CN106245076B - The preparation of double whisker reinforcement sponge structure type nickel cobalt molybdenum evanohm high temperature energy-absorbing materials - Google Patents
The preparation of double whisker reinforcement sponge structure type nickel cobalt molybdenum evanohm high temperature energy-absorbing materials Download PDFInfo
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- CN106245076B CN106245076B CN201610718166.6A CN201610718166A CN106245076B CN 106245076 B CN106245076 B CN 106245076B CN 201610718166 A CN201610718166 A CN 201610718166A CN 106245076 B CN106245076 B CN 106245076B
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- Prior art keywords
- sponge structure
- silicon carbide
- nickel cobalt
- aluminium borate
- carbide whisker
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- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000011358 absorbing material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000002787 reinforcement Effects 0.000 title abstract description 7
- 239000004698 Polyethylene Substances 0.000 claims abstract description 51
- -1 polyethylene Polymers 0.000 claims abstract description 51
- 229920000573 polyethylene Polymers 0.000 claims abstract description 51
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 46
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims abstract description 37
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000004070 electrodeposition Methods 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 230000002708 enhancing effect Effects 0.000 claims abstract description 23
- PRQRQKBNBXPISG-UHFFFAOYSA-N chromium cobalt molybdenum nickel Chemical compound [Cr].[Co].[Ni].[Mo] PRQRQKBNBXPISG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004411 aluminium Substances 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000011733 molybdenum Substances 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
- 239000002659 electrodeposit Substances 0.000 claims description 13
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- 238000009792 diffusion process Methods 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002134 carbon nanofiber Substances 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 7
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 claims description 7
- 229940078494 nickel acetate Drugs 0.000 claims description 7
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 claims description 7
- DITXJPASYXFQAS-UHFFFAOYSA-N nickel;sulfamic acid Chemical compound [Ni].NS(O)(=O)=O DITXJPASYXFQAS-UHFFFAOYSA-N 0.000 claims description 7
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- XVVZSEXTAACTPS-UHFFFAOYSA-N 5-[hydroxy-(4-nitrophenoxy)phosphoryl]pentanoic acid Chemical compound OC(=O)CCCCP(O)(=O)OC1=CC=C([N+]([O-])=O)C=C1 XVVZSEXTAACTPS-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 150000004040 pyrrolidinones Chemical class 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 3
- 229910052804 chromium Inorganic materials 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 abstract description 2
- ZXNKRXWFQRLIQG-UHFFFAOYSA-N silicon(4+);tetraborate Chemical compound [Si+4].[Si+4].[Si+4].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] ZXNKRXWFQRLIQG-UHFFFAOYSA-N 0.000 abstract 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
Abstract
The invention provides a kind of preparation method of the sponge structure type nickel cobalt molybdenum evanohm high temperature resistant energy-absorbing material of aluminium borate/silicon carbide whisker enhancing, it is specially：Conductive treatment is carried out to sponge structure polyethylene model first；Secondly, nickel cobalt molybdenum chromium/aluminium borate silicon carbide whisker composite electrodeposition is carried out in sponge structure polyethylene model surface；Then sponge structure polyethylene model removal processing is carried out；Finally carry out the heat treatment of nickel cobalt molybdenum chromium/aluminium borate silicon carbide whisker whisker composite material.Nickel cobalt molybdenum chromium matrix, aluminium borate and the silicon carbide whisker reinforcement of aluminium borate prepared by the present invention/silicon carbide whisker enhancing nickel cobalt molybdenum evanohm high temperature resistant energy-absorbing composite all have good resistance to elevated temperatures, due to aluminium borate and the high elastic modulus and high intensity of silicon carbide whisker, therefore it can assign sponge structure type nickel cobalt molybdenum chromium matrix excellent high temperature energy absorption performance, intensity and toughness.
Description
Technical field
The present invention relates to high temperature resistant energy-absorbing material technical field, the sea of particularly a kind of aluminium borate/silicon carbide whisker enhancing
The preparation method of continuous structural type nickel cobalt molybdenum evanohm high temperature resistant energy-absorbing composite.
