintering technology, a hot pressing sintering technology and a plasma sintering technology, and the one-dimensional-diamond-reinforced aluminum matrix composite material in which the one-dimensional diamond wires are combined with the aluminum matrix in the metallurgical manner is obtained. According to the one-dimensional-diamond-reinforced aluminum matrix composite material and the preparing method, the one-dimensional diamond wires are distributed in the aluminum matrix in the array manner, a series-parallel connection composite heat conduction structure is formed by adding the diamond particles, the heat conducting efficiency is further improved, the composite material can be used as an electronic packaging material, a heat sink material and the like, and packaging of high-temperature, high-frequency and high-power electronic devices is achieved.
Description
Technical field
The present invention relates to a kind of diamond composite, more particularly to a kind of one-dimensional diamond enhancing aluminum-base composite material
Material, the invention further relates to the preparation method of the one-dimensional diamond reinforced aluminum matrix composites.
Background technology
Electronic Packaging be constitute all parts of electronic device or integrated circuit by the requirement of regulation realize reasonable Arrangement,
The operating procedure assemble, be bonded, connect, being environmentally isolated with, it is desirable to which encapsulating material has a high thermal conductivity, low thermal coefficient of expansion,
Good mechanical support, physical protection, electrical connection, radiate moistureproof, outer field shield, dimensional transitions and stable element parameter etc.
Effect.With the fast development of electronic information technology, electronic machine forward direction high-performance, low cost, miniaturization, facilitation, many work(
Energy integrated direction is fast-developing, and electronic devices and components integrated level and the speed of service are constantly raised, and cause IC products to send
Heat be significantly increased, so as to affect the stability of electronic device.Although electronic package material has gone through 1st generation copper at present
Alloy, 2nd generation tungsten copper and molybdenum-copper, to alloys such as the 3rd generation Al/SiC, Al/Si, these materials have very big in density
It is progressive, but be also difficult to meet the demand of integrated circuit and chip technology high speed development on heat conductivility.
Diamond is the best material of heat conductivility in nature, and the thermal conductivity under room temperature can reach 2200W/ (mK),
It is 10 times of aluminum, and its thermal coefficient of expansion (CTE) only 0.8 × 10-6/ K, less than the 1/20 of aluminum.The thermal conductivity height of metallic aluminium,
Price is low, easy processing, is traditional electronic package material.Make composite wood after special handling being carried out to aluminum and diamond
It is material so as to have the characteristic of aluminum and diamond concurrently, such as high connductivity, high heat conduction, high intensity, controllable thermal coefficient of expansion, relatively low close
The combination properties such as degree, overcome aluminum low intensity inherently, it is wear-resisting poor the shortcomings of, replace be widely used at present Cu, W-Cu,
The electronic package materials such as Al/SiC, AlN, are the study hotspots for currently solving modern electronic devices heat dissipation problem.
It is relatively early for the external starting of the research of diamond/metal (Cu, Al and all kinds of alloys) composite, it is concentrated mainly on
The developed countries such as the U.S., Japan and Europe, achievement in research are also more, and almost the overwhelming majority concentrates on diamond particles enhancing
Metal-base composites.For diamond/aluminum composite, the Johnson in the U.S. etc. utilizes pressureless infiltration diamond particles
Skeleton successfully obtains diamond/aluminum composite, and the heat conductivity of preparation is 259W/ (mK)；Natishan etc. will
Prior powder metallurgy method is applied to the preparation of diamond/aluminum composite, it is desirable to can realize the optimization to composite, but effect
It is unobvious.2004, O.Beffort etc. prepared diamond particles reinforced aluminum matrix composites using conventional pressure infiltration method,
But heat conductivity only has 130W/ (mK).And for diamond/copper composite, nineteen ninety-five, U.S. Sun
Microsystems companies and Lawrence Livermore National Laboratories have developed jointly diamond particles/composite copper material
Material, uses as the substrate of multi-chip module, and thermal conductivity is 420W/ (mK), and CTE when 25～200 DEG C is (5.48～6.5)
×10-6K-1, match with the CTE of GaAs, but preparation technology be more complicated, cost is also very high.
In theory, the thermal conductivity of diamond/metal-base composites should be between diamond and metallic matrix, so will be big
The big heat conductivity for improving composite；But in fact, the thermal conductivity of diamond/aluminum is often less than 300W/ (mK), and Buddha's warrior attendant
The thermal conductivity of stone/carbon/carbon-copper composite material is often less than 400W/ (mK).This is because diamond and aluminum, the wettability extreme difference of copper, two
Combining in many faults of construction and the space of can closely not cause, and causes and very big thermal resistance is defined at composite material interface.
According to heat conduction theory, exist between matrix and reinforcement in composite and connect and two kinds of distributions in parallel, gold
Hard rock granule reinforced copper base composite material belongs to series model, and bortz powder content in the composite needs very high (generally
More than 70%) preferable heat conductivility could be obtained.For example：2008, Russian Ekimov et al. was in diamond particles matter
Up under 90～95% maximum conditions, High Temperature High Pressure sintering is prepared for a kind of new bortz powder/carbon/carbon-copper composite material to amount fraction,
The matrix of the compound material is bortz powder (particle size range is 0～500 μm), and copper makes diamond high in high temperature as binding agent
The continuous framing structure that pressure is formed, the thermal conductivity of the composite reach as high as 920W/ (mK).Illustrate this series connection mould
Formula, even if diamond content up to more than 90%, as intercrystalline has copper Binder Phase, cannot form between diamond and continuously lead
The passage of heat so as to which thermal conductivity is far below diamond.In other words, number of interfaces between diamond is reduced, forms continuous diamond and lead
The passage of heat, is to improve one of most effective approach of diamond/copper composite heat conductivility.
Diamond Electronic Packaging field application earliest by cvd diamond self-supporting thick film realizing, due to
Larger thickness is required, use cost is greatly improved.Chemical vapour deposition technique can be prepared in the substrate surface of complicated shape
Continuous fine and close High Quality Diamond Films, can make continuous passage of heat is formed between diamond crystalses, therefore have some scholars one
It is straight exploring using CVD preparing diamond film/carbon/carbon-copper composite material.
