CN105734535A - Method capable of improving bonding strength of composite and nickel plating layer - Google Patents
Method capable of improving bonding strength of composite and nickel plating layer Download PDFInfo
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- CN105734535A CN105734535A CN201610158784.XA CN201610158784A CN105734535A CN 105734535 A CN105734535 A CN 105734535A CN 201610158784 A CN201610158784 A CN 201610158784A CN 105734535 A CN105734535 A CN 105734535A
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- nickel plating
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- fiber
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
- B29C70/12—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat
- B29C70/14—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat oriented
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/36—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and impregnating by casting, e.g. vacuum casting
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
Abstract
The invention relates to the field of composite surface metallization, and provides a technological method capable of improving bonding strength of a composite and a nickel plating layer. According to the method, firstly, a transition layer with nickel plating short fibers is added on the surface of the composite, and the nickel plating short fibers are randomly distributed or can be distributed in the transition layer according to certain directivity under the magnetic field action according to the performance requirement; the composite and the transition layer are subject to co-curing forming, the surface of the transition layer is subject to chemical nickel plating, and a composite product with the surface subject to nickel plating is obtained; and compared with the traditional method that different coarsening manners are adopted to improve the bonding strength of the plating layer and the composite, the method has the beneficial effects that the nickel plating short fibers in the transition layer penetrate the transition layer and are embedded in the nickel plating layer, the effect of fiber bridging of the composite and the nickel plating layer is achieved, the bonding strength of the plating layer can be greatly improved, the direction of the nickel plating short fibers in the transition layer can be regulated and controlled through a magnetic field, and the mechanical property of the plating layer has certain designability.
Description
Technical field
The present invention relates to non-metal material surface metallizing art, particularly relate to and a kind of use nickel plating chopped fiber to improve the process of composite and nickel coating bond strength.
Background technology
Fiber-reinforced resin matrix compound material has the advantage of high-strength light, has been widely used in the fields such as transportation, Aero-Space and energy source and power.But, the performance of composite is had important impact by applied environment, as the environmental factorss such as abrasion, oxidation, corrosion will cause the premature failure of composite.Such as in a humidity environment, steam can penetrate in composite by interface between crizzle or fiber/matrix, makes resin plasticizing and degraded, thus changing the physics of resin, chemical property, and then reduces the mechanical property of composite.In the air of heat, resin surface is easily aging, when not having any load, also can produce micro-crack.Additionally, due to composite is non-conductive, not heat conduction, wear no resistance, oxidative resistance difference etc. feature also limit its range of application.Composite material surface metallization both can improve composite usage performance under extreme service condition, the advantage that can retain again its high-strength light.
The major issue that the metallization of current composite material surface is faced with is that composite is not enough with the bond strength of the coat of metal.Current research is concentrated mainly on the different technique of proposition or method carries out surface metalation at composite material surface, but, how to improve the work of bond strength between composite and coating for certain surface metalation technical study also less.It is called in " a kind of method for surface metallation containing epoxy silicone " in Patent publication No CN104005027A name, the alligatoring effect being formed with effect containing epoxy silicone cannot be caused the hypodynamic problem of attachment of coating for single chemical method of roughening, adopt the method that physics alligatoring combines with chemistry alligatoring to improve binding force of cladding material.It improves composite with coat binding strength side's ratio juris is that siliceous epoxy resin surface carries out physics and chemistry alligatoring in preprocessing process, thus changing the surface topography containing epoxy silicone or increasing hydrophilic oxide group at its microcosmic surface, to increase mechanical bond effect and the chemisorption of coating and matrix.But, this method still can not meet some for the increase of coating Yu composite bond strength and require higher occasion for the adhesion of coating.Such as, use the spacing reflection mirror that composite makes, in order to make mirror surface can reach the effect of minute surface, need the composite after surface metalation is carried out machine glazed finish, the coat of metal needs to bear huge machining stress, and only strengthens the technique of coating and composite adhesion by roughening process at present and be difficult to meet such engineering demand.