Background technology
Sponge structure metal has initial elasticity stage, middle plasticity platform phase, stress anxious under compressive load effect
Play rises the three stage stress-strain characteristics in fine and close stage, is the ideal material for impacting energy-absorbing, thus is used as normal temperature energy-absorbing material
It is widely applied.But high temperature energy-absorbing material is used as, sponge structure metal is but difficult to the requirement for reaching impact energy-absorbing, and this is
Since general elemental metals limited mechanical properties, and most metals will be oxidized so as to which performance significantly drops under the high temperature conditions
It is low.Currently, it would be highly desirable to which development is suitable to the high temperature energy-absorbing material of the recoil of the flame combustions such as rocket, cannon, aircraft and aircraft carrier and blast.
The content of the invention
For overcome the deficiencies in the prior art, the invention provides a kind of sponge knot of aluminium borate/silicon carbide whisker enhancing
The preparation method of configuration nickel cobalt molybdenum evanohm high temperature resistant energy-absorbing material, prepared high temperature resistant energy-absorbing composite is with nickel cobalt molybdenum
Evanohm is the composite that matrix, aluminium borate and silicon carbide whisker are reinforcement.Due to nickel cobalt molybdenum chromium matrix, aluminium borate and carbon
SiClx Researches On Whiskers all have good resistance to elevated temperatures, particularly aluminium borate and silicon carbide whisker have high elastic modulus and
High intensity, it can assign sponge structure type nickel cobalt molybdenum chromium matrix excellent high temperature energy absorption performance, intensity and toughness, therefore especially suitable for
High temperature energy-absorbing material, has broad application prospects.
The technical solution adopted for the present invention to solve the technical problems is：A kind of sea of aluminium borate/silicon carbide whisker enhancing
The preparation method of continuous structural type nickel cobalt molybdenum evanohm high temperature resistant energy-absorbing material, is made up of following step：
S1. sponge structure polyethylene model conductive treatment；
S2. sponge structure polyethylene model surface nickel cobalt molybdenum chromium/aluminium borate-silicon carbide whisker composite electrodeposition；
S3. the removal of sponge structure polyethylene model is handled；
S4. the heat treatment of nickel cobalt molybdenum chromium/aluminium borate-silicon carbide whisker whisker composite material.
As further preferred embodiment, step S1 specifically includes following operation：
A1. electrocondution slurry is prepared：By carbon nano-fiber, nano carbon particle, hydroxyethylmethylcellulose, methacrylic acid,
1-METHYLPYRROLIDONE is added to suspension formed in deionized water, as electrocondution slurry.
A2. sponge structure polyethylene model conductive treatment：Sponge structure polyethylene model is sufficiently submerged in conductive paste
In material, after the abundant hanging of sponge structure polyethylene model surface, 10~50 minutes are dried at 30~50 DEG C to complete sponge
Structure polyethylene model conductive treatment.
As further preferred embodiment, the mass percent of each component is respectively in the electrocondution slurry：Nanometer
Carbon fiber 3~22%, nano carbon particle 2~18%, hydroxyethylmethylcellulose 0.8~4%, methacrylic acid 0.5~12%,
1-METHYLPYRROLIDONE 1.5~6%, remaining is deionized water.
As further preferred embodiment, step S2 specifically includes following operation：
B1. the preparation of nickel cobalt molybdenum chromium electrodeposit liquid：By concentration be analytically pure nickel sulfamic acid, nickelous hypophosphite, nickel acetate,
Nickelous bromide, cobaltous fluoride, cobalt chloride, NPE, tributyl phosphate, sulfuric acid, citric acid, DBSA
Sodium, nanometer chromium powder, nano Mo powder, aluminium borate whisker and silicon carbide whisker are added sequentially in deionized water, form electrodeposit liquid.