It is heat-conducting copper-based that patent of invention CN102244051A of the present inventor seminar early stage discloses a kind of high-performance orientation
Diamond composite and preparation method thereof：1) diamond rod is inserted in the columnar through holes of Copper substrate, and copper is made by extruding
There is plastic deformation in matrix, so that copper is completely attached to diamond rod coupling；2) diamond rod is inserted the column of Copper substrate
In through hole, then copper is deposited along diamond rod direction in copper sheet by electro-deposition techniques, make the complete cladding diamond rod of copper, with Buddha's warrior attendant
Stone completely attaches to coupling.Copper base diamond composite prepared by the method has preferably orientation heat conductivility, but due to its gold
Wettability extreme difference between hard rock rod and parent metal, two-phase interface are combined not closely, between diamond rod and parent metal
Interface defines very big thermal resistance, and its thermal conductivity need further to optimize.
The content of the invention
First technical problem to be solved by this invention is to provide a kind of Vygen that can realize that high-performance orients heat conduction
Hard rock reinforced aluminum matrix composites.
Second technical problem to be solved by this invention provides one kind and realizes the one-dimensional diamond of high-performance orientation heat conduction
The preparation method of reinforced aluminum matrix composites.
To solve above-mentioned first technical problem, one-dimensional diamond reinforced aluminum matrix composites of the invention, including aluminum substrate,
It is characterized in that：The diamond array being made up of some one-dimensional diamond wires, a Vygen are distributed in described aluminum substrate
Hard rock line and aluminum substrate metallurgical binding.
The one-dimensional diamond reinforced aluminum matrix composites of the present invention, the one-dimensional diamond wire in described diamond array is in gold
Arranged in parallel in category base material, relative position is uniformly arranged or random arrangement.
The one-dimensional diamond reinforced aluminum matrix composites of the present invention, described one-dimensional diamond wire be self-supporting diamond line or
Center is provided with the line of linear core and supports diamond wire, a diameter of 0.015～2.0mm of self-supporting diamond line, line to support Buddha's warrior attendant
A diameter of 0.015～3.0mm of stone line；Described linear core selects tungsten, molybdenum, copper, titanium, silver, gold, carbon fiber, silicon carbide fibre
In a kind of filamentous silk material；A diameter of 0.014～2.0mm of described linear core.
The one-dimensional diamond reinforced aluminum matrix composites of the present invention, the one-dimensional diamond wire are surface modified diamond line,
Surface modified diamond line is that one-dimensional diamond wire surface is provided with metal film to be modified, and the effect of metal film is to improve
Wettability between diamond and parent metal, therefore, the preferable film material of wettability should be selected between adjacent film layers；Institute
The one kind of metal film in titanium film, tungsten film/copper film, chromium film/copper film is stated, wherein：Titanium film thicknesses of layers is 0.1～1.0 μm, tungsten
Film/copper film thicknesses of layers is 0.02～0.2 μm/1.0～10.0 μm, and chromium film/copper film thicknesses of layers is 0.05～0.5 μm/2～20
μm。
The one-dimensional diamond reinforced aluminum matrix composites of the present invention, are also distributed with surface in described aluminum substrate through molybdenum
The modified diamond particles of film/copper film, diamond particles are metallurgical binding with aluminum substrate, and diamond particles granularity is 1～200 μ
M, it is 0～50% that the diamond particles account for the percentage composition of total composite volume；The thicknesses of layers of the molybdenum film/copper film is
0.05～0.5 μm/0.5～5.0 μm, and molybdenum film inner surface combined with diamond surface, copper film is coated on molybdenum film outer surface.
To solve above-mentioned second technical problem, the preparation method of one-dimensional diamond reinforced aluminum matrix composites of the invention,
The one-dimensional diamond wire arrangement that first surface is modified is random distribution or equally distributed diamond wire array；Then, adopt
Founding, infiltration, cold-rolled sintered, hot pressed sintering, a kind of technique in plasma agglomeration, by aluminum or aluminum alloy and diamond wire array
It is compound, obtain the one-dimensional diamond reinforced aluminum matrix composites of one-dimensional diamond wire and aluminum substrate metallurgical binding；Or
Using a kind of technique in founding, infiltration, cold-rolled sintered, hot pressed sintering, plasma agglomeration, will be modified comprising surface
The aluminum or aluminum alloy of diamond particles is combined with diamond wire array, obtains the one of one-dimensional diamond wire and aluminum substrate metallurgical binding
Vygen hard rock reinforced aluminum matrix composites.
The preparation method of the one-dimensional diamond reinforced aluminum matrix composites of the present invention, surface is modified one-dimensional diamond wire or surface
Modified diamond particles are using one or more plating side in magnetron sputtering, multi-arc ion coating, vacuum evaporation, chemical plating, plating
Formula realizes that surface is modified.
The preparation method of the one-dimensional diamond reinforced aluminum matrix composites of the present invention, described surface is modified one-dimensional diamond wire
The line that linear core is provided with for self-supporting diamond Xian Huo centers supports diamond wire.
The preparation method of the one-dimensional diamond reinforced aluminum matrix composites of the present invention, the self-supporting diamond line preparation technology
Method, flame combustion process, direct-current discharge method, DC arc plasma jet, low pressure are strengthened using heated filament auxiliary law, microwave plasma
A kind of chemical gaseous phase depositing process in radio frequency method, normal-pressure radio-frequency method, electron cyclotron resonace method is in linear core or flat substrates
Surface depositing diamond, after etching linear core or flat substrates, obtains the one-dimensional diamond wire of self-supporting or lamellar self-supporting gold
Hard rock piece, lamellar self-supporting diamond piece obtain the one-dimensional diamond wire of self-supporting, the one-dimensional diamond of self-supporting through cut
Linear diameter is 0.015～2.0mm；
The line support diamond wire preparation technology using heated filament auxiliary law, microwave plasma strengthen method, flame combustion process,
One kindization in direct-current discharge method, DC arc plasma jet, low pressure radio frequency method, normal-pressure radio-frequency method, electron cyclotron resonace method
CVD method is learned in linear core surfaces depositing diamond, diamond thicknesses of layers is 0.001～1mm, linear core choosing
With a kind of filamentous silk material in tungsten, molybdenum, copper, titanium, silver, gold, carbon fiber, silicon carbide fibre；The diameter of described linear core
For 0.014～2.0mm.