Summary of the invention
Present invention aims to coating and composite bond strength in current composite material surface metallization process and can not meet the problem of engine request under specific environment, propose plating process introduces the method being added with nickel plating chopped fiber transition zone between the interface of composite and the coat of metal, on a microscopic scale, nickel plating chopped fiber can run through whole interfacial thickness, play the effect of the bridging coat of metal and composite, thus improving the bond strength of the coat of metal and composite.
Technical scheme:
A kind of method improving composite nickel coating bond strength, step is as follows:
1) it is placed in degreasing fluid by nickel plating chopped fiber ultrasonic cleaning, then with deionized water rinsing, dries；Being placed in concentration 5%-25% hydrochloric acid solution by above-mentioned nickel plating chopped fiber acid activation again removes the sull on its surface, then with deionized water rinsing, dries；Treated nickel plating chopped fiber being scattered in resin, obtains finely dispersed resin colloid, the mass percent of wherein nickel plating chopped fiber is 5%-50%；Resin colloid is coated on die surface, fiber-reinforced resin matrix compound material is prepared in a mold by composite material process planning, the colloid of composite material surface is transition zone, composite and transition zone co-curing molding, must arrive surface and have the composite of nickel plating chopped fiber transition zone；
2) to step 1) surface must be arrived there is the transition zone surface of the composite containing nickel plating chopped fiber transition zone carry out mechanical grinding, make nickel plating chopped fiber manifest, then be placed in degreasing fluid ultrasonic cleaning, deionized water rinsing, dries；After mechanical grinding, nickel plating chopped fiber reveals is in order to, in follow-up chemical plating process, coating can grow along one end of nickel plating chopped fiber, increases over time, and coating covers whole transition zone surface gradually.
3) to step 2) process after composite according to step 1) acid activation processing mode remove nickel plating chopped fiber surface sull, deionized water rinsing, dry；Then being placed in chemical nickel-plating liquid by composite, the nickel plating chopped fiber one end deposition growing on transition zone surface forms metallic nickel plated layer one layer fine and close；Again with deionized water rinsing, dry；Then above-mentioned composite is carried out plating and improves the thickness of metallic nickel plated layer, finally obtain the interface composite material surface metallized product through strengthening.
Described nickel plating chopped fiber can be random distribution in transition zone, can be maybe by certain directional distribution: nickel plating chopped fiber and the angle o directional spreding of composite material surface normal direction, θ span is 0 ° to 90 ° degree, by regulating and controlling nickel plating chopped fiber and composite material surface normal direction, metallic nickel plated layer is made to obtain different mechanical properties；Such as, when nickel plating chopped fiber and composite material surface normal direction are 0 ° of distribution, when being namely parallel to the distribution of composite material surface normal direction, it is possible to improve tension and compression modulus and the intensity at composite and coat of metal interface；To obtain good anti-shear performance, it is necessary to by nickel plating chopped fiber with composite material surface normal direction at an angle.According to nickel plating chopped fiber characteristic of magnetic field force induced regulation and control in magnetic field, regulate and control nickel plating chopped fiber directivity in transition zone by externally-applied magnetic field.
Described resin is epoxy resin, unsaturated polyester resin, vinyl ester resin or bimaleimide resin.
Described composite material process planning is low pressure contact moulding process, RTM moulding process, VARTM moulding process or VARIM moulding process.
Fortifying fibre in fiber-reinforced resin matrix compound material is one or more mixing in glass fibre, carbon fiber, aramid fiber.
Nickel plating chopped fiber specification 20-2000 order, and the nickel plating chopped fiber being mixed in transition zone can be single order number, it is also possible to it is the mixing of several order number.Described nickel plating chopped fiber can be one or more mixing in nickel plating short glass fiber, nickel plating short carbon fiber, nickel plating short aramid fiber.