B2. composite electrodeposition process：It is sun using the sponge structure polyethylene model of conductive treatment as negative electrode, nickel plate
Pole, in 120~350mA/cm2Current density under carry out electro-deposition, electrodeposit liquid temperature maintains 30~60 DEG C, during electro-deposition
Between be 0.5~2 hour, whole electrodeposition process is stirred with ultrasonic wave.
As further preferred embodiment, in the electrodeposit liquid each component concentration be respectively nickel sulfamic acid 20~
100g/L, 15~120g/L of nickelous hypophosphite, 10~70g/L of nickel acetate, 2~15g/L of nickelous bromide, 15~60g/L of cobaltous fluoride, chlorination
10~50g/L of cobalt, 10~50mL/L of NPE, 5~30mL/L of tributyl phosphate, 1.5~10mL/L of sulfuric acid, lemon
3~10g/L of lemon acid, 10~40g/L of neopelex, 20~40g/L of nanometer chromium powder, 0.5~10g/L of nano Mo powder,
40~120g/L of aluminium borate whisker, 30~80g/L of silicon carbide whisker.
As further preferred embodiment, step S3 is specially：
Sponge structure polyethylene model after the completion of composite electrodeposition is fitted into electric furnace and in 0.1~4Mpa blanket of nitrogen
Enclose and 100~360 DEG C are heated up under protection, be incubated 10~30 minutes so that sponge structure polyethylene model decomposition removes.
As further preferred embodiment, step S4 is specially：
After the completion for the treatment of that sponge structure polyethylene model decomposition removes, furnace temperature is increased to 420~580 DEG C, insulation 1.2
~5 hours to realize the diffusion of cobalt atom；Then furnace temperature is increased to 600~1200 DEG C, is incubated 3~8 hours to realize
The diffusion of molybdenum atom and cobalt atom, closed so as to finally obtain the sponge structure type nickel cobalt molybdenum chromium of aluminium borate/silicon carbide whisker enhancing
Golden high temperature resistant energy-absorbing material.
The positive effect of the present invention：The present invention as matrix and adds the different-alloy element such as chromium, molybdenum, aluminium, cobalt using nickel, obtains
There is the nickel base superalloy of the different premium properties such as good elevated temperature strength, corrosion and heat resistant；Simultaneously with aluminium borate and carborundum
Whisker is as reinforcement, because aluminium borate and silicon carbide whisker have good resistance to elevated temperatures and high elastic modulus and high-strength
And sponge structure degree, thus can assign sponge structure type nickel cobalt molybdenum chromium matrix excellent high temperature energy absorption performance, intensity and toughness, i.e.,
Type nickel cobalt molybdenum evanohm matrix forms the sponge structure type nickel cobalt molybdenum evanohm composite tool of aluminium borate/silicon carbide whisker enhancing
There is good high temperature resistant energy absorption performance, have broad application prospects.
Brief description of the drawings
Fig. 1 is the preparation method flow chart of high temperature resistant energy-absorbing material of the present invention.
Embodiment
Below in conjunction with the accompanying drawings to a preferred embodiment of the present invention will be described in detail.
Reference picture 1, the preferred embodiment of the present invention provide a kind of sponge structure type nickel of aluminium borate/silicon carbide whisker enhancing
The preparation method of cobalt molybdenum evanohm high temperature resistant energy-absorbing material, it carries out sponge structure polyethylene model conductive treatment first, its
Secondary progress sponge structure polyethylene model surface nickel cobalt molybdenum chromium/aluminium borate-silicon carbide whisker composite electrodeposition, then carries out sponge
The removal of structure polyethylene model is handled, and finally carries out the heat treatment of nickel cobalt molybdenum chromium/aluminium borate-silicon carbide whisker whisker composite material, tool
Body, order is carried out in the steps below：
1. electrocondution slurry is prepared：By carbon nano-fiber, nano carbon particle, hydroxyethylmethylcellulose, methacrylic acid, N-
Methyl pyrrolidone is added to suspension formed in deionized water, as electrocondution slurry, each component in the electrocondution slurry
Mass percent is respectively：Carbon nano-fiber 3~22%, nano carbon particle 2~18%, hydroxyethylmethylcellulose 0.8~
4%, methacrylic acid 0.5~12%, 1-METHYLPYRROLIDONE 1.5~6%, remaining is deionized water.