The preparation method of the one-dimensional diamond reinforced aluminum matrix composites of the present invention, the line support diamond wire, are adopting
Chemical gaseous phase depositing process carried out pretreatment, pretreatment to linear core surfaces before linear core surfaces depositing diamond
Technique is：
For the linear core that can form strong carbide, core is carried out oil removing, scale removal successively, after electrochemical polish, directly
Connect；The linear of strong carbide can be formed
The one kind of core in W, Mo, Ti, Cr, Ta, Si, Nb；
Or
For the linear core that can not form strong carbide, core is carried out oil removing, scale removal successively, after electrochemical polish,
The thin film that can form strong carbide is prepared using physical vapour deposition (PVD) or chemical vapour deposition technique in core surfaces, thin film is single
One kind in layer film, plural layers, alloy firm, then, carries out ultrasound wave shake in being soaked in fine diamond powder suspension
Swing plantation seed crystal pretreatment；The one kind of the linear core of strong carbide in Cu, Ag, Au, Ni, Al, Co can not be formed.
The preparation method of the one-dimensional diamond reinforced aluminum matrix composites of the present invention, the founding are by containing modified diamond
Grain or the aluminum or aluminum alloy without modified diamond particles are put in graphite jig in the lump with one-dimensional diamond array, then by which
600～1000 DEG C of meltings are heated in being put into vacuum melting furnace or atmosphere protection smelting furnace, cooling and demolding obtains one-dimensional diamond
Reinforced aluminum matrix composites；Or
Aluminum or aluminum alloy is heated to into 600～800 DEG C in crucible first, melting aluminum or aluminum alloy is obtained, directly will be in battle array
The one-dimensional diamond wire leaching of row arrangement is placed in the aluminum or aluminum alloy of liquid, or to the modified Buddha's warrior attendant of addition in melting aluminum or aluminum alloy
Stone granule, stir after, the one-dimensional diamond wire being arranged in array leaching is placed in the aluminum or aluminum alloy of liquid, is cooled down, is obtained
To one-dimensional diamond reinforced aluminum matrix composites.
The preparation method of the one-dimensional diamond reinforced aluminum matrix composites of the present invention, the infiltration is for being arranged in array
Dimension diamond wire be placed in infiltration mould, preheated, under vacuum or protective atmosphere environment, will contain modified diamond particles or
The aluminum or aluminum alloy of the molten state without modified diamond particles pressurizes infiltration into infiltration mould, carries out with diamond rod multiple
Close, in 500～700 DEG C of scopes, the pouring temperature of molten state aluminum is 700～900 DEG C for the preheating temperature control of diamond rod array,
Infiltration pressure is 5～30MPa, and temperature retention time is 0.5～3 hour, obtains one-dimensional diamond reinforced aluminum matrix composites.
The preparation method of the one-dimensional diamond reinforced aluminum matrix composites of the present invention, the hot pressed sintering are to close aluminium powder or aluminum
After bronze or the aluminium powder containing modified diamond particles or Al alloy powder add one-dimensional diamond array, vacuum or protective atmosphere are put into
Hot pressed sintering in hot pressing furnace, sintering temperature are 550～655 DEG C, and pressure is 5～200MPa, and the time is 30～240 minutes, cooling
The demoulding, obtains one-dimensional diamond reinforced aluminum matrix composites.
The preparation method of the one-dimensional diamond reinforced aluminum matrix composites of the present invention, the plasma agglomeration is by aluminium powder or aluminum
During alloyed powder or the aluminium powder containing modified diamond particles or Al alloy powder add one-dimensional diamond array, after compacting, be put into etc. from
It is sintered in sub- sintering furnace, 5～70MPa of pressure, sintering process is：500～700 DEG C of sintering temperature, programming rate 10～300
DEG C/min, and 5～10min is incubated, atmosphere is vacuum.
Inventor according to the effect of " water pump " to current in nature, dexterously by " heat pump " concept be incorporated into diamond/
In carbon/carbon-copper composite material, by diamond wire array of arranging in a metal, diamond wire is made to form parallel-connection structure with metal, as " water
Hot-fluid is equally constantly extracted out by pump ", is quickly drawn out in the diamond wire for heat in copper around constantly being sucked arest neighbors.This
Invention is first sequentially prepared the thin film good with diamond wettability and base material on one-dimensional diamond wire surface using process for modifying surface
Aluminum has the film layer of good wettability, effectively improves the wettability between diamond thin and aluminium；It is modified to surface
Diamond wire carries out pre- arrangement, then again using the side such as fine vacuum infiltration or protective atmosphere infiltration, hot pressed sintering, plasma agglomeration
Method prepares diamond wire reinforced aluminum matrix composites, promotes the interface diffusion between diamond wire and parent metal, improves
Interface cohesion condition, realizes metallurgical binding, reduces interface thermal conductivity, make " heat pump " effect further be effectively played；It is compound
The diamond particles of Jing duplex surface modifications are with the addition of in material, heat transfer efficiency is further increased.Overcome in prior art
There is the dissatisfactory defect of thermal conductivity in patent CN102244051A.In other words, no matter the present invention is constituted in composite structure
Aspect, or huge innovation and improvement are all made that in terms of technology of preparing.