The invention has the beneficial effects as follows to propose a kind of uses nickel plating chopped fiber to improve the process of composite and nickel coating bond strength, relative to the method that traditional method improves composite and coat of metal bond strength by composite material surface roughening process, the method is by adding the transition zone containing nickel plating chopped fiber at composite material surface, utilize nickel plating chopped fiber bridging composite and the coat of metal in transition zone, when coating is subject to extraneous load effect and cracks, crackle extends along interface, the stripping of nickel plating chopped fiber is will appear from and nickel plating chopped fiber such as extracts at the process at crack front, add dissipation of energy, thus the bond strength improved between composite and metallic nickel plated layer；It addition, the direction of nickel plating chopped fiber can be subject to the regulation and control in magnetic field in transition zone, thus the metallic nickel plated layer for obtaining different mechanical properties provides possibility, the mechanical property of metallic nickel plated layer is made to be provided with certain designability.Meanwhile, in plating process, coating can directly grow near nickel plating chopped fiber, it is not necessary to sensitization, dispergation etc., simplifies technological process.
Accompanying drawing explanation
Fig. 1 is the principle schematic of nickel plating chopped fiber bridging composite of the present invention and nickel coating.
Fig. 2 is without nickel plating chopped fiber random distribution view in the transition zone of field orientation.Nickel plating chopped fiber random distribution in the longitudinal direction under the combined effect of self gravitation and resin viscous resistance in figure.
Fig. 3 be after field orientation in transition zone nickel plating staple length direction along the directional spreding view of the magnetic line of force.In figure, nickel plating chopped fiber is under the combined effect of magnetic field force, self gravitation and resin viscous resistance, magnetic field force overcomes the gravity of nickel plating chopped fiber self and the viscous drag of resin to make nickel plating chopped fiber longitudinally along the directional spreding of the magnetic line of force, thus realizing the regulation and control to nickel plating chopped fiber direction.
Fig. 4 is the composite material test piece schematic diagram that VARIM technique prepares surface interpolation transition zone.
In figure: 1 composite；2 nickel plating chopped fiber；3 transition zones；4 nickel coatings；5 sealant tapes；
6 moulds；7 releasing agents；8 transition zones containing nickel plating chopped fiber；9 fiber cloth；10 gum-injecting ports；
11 vacuum bag film；12 flow-guiding screens；13 release cloths；14 vacuum ports.
Detailed description of the invention
Below according to technical scheme and accompanying drawing, detailed description detailed description of the invention being described, select a kind of fiber-reinforced resin matrix compound material to apply method of the present invention to improve the bond strength of composite and nickel coating, detailed description of the invention is as follows:
Embodiment 1
The nickel plating short carbon fiber that specification is 200 orders is put in degreasing fluid, it is placed in ultrasonic washing unit ultrasonic cleaning 5min again and removes greasy dirt and the dust of attachment in processing or transportation, dry after cleaning with deionized water, it is then placed in hydrochloric acid solution acid activation and removes the sull on nickel plating short carbon fiber surface, clean after drying again with deionized water, the nickel plating short carbon fiber handled well is joined in epoxy resin LY5288 according to mass fraction 35%, the stirring of reinforcement electric blender is used to be distributed in epoxy resin standby uniformly to nickel plating short carbon fiber, now nickel plating short carbon fiber random distribution in transition zone.Resin colloid containing nickel plating short carbon fiber is evenly applied to die surface as shown in Figure 3, glass fabric EW200 and epoxy resin LY5288 is selected to adopt low pressure contact moulding process to prepare glass fiber reinforced epoxy resin base composite material laminated plate test specimen in the mould shown in Fig. 3, specimen size 120mm × 120mm, the number of plies 10, composite and transition zone co-curing molding.With sand paper, transition zone surface being carried out mechanical grinding after curing molding, the purpose of mechanical grinding is that the one layer of resin removing transition zone surface softer makes nickel plating short carbon fiber one end in transition zone reveal.After mechanical grinding, greasy dirt and the dust on transition zone surface is removed with degreasing fluid ultrasonic cleaning, dry with after deionized water rinsing test specimen after oil removing, use hydrochloric acid that transition zone surface open nickel plating short carbon fiber out is carried out acid activation process, dry after deionized water rinsing, then sample is put in chemical plating fluid and carry out chemical plating, coating is depositing around the nickel plating short carbon fiber on transition zone surface, form metallic nickel plated layer one layer fine and close, finally adopt routine plating to thicken nickel coating and obtain final composite material surface metallized product.