2. sponge structure polyethylene model conductive treatment：Sponge structure polyethylene model is sufficiently submerged in electrocondution slurry
In, after the abundant hanging of sponge structure polyethylene model surface, 10~50 minutes are dried at 30~50 DEG C to complete sponge knot
Structure polyethylene model conductive treatment.
3. it is analytically pure nickel sulfamic acid, nickelous hypophosphite, nickel acetate, nickelous bromide, cobaltous fluoride, cobalt chloride, nonyl by concentration
Base phenol polyethenoxy ether, tributyl phosphate, sulfuric acid, citric acid, neopelex, nanometer chromium powder, nano Mo powder, boric acid
Al whisker and silicon carbide whisker are added sequentially in deionized water, and it is respectively 20~100g/L, 15 to form above each component concentration
~120g/L, 10~70g/L, 2~15g/L, 15~60g/L, 10~50g/L, 10~50mL/L, 5~30mL/L, 1.5~
10mL/L, 3~10g/L, 10~40g/L, 20~40g/L, 0.5~10g/L, 40~120g/L and 30~80g/L electro-deposition
Liquid.
4. composite electrodeposition process：It is sun using the sponge structure polyethylene model of conductive treatment as negative electrode, nickel plate
Pole, in 120~350mA/cm2Current density under carry out electro-deposition, electrodeposit liquid temperature maintains 30~60 DEG C, during electro-deposition
Between be 0.5~2 hour, whole electrodeposition process is stirred with ultrasonic wave.
5. the sponge structure polyethylene model after the completion of composite electrodeposition is fitted into electric furnace and in 0.1~4MPa nitrogen
100~360 DEG C are heated up under atmosphere protection, is incubated 10~30 minutes so that sponge structure polyethylene model decomposition removes.
6. after the completion for the treatment of that sponge structure polyethylene model decomposition removes, furnace temperature is increased to 420~580 DEG C, insulation
1.2~5 hours to realize the diffusion of cobalt atom；Then furnace temperature is increased to 600~1200 DEG C, is incubated 3~8 hours with reality
The diffusion of existing molybdenum atom and cobalt atom, so as to finally obtain the sponge structure type nickel cobalt molybdenum chromium of aluminium borate/silicon carbide whisker enhancing
Alloy high temperature resistant energy-absorbing material.
With reference to specific comparative analysis situation, embodiment is provided.
Embodiment 1
The embodiment of the present invention 1 provides a kind of preparation method of sponge structure type nickel cobalt molybdenum evanohm energy-absorbing material, by following
Sequence of steps is carried out：
1. electrocondution slurry is prepared：By carbon nano-fiber, nano carbon particle, hydroxyethylmethylcellulose, methacrylic acid, N-
Methyl pyrrolidone is added to suspension formed in deionized water, as electrocondution slurry, each component in the electrocondution slurry
Mass percent is respectively：Carbon nano-fiber 18%, nano carbon particle 11%, hydroxyethylmethylcellulose 3%, methacrylic acid
4%, 1-METHYLPYRROLIDONE 2.5%, remaining is deionized water.
2. sponge structure polyethylene model conductive treatment：Sponge structure polyethylene model is sufficiently submerged in electrocondution slurry
In, after the abundant hanging of sponge structure polyethylene model surface, 40 minutes are dried at 30 DEG C to complete sponge structure polyethylene
Model conductive treatment.
3. it is analytically pure nickel sulfamic acid, nickelous hypophosphite, nickel acetate, nickelous bromide, cobaltous fluoride, cobalt chloride, nonyl by concentration
Base phenol polyethenoxy ether, tributyl phosphate, sulfuric acid, citric acid, neopelex, nanometer chromium powder and nano Mo powder are successively
Be added in deionized water, formed above each component concentration be respectively 80g/L, 90g/L, 70g/L, 8g/L, 30g/L, 35g/L,
40mL/L, 20mL/L, 7.5mL/L, 9g/L, 30g/L, 25g/L and 6g/L electrodeposit liquid.