Compared with prior art, the present invention is by assembling some column diamond with high heat conductance in the same direction in aluminum substrate
Linear array makes the composite have orientation heat conductivility well in the direction, realizes high-performance orientation heat conduction.Wherein, own
Diamond wire is arranged in parallel in the same direction, and each diamond wire becomes a quick conductive passage, makes heat constantly edge
Diamond column direction distributes rapidly, the joint effect of all diamond wires, allows for the composite and has orientation well
Heat conductivility；By in one or more layers metallic film good with diamond wettability of diamond wire coating surface, then existing again
Prepared by its most top layer has good wettability one or more layers thin film with base material aluminum, then by different sintering and densification process,
There is interface diffusion to diamond and Al matrixes or react in metal or carbide of diamond surface etc., realize metallurgical binding, make
Compound interface is combined substantially to be strengthened, and the thermal conductivity of material can acquire the improvement of high degree；Composite preparation process
In, during the diamond particles after surface modification treatment are added to aluminium powder or Al alloy powder, by sintering densification technique,
Its Dispersed precipitate is made in aluminum substrate, the thermal conductivity of one-dimensional diamond reinforced aluminum matrix composites can be further lifted；Buddha's warrior attendant
Stone has high thermal conductivity (1300～2200W/ (mK)), low thermal coefficient of expansion (0.8 × 10-6～1.5 × 10-6K-1) and
The premium properties such as high elastic modelling quantity, aluminum have the advantages that density is low, thermal conductivity is high, low cost, corrosion-resistant and easy machining,
Therefore, composite is prepared into using diamond as reinforcement and aluminum, the characteristic of diamond and aluminum can be combined, obtain
With high heat conductance, low thermal coefficient of expansion and low-density encapsulating material, the composite can be applicable to military pocket computer,
The fields such as high-performance server, aero-space electronic equipment, photonicss and ion display.
Description of the drawings
Accompanying drawing 1 is one-dimensional diamond wire reinforced aluminum matrix composites preparation method schematic flow sheet.
Accompanying drawing 2 is the modified cross-sectional structure schematic diagram in belt carcass diamond wire surface.
Vertical cross section structure diagram of the accompanying drawing 3 for Fig. 2.
Accompanying drawing 4a is a kind of cross-sectional view of array arrangement that the modified belt carcass diamond wire in surface is evenly arranged.
Accompanying drawing 4b is another kind of array arrangement cross-sectional view that the modified belt carcass diamond wire in surface is evenly arranged.
Cross-sectional views of the accompanying drawing 4c for a kind of array arrangement of the modified belt carcass diamond wire random arrangement in surface.
Another kind of array arrangement cross-sectional views of the accompanying drawing 4d for the modified belt carcass diamond wire random arrangement in surface.
Longitudinal section of the accompanying drawing 5 for Fig. 4 a.
In accompanying drawing 2：1-linear core 2-cvd diamond, 3-metallic diaphragm of film
Specific embodiment
Technical scheme is further described below by specific embodiment.
The embodiment of the present invention is carried out by following technique or step：
(1) early stage process is carried out to tinsel or carbide silk material
Processed according to the following steps：(1) polished using 800# abrasive paper for metallograph, then carried out ultrasonic shake in acetone
Swing cleaning；(2) and then, silk material be soaked in fine diamond powder acetone suspension ultrasonic vibration process 30min；
(2) using hot-wire chemical gas-phase deposition in silk or the continuous fine and close diamond film of flat substrates surface deposition
Using heat wire method, microwave plasma method, flame method, direct-current discharge method, DC arc plasma jet, low pressure radio frequency
The various chemical gaseous phase depositing process such as method, normal-pressure radio-frequency, electron cyclotron resonace method are deposited in linear core or flat substrates surface
Diamond, diamond thicknesses of layers are 0.001～1.0mm.After etching linear core or flat substrates, the one-dimensional gold of self-supporting is obtained
Hard rock line or lamellar self-supporting diamond, lamellar self-supporting diamond obtain the one-dimensional diamond wire of self-supporting through cut,
I.e. full diamond wire.
(3) belt carcass diamond wire or full diamond wire surface modification treatment
Using any one plating mode such as magnetron sputtering, multi-arc ion coating, vacuum evaporation or chemical plating in one-dimensional Buddha's warrior attendant
Stone line surface deposits simple substance or composite film.
(4) oriented alignment of modified belt carcass diamond wire
Be able to can also be uniformly distributed with random distribution, it is uniform to arrange
(5) aluminium filling and densification process
Heat treatment or the densification processes such as hot pressed sintering, infiltration or protective atmosphere melting
Embodiment one:
Select the tungsten filament of a diameter of 0.03mm and 0.4mm as core respectively, be first according to step (1) and core surfaces are entered
The process of row early stage；Then according to step (2) is using HF CVD depositing diamond film, deposition process parameters：Heated filament is apart from 6mm, base
800 DEG C of temperature, 2200 DEG C of hot-wire temperature, deposition pressure 3KPa, sedimentation time 40 hours, CH4/H2 volume flow ratios 1:99,
60 μm of diamond film thickness is obtained, that is, obtains belt carcass diamond filament；(3) using magnetically controlled sputter method in belt carcass diamond wire table
Face first sputters layer of metal tungsten film, and sputtering power is 150W, pressure 0.4Pa, 400 DEG C of substrate temperature, argon flow amount 20sccm, W
Film thickness is 0.2 μm；Sputter layer of metal copper film again, sputtering power is 100W, pressure 0.5Pa, 300 DEG C of substrate temperature, argon
Flow 20sccm, 5.0 μm of thicknesses of layers；(4) the belt carcass diamond wire orientation of plated surface W/Cu is uniformly arranged in mould, is arranged
Cloth is apart from 1mm；(4) the belt carcass diamond wire orientation of plated surface W/Cu is uniformly arranged in mould, arranges apart from 1mm, obtain final product
To one-dimensional diamond array backbone；(5) one-dimensional diamond array backbone is fixed and is put in mould, while by fine aluminium in crucible
Heating is melted to 800 DEG C, and melt is poured in mould, the pressure of the 60Mpa that pressed using hydraulic press, forces aluminum or aluminum to close
Golden melt is infiltrated into the gap location of diamond wire in skeleton, keeps pressure 15 seconds, and cooling and demolding takes out composite.Performance
Test result：Thermal conductivity is respectively 630W/ (mK) (core is thin tungsten filament), 528W/ (mK) (core is thick tungsten filamen).