Embodiment 2
Put into after the nickel plating short carbon fiber that specification is 200 orders and 400 orders is mixed in 1:1 ratio and degreasing fluid is placed in ultrasonic washing unit again and cleans 5min removes greasy dirt and the dust of attachment in processing or transportation, dry with deionized water rinsing after ultrasonic cleaning, place into acid activation in hydrochloric acid solution and remove the sull on nickel plating short carbon fiber surface, deionized water cleans after drying, the nickel plating short carbon fiber handled well is added in epoxy resin 2040 according to mass fraction 40%, the stirring of reinforcement electric blender is used to be distributed in epoxy resin standby uniformly to nickel plating short carbon fiber, now nickel plating short carbon fiber random distribution in transition zone.Resin colloid containing nickel plating short carbon fiber is evenly applied to die surface as shown in Figure 2, then mould is placed in magnetic field, the magnetic line of force is oriented parallel to die surface normal direction as shown in Figure 3, complete the orientation to nickel plating short carbon fiber, distribution in transition zone after nickel plating short carbon fiber orientation is as it is shown on figure 3, nickel plating short carbon fiber is parallel with the surface normal direction of mould in the longitudinal direction.On mould in figure 3 order shown in Fig. 4 on transition zone successively paving cover glass fabric, release cloth, flow-guiding screen, then with vacuum bag film and sealing joint strip by test specimen regional seal, and location arrangements gum-injecting port shown in Fig. 4 and vacuum port.Select glass fabric EW100 and epoxy resin 2040 to adopt VARIM technique to prepare composite laminated plate test specimen herein, specimen size 120mm × 120mm, the number of plies 10, resin is injected by gum-injecting port 10, the flowing of direction shown in arrow sized glass fibres cloth along Fig. 4, after glass fabric complete wetting, stop resin by injection, gum-injecting port 10 and vacuum port 14 are sealed, composite and transition zone co-curing molding in a mold.After molding, adopt mechanical grinding mode remove one layer of resin that transition zone surface is softer so that nickel plating short carbon fiber reveals, then with degreasing fluid air exercise honed after surface carry out ultrasonic cleaning oil removing, after ultrasonic cleaning, test specimen deionized water rinsing is dried.Then, test specimen is carried out acid activation process, after being disposed, dries with after deionized water rinsing test specimen, again sample is placed in chemical plating fluid and carries out chemical plating acquisition metallic nickel plated layer, finally adopt conventional plating process to thicken metallic nickel plated layer and obtain composite material surface metallized product.
Claims (10)
1. the method improving composite nickel coating bond strength, it is characterised in that step is as follows:
1) it is placed in degreasing fluid by nickel plating chopped fiber ultrasonic cleaning, then with deionized water rinsing, dries；Above-mentioned nickel plating chopped fiber is placed in concentration 5% 25% hydrochloric acid solution acid activation again removes the sull on its surface, then with deionized water rinsing, dries；Treated nickel plating chopped fiber being scattered in resin, obtains finely dispersed resin colloid, the mass percent of wherein nickel plating chopped fiber is 5% 50%；Resin colloid is coated on die surface, fiber-reinforced resin matrix compound material is prepared in a mold by composite material process planning, the colloid of composite material surface and transition zone, composite and transition zone co-curing molding, must arrive surface and have the composite of nickel plating chopped fiber transition zone；
2) to step 1) surface that obtains has the transition zone surface of the composite containing nickel plating chopped fiber transition zone and carries out mechanical grinding, makes nickel plating chopped fiber manifest, then it is placed in degreasing fluid ultrasonic cleaning, deionized water rinsing, dries；
3) to step 2) process after composite according to step 1) acid activation processing mode remove nickel plating chopped fiber surface sull, deionized water rinsing, dry；Then being placed in chemical nickel-plating liquid by composite, the nickel plating chopped fiber one end deposition growing on transition zone surface forms metallic nickel plated layer one layer fine and close；Again with deionized water rinsing, dry；Then above-mentioned composite is carried out plating and improves the thickness of metallic nickel plated layer, finally obtain the interface composite material surface metallized product through strengthening.