4. it is anode using the sponge structure polyethylene model of conductive treatment as negative electrode, nickel plate, in 320mA/cm2's
Electro-deposition is carried out under current density, electrodeposit liquid temperature maintains 40 DEG C, and electrodeposition time is 1.5 hours, whole electro-deposition
Journey is stirred with ultrasonic wave.
5. the sponge structure polyethylene model after the completion of electro-deposition is fitted into electric furnace and protected in 0.2MPa nitrogen atmosphere
360 DEG C are heated up under shield, is incubated 30 minutes so that sponge structure polyethylene model decomposition removes.
6. after the completion for the treatment of that sponge structure polyethylene model removes processing step, furnace temperature is increased to 580 DEG C, insulation
3.5 hours to realize the diffusion of cobalt atom；Then furnace temperature is increased to 1100 DEG C, insulation 5 hours with realize molybdenum atom and
The diffusion of cobalt atom, so as to obtain sponge structure type cobalt molybdenum evanohm (sample 1).
The sponge structure type nickel cobalt molybdenum evanohm of preparation is heated to 900 DEG C, then enters Mobile state Charpy impact test simultaneously
Energy-absorbing parameter when analyzing its 900 DEG C.As shown in table 1, the ratio energy-absorbing of sponge structure type nickel cobalt molybdenum evanohm is 78.4Nm/g, is carried
Lotus efficiency is 0.82, and load stationarity is general.
Embodiment 2
The sponge structure type nickel cobalt molybdenum evanohm that the embodiment of the present invention 2 provides a kind of aluminium borate/silicon carbide whisker enhancing is resistance to
High temperature energy-absorbing material preparation method, in the steps below order progress：
1. electrocondution slurry is prepared：By carbon nano-fiber, nano carbon particle, hydroxyethylmethylcellulose, methacrylic acid, N-
Methyl pyrrolidone is added to suspension formed in deionized water, as electrocondution slurry, each component in the electrocondution slurry
Mass percent is respectively：Carbon nano-fiber 18%, nano carbon particle 11%, hydroxyethylmethylcellulose 3%, methacrylic acid
4%, 1-METHYLPYRROLIDONE 2.5%, remaining is deionized water.
2. sponge structure polyethylene model conductive treatment：Sponge structure polyethylene model is sufficiently submerged in electrocondution slurry
In, after the abundant hanging of sponge structure polyethylene model surface, 40 minutes are dried at 30 DEG C to complete sponge structure polyethylene
Model conductive treatment.
3. it is analytically pure nickel sulfamic acid, nickelous hypophosphite, nickel acetate, nickelous bromide, cobaltous fluoride, cobalt chloride, nonyl by concentration
Base phenol polyethenoxy ether, tributyl phosphate, sulfuric acid, citric acid, neopelex, nanometer chromium powder, nano Mo powder, boric acid
Al whisker and silicon carbide whisker are added sequentially in deionized water, formed above each component concentration be respectively 80g/L, 90g/L,
70g/L, 8g/L, 30g/L, 35g/L, 40mL/L, 20mL/L, 7.5mL/L, 9g/L, 30g/L, 25g/L, 6g/L, 110g/L and
70g/L electrodeposit liquid.
4. it is anode using the sponge structure polyethylene model of conductive treatment as negative electrode, nickel plate, in 350mA/cm2's
Electro-deposition is carried out under current density, electrodeposit liquid temperature maintains 45 DEG C, and electrodeposition time is 2 hours, whole electrodeposition process
Stirred with ultrasonic wave.
5. the sponge structure polyethylene model after the completion of composite electrodeposition is fitted into electric furnace and in 0.2Mpa blanket of nitrogen
Enclose and 360 DEG C are heated up under protection, be incubated 30 minutes so that sponge structure polyethylene model decomposition removes.