Embodiment two：
It is first according to step (1) and core surfaces is entered as core from a diameter of 0.3 μm of copper wire, 0.3 μm of titanium silk respectively
The process of row early stage；Then according to step (2) is using HF CVD depositing diamond film, deposition process parameters：Heated filament is apart from 6mm, base
850 DEG C of temperature, 2200 DEG C of hot-wire temperature, deposition pressure 3KPa, sedimentation time 50 hours, CH4/H2 volume flow ratios 1:99,
100 μm of diamond film thickness is obtained, that is, obtains belt carcass diamond wire；(3) using vacuum vapor deposition method on belt carcass diamond wire surface
Layer of metal chromium film, evaporation current are 36A, pressure 0.1Pa, and 400 DEG C of substrate temperature, chromium film thickness are 0.5 μm, then are evaporated in vacuo
Layer of metal copper film, evaporation current is 30A, pressure 0.1Pa, 300 DEG C of substrate temperature, 2.0 μm of thicknesses of layers；(4) by plated surface
The belt carcass diamond wire orientation of Cr/Cu is uniformly arranged in mould, is arranged apart from 2mm, that is, is obtained one-dimensional diamond array backbone；
(5) one-dimensional diamond array backbone is fixed and is put in mould, 2 times of Al-Si alloys of diamond framework volume are placed on into bone
Above frame, wherein the mass content of Si is 15%, is then placed in heating furnace, 900 DEG C of insulations under high pure nitrogen protection
30min, you can the one-dimensional diamond reinforced aluminum matrix composites of highly directional heat conduction are obtained, heat conductivity is respectively 725W/
(mK) (core is copper wire), 689W/ (mK) (core is titanium silk).
Embodiment three：
Step (1) is first according to core table as core from the thin molybdenum filaments of a diameter of 0.1mm, the thick molybdenum filaments of 0.8mm respectively
Face carries out early stage process；Then according to step (2) is using HF CVD depositing diamond film, deposition process parameters：Heated filament distance
8mm, 900 DEG C of substrate temperature, 2200 DEG C of hot-wire temperature, deposition pressure 3KPa, sedimentation time 50 hours, CH4/H2 volume flow ratios
2:98,100 μm of diamond film thickness is obtained, that is, obtains belt carcass diamond filament；(3) using magnetically controlled sputter method in belt carcass Buddha's warrior attendant
Stone line surface first sputters layer of metal titanium film, and sputtering power is 92W, pressure 0.5Pa, 300 DEG C of substrate temperature, argon flow amount
20sccm, thicknesses of layers 500nm；(4) the belt carcass diamond wire orientation of plated surface Ti is uniformly arranged in mould, distance of arranging
3mm, that is, obtain one-dimensional diamond array backbone；(5) the gap location filling pure aluminium powder and bortz powder mixed-powder of diamond wire
(Al powder purities are 99.9%, diamond particles pattern rule, particle size：80～100 μm), diamond particles are steamed using vacuum
The technology of sending out is prepared for Mo/Cu composite films on surface, and molybdenum evaporation current is 32A, pressure 0.1Pa, 400 DEG C of substrate temperature, chromium film
Thickness is 0.3 μm, then is evaporated in vacuo layer of metal copper film, and evaporation current is 30A, pressure 0.1Pa, 300 DEG C of substrate temperature, film layer
1.0 μm of thickness；(6) radially it is pressed, pressure is 120MPa, compressing sample is carried out into hot pressing then
Sintering, is obtained one-dimensional diamond reinforced aluminum matrix composites：Sintering temperature is 550 DEG C, sintering pressure 30MPa, and heating rate is,
Temperature retention time 5min, atmosphere are vacuum.Using the one-dimensional diamond reinforced aluminum matrix composites of highly directional heat conduction obtained in this technique
Thermal conductivity is respectively 802W/ (mK) (core is thin molybdenum filament), 873W/ (mK) (core is thick molybdenum filament).
Example IV：
Step (1) is first according to core table as core from a diameter of 0.014 μm of spun gold, 0.03 μm of filamentary silver respectively
Face carries out early stage process；Then according to step (2) is using HF CVD depositing diamond film, deposition process parameters：Heated filament distance
6mm, 850 DEG C of substrate temperature, 2300 DEG C of hot-wire temperature, deposition pressure 3KPa, sedimentation time 80 hours, CH4/H2Volume flow ratio
1:99, obtain 100 μm of diamond film thickness；(3) using magnetically controlled sputter method belt carcass diamond wire surface first sputter one layer it is golden
Category chromium film, sputtering power is 200W, pressure 0.3Pa, 350 DEG C of substrate temperature, argon flow amount 50sccm, and Cr film thicknesses are 0.5 μm；
Sputter layer of metal copper film again, sputtering power is 150W, pressure 0.4Pa, 300 DEG C of substrate temperature, argon flow amount 20sccm, film layer
10.0 μm of thickness；(4) the belt carcass diamond wire orientation of plated surface Cr/Cu is uniformly arranged in mould, arranging distance 2mm；(5)
(Al powder purities are 99.9%, diamond particles pattern for the gap location filling pure aluminium powder of diamond wire and bortz powder mixed-powder
Rule, particle size：80～100 μm, diamond particle surfaces through with Mo/Cu surface modification treatment as embodiment three-phase),
Radially it is pressed, pressure is 120MPa, compressing sample is carried out into discharge plasma sintering then
(SPS) one-dimensional diamond reinforced aluminum matrix composites are obtained,：Sintering temperature is 550 DEG C, sintering pressure 30MPa, heating rate
For temperature retention time 5min, atmosphere are vacuum.Aluminum-base composite material is strengthened using the one-dimensional diamond of highly directional heat conduction obtained in this technique
Material highest thermal conductivity is respectively 856W/ (mK) (core is spun gold), 928W/ (mK) (core is filamentary silver).