2. method according to claim 1, it is characterized in that, described nickel plating chopped fiber is at transition zone random distribution or by certain directional distribution: nickel plating chopped fiber and the angle o directional spreding of composite material surface normal direction, θ span is 0 ° to 90 ° degree, regulates and controls nickel plating chopped fiber in transition zone relative to the angle of composite material surface normal by externally-applied magnetic field.
3. method according to claim 1 and 2, it is characterised in that the described fortifying fibre in fiber-reinforced resin matrix compound material is one or more mixing in glass fibre, carbon fiber, aramid fiber.
4. method according to claim 1 and 2, it is characterised in that described resin is epoxy resin, unsaturated polyester resin, vinyl ester resin or bimaleimide resin.
5. method according to claim 3, it is characterised in that described resin is epoxy resin, unsaturated polyester resin, vinyl ester resin or bimaleimide resin.
6. the method according to claim 1,2 or 5, it is characterised in that described composite material process planning is low pressure contact moulding process, RTM moulding process, VARTM moulding process or VARIM moulding process.
7. method according to claim 3, it is characterised in that described composite material process planning is low pressure contact moulding process, RTM moulding process, VARTM moulding process or VARIM moulding process.
8. method according to claim 4, it is characterised in that described composite material process planning is low pressure contact moulding process, RTM moulding process, VARTM moulding process or VARIM moulding process.
9. the method according to claim 1,2,5,7 or 8, it is characterised in that described nickel plating chopped fiber is 20 2000 orders, and the nickel plating chopped fiber being mixed in transition zone is single order number or the mixing of several order number；Described nickel plating chopped fiber is one or more mixing in nickel plating short glass fiber, nickel plating short carbon fiber, nickel plating short aramid fiber.
10. method according to claim 6, it is characterised in that described nickel plating chopped fiber is 20 2000 orders, and the nickel plating chopped fiber being mixed in transition zone is single order number or the mixing of several order number；Described nickel plating chopped fiber is one or more mixing in nickel plating short glass fiber, nickel plating short carbon fiber, nickel plating short aramid fiber.
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| CN201610158784.XA CN105734535B (en) | 2016-03-18 | 2016-03-18 | A method of improving composite material nickel coating bond strength |
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| CN201610158784.XA CN105734535B (en) | 2016-03-18 | 2016-03-18 | A method of improving composite material nickel coating bond strength |
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| CN110914490A (en) * | 2017-03-23 | 2020-03-24 | 波士顿材料公司 | Fiber reinforced composite, method thereof and articles containing the composite |
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| CN112976698A (en) * | 2019-12-02 | 2021-06-18 | 中国石油化工股份有限公司 | Fatigue-resistant composite material continuous sucker rod and preparation device and preparation method thereof |
| US11479656B2 (en) | 2019-07-10 | 2022-10-25 | Boston Materials, Inc. | Systems and methods for forming short-fiber films, composites comprising thermosets, and other composites |
| CN116377501A (en) * | 2023-04-10 | 2023-07-04 | 陕西华秦新能源科技有限责任公司 | Electrocatalytic hydrogen evolution material and preparation method and application thereof |
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| CN110914490A (en) * | 2017-03-23 | 2020-03-24 | 波士顿材料公司 | Fiber reinforced composite, method thereof and articles containing the composite |
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| CN112976698A (en) * | 2019-12-02 | 2021-06-18 | 中国石油化工股份有限公司 | Fatigue-resistant composite material continuous sucker rod and preparation device and preparation method thereof |
| CN111844831A (en) * | 2020-07-06 | 2020-10-30 | 大连理工大学 | Manufacturing method of light base material thin-wall reflector |
| CN116377501A (en) * | 2023-04-10 | 2023-07-04 | 陕西华秦新能源科技有限责任公司 | Electrocatalytic hydrogen evolution material and preparation method and application thereof |
| CN116377501B (en) * | 2023-04-10 | 2024-01-02 | 陕西华秦新能源科技有限责任公司 | Electrocatalytic hydrogen evolution material and preparation method and application thereof |
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| CN105734535B (en) | 2019-03-05 |
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