6. after the completion for the treatment of that sponge structure polyethylene model removes processing step, furnace temperature is increased to 580 DEG C, insulation
3.5 hours to realize the diffusion of cobalt atom；Then furnace temperature is increased to 1150 DEG C, is incubated 5.5 hours to realize molybdenum atom
And the diffusion of cobalt atom, inhaled so as to obtain the sponge structure type nickel cobalt molybdenum evanohm high temperature resistant of aluminium borate/silicon carbide whisker enhancing
Can material (sample 2).
The sponge structure type nickel cobalt molybdenum chromium composite of the aluminium borate of preparation/silicon carbide whisker enhancing is heated to 1100
DEG C, energy-absorbing parameter when then entering Mobile state Charpy impact test and analyzing its 1100 DEG C.As a result as shown in table 1, aluminium borate/carbon
The ratio energy-absorbing of the sponge structure type nickel cobalt molybdenum evanohm composite of SiClx whisker reinforcement is 132.6Nm/g, and load to weight ratio is
0.91, load stationarity is fine.
Obviously, the sponge structure type nickel cobalt molybdenum chromium that the aluminium borate/silicon carbide whisker for describing to prepare according to the present invention strengthens closes
Nickel cobalt molybdenum chromium matrix, aluminium borate and the silicon carbide whisker reinforcement of golden high temperature resistant energy-absorbing material all have good heat-resisting quantity
Energy.As shown in Table 1,1100 DEG C when aluminium borate/silicon carbide whisker enhancing sponge structure type nickel cobalt molybdenum evanohm composite
Than energy-absorbing (sample 2：132.6Nm/g) sponge structure type nickel cobalt molybdenum evanohm (sample 1 when being 900 DEG C：78.4Nm/g) 1.7
Times；Its load to weight ratio is 0.91, also above the 0.82 of sponge structure type nickel cobalt molybdenum evanohm；In addition, aluminium borate/silicon carbide whisker
The counterweight balance of the sponge structure type nickel cobalt molybdenum evanohm composite of enhancing is fine, and this is due to the high-elastic of silicon carbide whisker
Property modulus and high intensity, can assign nickel cobalt molybdenum chromium matrix excellent high temperature energy absorption performance, intensity and toughness, thus make aluminium borate/
The sponge structure type nickel cobalt molybdenum evanohm of silicon carbide whisker enhancing has good high temperature energy absorption performance.
Table 1
Above-described is only the preferred embodiments of the present invention, should be understood that the explanation of above example is simply used
In help understand the present invention method and its core concept, the protection domain being not intended to limit the present invention, it is all the present invention
Any modification for being made within thought and principle, equivalent substitution etc., should be included in the scope of the protection.
Claims (7)
- A kind of 1. preparation side of the sponge structure type nickel cobalt molybdenum evanohm high temperature resistant energy-absorbing material of aluminium borate/silicon carbide whisker enhancing Method, it is characterised in that：It is made up of following step：S1. sponge structure polyethylene model conductive treatment；S2. sponge structure polyethylene model surface nickel cobalt molybdenum chromium/aluminium borate-silicon carbide whisker composite electrodeposition；S3. the removal of sponge structure polyethylene model is handled；S4. the heat treatment of nickel cobalt molybdenum chromium/aluminium borate-silicon carbide whisker whisker composite material.
- 2. a kind of sponge structure type nickel cobalt molybdenum evanohm of aluminium borate according to claim 1/silicon carbide whisker enhancing is resistance to The preparation method of high temperature energy-absorbing material, it is characterised in that：Step S1 specifically includes following operation：A1. electrocondution slurry is prepared：By carbon nano-fiber, nano carbon particle, hydroxyethylmethylcellulose, methacrylic acid, N- first Base pyrrolidones is added to suspension formed in deionized water, as electrocondution slurry；A2. sponge structure polyethylene model conductive treatment：Sponge structure polyethylene model is sufficiently submerged in electrocondution slurry, After the abundant hanging of sponge structure polyethylene model surface, dry 10~50 minutes at 30~50 DEG C and gathered with completing sponge structure Ethene model conductive treatment.