Embodiment five：
From thickness be 1mm silicon chips as flat substrates, being first according to step (1) is carried out at early stage to silicon substrate surface
Reason；Then according to step (2) is using HF CVD depositing diamond film, deposition process parameters：Heated filament is apart from 6mm, substrate temperature
900 DEG C, 2300 DEG C of hot-wire temperature, deposition pressure 3KPa, sedimentation time 300 hours, CH4/H2Volume flow ratio 3:97, obtain gold
600 μm of hard rock film thickness, after etching lamellar silicon substrate, obtains lamellar self-supporting diamond, then is derived from through cut
Support one-dimensional diamond wire, i.e., full diamond wire, a diameter of 0.5mm；(3) using magnetically controlled sputter method in full diamond wire surface elder generation
Sputtering layer of metal chromium film, sputtering power is 200W, pressure 0.3Pa, 350 DEG C of substrate temperature, argon flow amount 50sccm, Cr thickness
Spend for 0.5 μm；Sputter layer of metal copper film again, sputtering power is 150W, pressure 0.4Pa, 300 DEG C of substrate temperature, argon flow amount
20sccm, 10.0 μm of thicknesses of layers；(4) the full diamond wire orientation of plated surface Cr/Cu is uniformly arranged in mould, between arrangement
Away from 2mm；(5) (Al powder purities are 99.9% to the gap location filling pure aluminium powder and bortz powder mixed-powder of diamond wire, diamond
Granule-morphology rule, particle size：80～100 μm, diamond particle surfaces are through changing with Mo/Cu surfaces as embodiment three-phase
Property process), sample is carried out into hot pressed sintering then, be obtained one-dimensional diamond reinforced aluminum matrix composites：Sintering temperature is 650
DEG C, sintering pressure 60MPa, temperature retention time 90min, atmosphere are vacuum.Using the one-dimensional Buddha's warrior attendant of highly directional heat conduction obtained in this technique
Stone reinforced aluminum matrix composites highest thermal conductivity is 980W/ (mK).
Therefore, in this patent, the thermal conductivity of the one-dimensional diamond reinforced aluminum matrix composites of obtained highly directional heat conduction can
Up to 980W/ (mK), hence it is evident that higher than thermal conductivity (100～600W/ (m of traditional diamond particles reinforced aluminum matrix composites
K))。
Claims (9)
1. a kind of one-dimensional diamond reinforced aluminum matrix composites, it is characterised in that：It is distributed in described aluminum substrate by some one
The diamond array of dimension diamond wire composition, the one-dimensional diamond wire and aluminum substrate metallurgical binding；The one-dimensional diamond wire
For surface modified diamond line；
The preparation method of one-dimensional diamond reinforced aluminum matrix composites, the one-dimensional diamond wire arrangement that first surface is modified be with
Machine is distributed or equally distributed diamond wire array；Then, burnt using founding, infiltration, cold-rolled sintered, hot pressed sintering, plasma
A kind of technique in knot, aluminum or aluminum alloy is combined with diamond wire array, obtains one-dimensional diamond wire and aluminum substrate metallurgical junction
The one-dimensional diamond reinforced aluminum matrix composites closed；Or
Using a kind of technique in founding, infiltration, cold-rolled sintered, hot pressed sintering, plasma agglomeration, will be comprising the modified Buddha's warrior attendant in surface
The aluminum or aluminum alloy of stone granule is combined with diamond wire array, obtains a Vygen of one-dimensional diamond wire and aluminum substrate metallurgical binding
Hard rock reinforced aluminum matrix composites；
The founding is by containing modified diamond particles or the aluminum or aluminum alloy without modified diamond particles and one-dimensional diamond
Array is put in graphite jig in the lump, is heated to 600 ~ 1000 in then putting it into vacuum melting furnace or atmosphere protection smelting furnace
DEG C melting, cooling and demolding obtain one-dimensional diamond reinforced aluminum matrix composites；Or
Aluminum or aluminum alloy is heated to into 600 ~ 800 DEG C in crucible first, melting aluminum or aluminum alloy is obtained, will be directly arranged in array
The leaching of one-dimensional diamond wire be placed in the aluminum or aluminum alloy of liquid, or to the modified diamond of addition in melting aluminum or aluminum alloy
Grain, stir after, the one-dimensional diamond wire being arranged in array leaching is placed in the aluminum or aluminum alloy of liquid, is cooled down, is obtained one
Vygen hard rock reinforced aluminum matrix composites；
The infiltration is that the one-dimensional diamond wire that will be arranged in array is placed in infiltration mould, is preheated, in vacuum or protection
Under atmosphere, by the aluminum or aluminum alloy pressurization infiltration containing modified diamond particles or the molten state without modified diamond particles
Into infiltration mould, it is combined with diamond rod, the preheating temperature of diamond rod array is controlled in 500 ~ 700 DEG C of scopes, is melted
The pouring temperature for melting state aluminum is 700 ~ 900 DEG C, and infiltration pressure is 5 ~ 30MPa, and temperature retention time is 0.5 ~ 3 hour, obtains a Vygen
Hard rock reinforced aluminum matrix composites；
The hot pressed sintering be aluminium powder or Al alloy powder or the aluminium powder containing modified diamond particles or Al alloy powder are added it is one-dimensional
After diamond array, hot pressed sintering in vacuum or protective atmosphere hot pressing furnace is put into, sintering temperature is 550 ~ 655 DEG C, pressure is 5 ~
200 MPa, time are 30 ~ 240 minutes, and cooling and demolding obtains one-dimensional diamond reinforced aluminum matrix composites；
The plasma agglomeration is by aluminium powder or Al alloy powder or the aluminium powder containing modified diamond particles or Al alloy powder addition one
In Vygen hard rock array, after compacting, it is sintered in being put into plasma agglomeration stove, 5 ~ 70MPa of pressure, sintering process is：Sintering
500 ~ 700 DEG C of temperature, 10 ~ 300 DEG C/min of programming rate are incubated 5 ~ 10min, and atmosphere is vacuum.
2. one-dimensional diamond reinforced aluminum matrix composites according to claim 1, it is characterised in that：Described diamond battle array
One-dimensional diamond wire in row is arranged in parallel in metal base, and relative position is uniformly arranged or random arrangement.