- 3. a kind of sponge structure type nickel cobalt molybdenum evanohm of aluminium borate according to claim 2/silicon carbide whisker enhancing is resistance to The preparation method of high temperature energy-absorbing material, it is characterised in that：The mass percent of each component is respectively in the electrocondution slurry：Nanometer Carbon fiber 3~22%, nano carbon particle 2~18%, hydroxyethylmethylcellulose 0.8~4%, methacrylic acid 0.5~12%, 1-METHYLPYRROLIDONE 1.5~6%, remaining is deionized water.
- 4. a kind of sponge structure type nickel cobalt molybdenum evanohm of aluminium borate according to claim 1/silicon carbide whisker enhancing is resistance to The preparation method of high temperature energy-absorbing material, it is characterised in that：Step S2 specifically includes following operation：B1. the preparation of nickel cobalt molybdenum chromium electrodeposit liquid：It is analytically pure nickel sulfamic acid, nickelous hypophosphite, nickel acetate, bromination by concentration Nickel, cobaltous fluoride, cobalt chloride, NPE, tributyl phosphate, sulfuric acid, citric acid, neopelex, receive Rice chromium powder, nano Mo powder, aluminium borate whisker and silicon carbide whisker are added sequentially in deionized water, form electrodeposit liquid；B2. composite electrodeposition process：It is anode using the sponge structure polyethylene model of conductive treatment as negative electrode, nickel plate, In 120~350mA/cm2Current density under carry out electro-deposition, electrodeposit liquid temperature maintains 30~60 DEG C, electrodeposition time For 0.5~2 hour, whole electrodeposition process was stirred with ultrasonic wave.
- 5. a kind of sponge structure type nickel cobalt molybdenum evanohm of aluminium borate according to claim 4/silicon carbide whisker enhancing is resistance to The preparation method of high temperature energy-absorbing material, it is characterised in that：Each component concentration is respectively nickel sulfamic acid 20 in the electrodeposit liquid ~100g/L, 15~120g/L of nickelous hypophosphite, 10~70g/L of nickel acetate, 2~15g/L of nickelous bromide, 15~60g/L of cobaltous fluoride, chlorine Change cobalt 10~50g/L, 10~50mL/L of NPE, 5~30mL/L of tributyl phosphate, 1.5~10mL/L of sulfuric acid, 3~10g/L of citric acid, 10~40g/L of neopelex, 20~40g/L of nanometer chromium powder, 0.5~10g/ of nano Mo powder L, 40~120g/L of aluminium borate whisker, 30~80g/L of silicon carbide whisker.
- 6. a kind of sponge structure type nickel cobalt molybdenum evanohm of aluminium borate according to claim 1/silicon carbide whisker enhancing is resistance to The preparation method of high temperature energy-absorbing material, it is characterised in that：Step S3 is specially：Sponge structure polyethylene model after the completion of composite electrodeposition is fitted into electric furnace and protected in 0.1~4Mpa nitrogen atmosphere 100~360 DEG C are heated up under shield, is incubated 10~30 minutes so that sponge structure polyethylene model decomposition removes.
- 7. a kind of sponge structure type nickel cobalt molybdenum evanohm of aluminium borate according to claim 1/silicon carbide whisker enhancing is resistance to The preparation method of high temperature energy-absorbing material, it is characterised in that：Step S4 is specially：After the completion for the treatment of that sponge structure polyethylene model decomposition removes, furnace temperature is increased to 420~580 DEG C, insulation 1.2~5 Hour to realize the diffusion of cobalt atom；Then furnace temperature is increased to 600~1200 DEG C, is incubated 3~8 hours to realize molybdenum original The diffusion of son and cobalt atom, it is resistance to so as to finally obtain the sponge structure type nickel cobalt molybdenum evanohm of aluminium borate/silicon carbide whisker enhancing High temperature energy-absorbing material.
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