3. one-dimensional diamond reinforced aluminum matrix composites according to claim 2, it is characterised in that：Described one-dimensional Buddha's warrior attendant
Stone line be self-supporting diamond Xian Huo centers be provided with linear core line support diamond wire, self-supporting diamond line it is a diameter of
0.015 ~ 2.0mm, line support a diameter of 0.015 ~ 3.0mm of diamond wire；Described linear core from tungsten, molybdenum, copper, titanium, silver,
A kind of filamentous silk material in gold, carbon fiber, silicon carbide fibre；A diameter of 0.014 ~ 2.0mm of described linear core.
4. one-dimensional diamond reinforced aluminum matrix composites according to claim 1-3 any one, it is characterised in that：Surface
Modified diamond wire is that one-dimensional diamond wire surface is provided with metal film to be modified；The metal film selected from titanium film, tungsten film/
One kind in copper film, chromium film/copper film, wherein：Titanium film thicknesses of layers be 0.1 ~ 1.0 μm, tungsten film/copper film thicknesses of layers be 0.02 ~
0.2 μm/1.0 ~ 10.0 μm, chromium film/copper film thicknesses of layers is 0.05 ~ 0.5 μm/2 ~ 20 μm.
5. one-dimensional diamond reinforced aluminum matrix composites according to claim 4, it is characterised in that：In described aluminum substrate
In be also distributed with the diamond particles that surface is modified through molybdenum film/copper film, diamond particles and aluminum substrate are metallurgical binding, Buddha's warrior attendant
Stone grain graininess is 1 ~ 200 μm, and it is 0 ~ 50% that the diamond particles account for the percentage composition of total composite volume；The molybdenum film/
The thicknesses of layers of copper film is 0.05 ~ 0.5 μm/0.5 ~ 5.0 μm, and molybdenum film inner surface is combined with diamond surface, and copper film is coated on
Molybdenum film outer surface.
6. the preparation method of one-dimensional diamond reinforced aluminum matrix composites according to claim 1, it is characterised in that：Surface
Be modified one-dimensional diamond wire or surface modified diamond granule using magnetron sputtering, multi-arc ion coating, vacuum evaporation, chemical plating,
In plating, one or more plating mode realizes that surface is modified.
7. the preparation method of one-dimensional diamond reinforced aluminum matrix composites according to claim 6, it is characterised in that：It is described
Surface be modified one-dimensional diamond wire for self-supporting diamond Xian Huo centers be provided with linear core line support diamond wire.
8. the preparation method of one-dimensional diamond reinforced aluminum matrix composites according to claim 7, it is characterised in that：It is described
Self-supporting diamond line preparation technology using heated filament auxiliary law, microwave plasma strengthen method, flame combustion process, direct-current discharge method,
A kind of chemical vapor deposition side in DC arc plasma jet, low pressure radio frequency method, normal-pressure radio-frequency method, electron cyclotron resonace method
Method obtains self-supporting one-dimensional in linear core or flat substrates surface depositing diamond after etching linear core or flat substrates
Diamond wire or lamellar self-supporting diamond piece, lamellar self-supporting diamond piece obtain the one-dimensional Buddha's warrior attendant of self-supporting through cut
Stone line, a diameter of 0.015 ~ 2.0mm of the one-dimensional diamond wire of self-supporting；
The line supports diamond wire preparation technology to strengthen method, flame combustion process, direct current using heated filament auxiliary law, microwave plasma
A kind of chemical gas in electric discharge, DC arc plasma jet, low pressure radio frequency method, normal-pressure radio-frequency method, electron cyclotron resonace method
In linear core surfaces depositing diamond, diamond thicknesses of layers is 0.001 ~ 1mm to phase deposition process, linear core from tungsten,
A kind of filamentous silk material in molybdenum, copper, titanium, silver, gold, carbon fiber, silicon carbide fibre；Described linear core it is a diameter of
0.014~2.0mm。
9. the preparation method of one-dimensional diamond reinforced aluminum matrix composites according to claim 7, it is characterised in that：It is described
Line support diamond wire, using chemical gaseous phase depositing process before linear core surfaces depositing diamond, to linear core
Surface carries out pretreatment, and pretreating process is：
For the linear core that can form strong carbide, core is carried out oil removing, scale removal successively, after electrochemical polish, is directly soaked
Steeping carries out ultrasonic wave concussion plantation seed crystal pretreatment in fine diamond powder suspension；The linear core of strong carbide can be formed
One kind in W, Mo, Ti, Cr, Ta, Si, Nb；
Or
For the linear core that can not form strong carbide, core is carried out oil removing, scale removal successively, after electrochemical polish, is adopted
Physical vapour deposition (PVD) or chemical vapour deposition technique prepare the thin film that can form strong carbide in core surfaces, and thin film is single thin layer
One kind in film, plural layers, alloy firm, then, carries out ultrasonic wave concussion kind in being soaked in fine diamond powder suspension
Plant seed crystal pretreatment；The one kind of the linear core of strong carbide in Cu, Ag, Au, Ni, Al, Co can not be formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510659346.7A CN105239026B (en) | 2015-10-12 | 2015-10-12 | One-dimensional diamond reinforced aluminum matrix composite material and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510659346.7A CN105239026B (en) | 2015-10-12 | 2015-10-12 | One-dimensional diamond reinforced aluminum matrix composite material and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105239026A CN105239026A (en) | 2016-01-13 |
| CN105239026B true CN105239026B (en) | 2017-04-26 |
Family
ID=55036844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510659346.7A Active CN105239026B (en) | 2015-10-12 | 2015-10-12 | One-dimensional diamond reinforced aluminum matrix composite material and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105239026B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105803242B (en) * | 2016-03-21 | 2017-10-31 | 中南大学 | A kind of sheet couples enhancing composite and preparation method with wire Heat Conduction Material |
| CN105803241B (en) * | 2016-03-21 | 2017-08-25 | 中南大学 | A kind of conveyor screw enhancing Metal Substrate or polymer matrix composite and preparation method |
| CN108203794B (en) * | 2018-01-04 | 2020-02-14 | 中南大学 | Short carbon fiber aluminum-based composite material and preparation method thereof |
| CN108405867B (en) * | 2018-03-09 | 2019-11-08 | 湖南东映碳材料科技有限公司 | A kind of preparation method of unidirectional high thermal conductivity Cf/Al composite material |
| GB201809206D0 (en) * | 2018-06-05 | 2018-07-25 | Pontificia Univ Catolica Madre Y Maestra Autopista Duarte Km 1 1/2 | Sp3-bonded carbon materials, methods of manufacturing and uses thereof |
| CN108796262A (en) * | 2018-06-14 | 2018-11-13 | 中国科学院金属研究所 | SiC reinforcement metal-base composites and preparation method thereof with microcosmic oriented structure |
| CN110589832A (en) * | 2019-09-24 | 2019-12-20 | 中国科学院深圳先进技术研究院 | SiC nanowire and preparation method and application thereof |
| CN111421141B (en) * | 2020-04-20 | 2022-05-24 | 浙江工业大学 | Preparation method of directional high-thermal-conductivity diamond/metal matrix composite material |
| CN111778506B (en) * | 2020-05-11 | 2023-10-03 | 中南大学 | Gradient boron doped diamond reinforced metal matrix composite material and preparation method and application thereof |
| CN115261747B (en) * | 2021-04-29 | 2023-08-22 | 苏州铜宝锐新材料有限公司 | Powder metallurgy composite functional material, manufacturing method and application thereof |
| CN113444988B (en) * | 2021-07-20 | 2022-03-08 | 沈阳工业大学 | Preparation method of high-thermal-conductivity double-carbon-material-reinforced aluminum-based composite material |
| CN113802180B (en) * | 2021-09-15 | 2023-03-24 | 中南大学 | Diamond/metal-based composite material and preparation method and application thereof |
| CN114457292A (en) * | 2021-12-23 | 2022-05-10 | 广东工业大学 | Amorphous alloy-based diamond composite material with controllable heat conduction and preparation method thereof |
| CN116162819B (en) * | 2023-03-23 | 2024-01-26 | 哈尔滨工业大学 | Preparation method of multiphase interface high-heat-conductivity diamond/aluminum composite material |
| CN117855157A (en) * | 2024-03-07 | 2024-04-09 | 中国电子科技集团公司第二十九研究所 | Encapsulation structure and method of millimeter wave solid-state power amplifier |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649400A (en) * | 2009-07-20 | 2010-02-17 | 温州宏丰电工合金有限公司 | Diamond reinforced metal-base composite material for electronic packaging and preparation method thereof |
| CN102352503A (en) * | 2011-10-31 | 2012-02-15 | 长沙岱勒新材料科技有限公司 | Preparation method of diamond wire and prepared diamond wire |
| CN102994815A (en) * | 2012-11-29 | 2013-03-27 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of high-thermal conductivity diamond/aluminum composite material |
-
2015
- 2015-10-12 CN CN201510659346.7A patent/CN105239026B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649400A (en) * | 2009-07-20 | 2010-02-17 | 温州宏丰电工合金有限公司 | Diamond reinforced metal-base composite material for electronic packaging and preparation method thereof |
| CN102352503A (en) * | 2011-10-31 | 2012-02-15 | 长沙岱勒新材料科技有限公司 | Preparation method of diamond wire and prepared diamond wire |
| CN102994815A (en) * | 2012-11-29 | 2013-03-27 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of high-thermal conductivity diamond/aluminum composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105239026A (en) | 2016-01-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105239026B (en) | One-dimensional diamond reinforced aluminum matrix composite material and preparing method thereof | |
| CN105112754B (en) | Three-dimensional network diamond framework strengthens metal-base composites and preparation method | |
| CN105220049B (en) | A kind of lamellar diamond reinforced metal-base composite material and preparation method | |
| CN110438444B (en) | Tungsten-plated diamond particles, tungsten plating method, application of tungsten-plated diamond particles as copper-based reinforcing phase and diamond/copper composite material obtained by tungsten-plated diamond particles | |
| CN101985702B (en) | Super-high thermal conductivity and low thermal expansivity diamond composite material and preparation method thereof | |
| CN105886849B (en) | Plate the preparation method of W diamond/aluminum composites | |
| CN102383014B (en) | Method for preparing diamond-copper composite material by virtue of metallization of high-temperature blending surface | |
| CN100472765C (en) | Heat sink made from diamond-copper composite material containing boron | |
| CN112981164B (en) | Preparation method of diamond reinforced metal matrix composite material with high reliability and high thermal conductivity | |
| CN107739948B (en) | A kind of diamond/aluminum composite material and its high efficiency preparation method | |
| CN105803241A (en) | Spiral-body-enhanced metal-based or polymer-based composite and preparation method | |
| CN103882349B (en) | A kind of preparation method of carbon nano fiber-carbon/carbon-copper composite material | |
| CN107760951B (en) | A kind of diamond/aluminum composite material and its low cost preparation method | |
| CN1944698A (en) | Super high heat conduction, low heat expansion coefficient composite material and its preparing method | |
| CN102071332A (en) | Method for preparing diamond enhanced copper based composite with high volume fraction | |
| CN111519076A (en) | Diamond particle reinforced metal matrix composite material and preparation method and application thereof | |
| CN112981163B (en) | Preparation method of diamond-reinforced metal matrix composite with high surface precision and high reliability | |
| CN109234593A (en) | A kind of diamond/copper based composites and preparation method thereof | |
| CN114309596A (en) | Preparation method of high-thermal-conductivity surface metallized diamond/copper composite substrate | |
| CN104625077A (en) | High-heat-conduction diamond/copper composite material and manufacturing method of high-heat-conduction diamond/copper composite material | |
| CN110284019B (en) | Method for directionally doping graphite in metal | |
| CN110724845A (en) | Diamond/aluminum composite material with high heat conductivity and high reliability and preparation process thereof | |
| CN113758325B (en) | VC radiator with built-in copper/diamond sintered liquid suction core and preparation method thereof | |
| CN112111669A (en) | High-thermal-conductivity diamond/copper material and application thereof | |
| US11094514B2 (en) | Rotatable sputtering target |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |