CN104561942A - Palladium-free activation method of silicon carbide powder - Google Patents
Palladium-free activation method of silicon carbide powder Download PDFInfo
- Publication number
- CN104561942A CN104561942A CN201410815056.2A CN201410815056A CN104561942A CN 104561942 A CN104561942 A CN 104561942A CN 201410815056 A CN201410815056 A CN 201410815056A CN 104561942 A CN104561942 A CN 104561942A
- Authority
- CN
- China
- Prior art keywords
- silicon carbide
- carbide powder
- activation
- palladium
- solvent
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
- C23C18/1879—Use of metal, e.g. activation, sensitisation with noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- 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
- C23C18/38—Coating with copper
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
The invention discloses a palladium-free activation method of silicon carbide powder. The method comprises the following steps: 1) pretreatment of a silicon carbide powder raw material, to be specific, cleaning the organic attachments on the surface of the silicon carbide powder by an organic solvent and cleaning the inorganic attachments on the surface of the silicon carbide powder by inorganic acid solution and/or alkaline solution; 2) activation of the silicon carbide powder, to be specific, adding the cleaned silicon carbide powder into a ferric salt-containing organic solvent system and adding a reducing agent to activate the silicon carbide powder; 3) separating the activated silicon carbide powder and carrying out chemical plating treatment. According to the activation method provided by the invention, the palladium-free activation of the SiC powder is realized, the activation liquor is stable in performance, the production cost is reduced and the pollution is avoided.
Description
Technical field
The present invention relates to the palladium-free activation process of silicon carbide powder, belong to chemical field.
Background technology
Silicon carbide (SiC) powder has wear-resisting, heat-resisting, high strength, the advantage such as cheap, can be used as particulates reinforcements, is widely used in and prepares metal-base composites.Although the chemical property of SiC powder is highly stable, prepare in the process of matrix material, if directly add in metallic matrix by SiC powder, then very easily chemical reaction occurs between SiC and metal interface, cause the interface compatibility of matrix material poor, affect its performance.
For the problems referred to above, need to carry out at SiC powder front modification of adulterating, as in the coated layer of metal of powder surface, thus avoid itself and metallic matrix to react.The method for coating of powder has chemical Vapor deposition process, vacuum sputtering, electrodip process and electroless plating method, and wherein electroless plating method is because of advantages such as processing unit are simple, easy to operate, covered effect is good, has good suitability.But electroless plating method also faces difficult point in a particular application, it is nonmetal basal body that the difficult point of SiC powder electroless is mainly reflected in SiC powder, does not have catalytic activity, needs to activate before electroless plating.Activation method conventional is at present palladium activation, and this mode cost is higher, and there is comparatively serious environmental pollution, is difficult to large-scale application.For this problem, some no-palladium activating technique has been attempted in this area, more traditional palladium activating cost is low, it is little to pollute, but still Shortcomings on activation effect, and in pollution problem, still do not find good solution, have such as recent years investigator to attempt utilizing reductive agent reduction nickelous acetate to carry out activation treatment to SiC powder, but nickel ion remain a kind of heavy metal ion environment being existed to larger pollution, is difficult to avoided by subsequent technique or clear up this source of pollution; Simultaneously this technique is very limited by the stability of the critical defect that the experiment of the author finds to exist to be the effect utilizing nickelous acetate to carry out activation treatment be activation solution, can lose efficacy in activation solution preparation 1h, cannot carry out activation treatment again, this makes it can only be now with the current.This feature greatly limit its practical application.
Summary of the invention
Applicant have extensively studied the no-palladium activating technique of silicon carbide powder, match with reductive agent with molysite, there iing the activation realizing silicon carbide powder under solvent environment, not only achieve the no-palladium activating of silicon carbide powder, and whole technological process heavy metal free ionic soil, the stable performance of activation solution, can be connected with traditional chemical technology process such as realizing electroless copper, thus farthest reduce production cost.
Specifically, the present invention is achieved through the following technical solutions:
A kind of palladium-free activation process of silicon carbide powder, comprise the steps: 1) pre-treatment of silicon carbide powder raw material: the organic dirt settling utilizing organic solvent cleaning sic powder surface, utilizes the inorganic dirt settling of inorganic acid solution and/or alkaline solution cleaning sic powder surface; 2) activation of silicon carbide powder: the silicon carbide powder after cleaning is joined in the solution containing molysite, then adds reductive agent wherein and silicon carbide powder is activated; 3) be separated the silicon carbide powder of activation, carry out electroless plating process.
In such scheme, reductive agent is matched with the solution of molysite, form active metal iron at SiC powder surface, realize the no-palladium activating of SiC powder; After by iron packaged silicon carbide particles, directly can carry out copper facing in the mode of electroless plating from the teeth outwards, compare with nickel parcel, not only avoid pollution, traditional chemical-copper-plating process more crucially directly can be utilized to carry out electroless plating, reduce production cost.
Wherein, in step 1) in, the various pollutent such as organic and inorganic in order to remove wherein to the cleaning of silicon carbide, specifically, dehydrated alcohol or acetone is adopted to clean under ultrasound environments as organic solvent, then the cleaning under ultrasound environments of NaOH solution, hydrochloric acid soln is used, final rinse water post-drying.
In aforesaid operations, adopting ultrasonic is to strengthen cleaning performance, ensures that particle fully contacts with scavenging solution; Adopt other mode, such as concussion etc. also can be used for the present invention at a high speed.
Wherein, in step 2) in, described molysite is one or more in ferrous sulfate, Ferrox, ferric oxide, iron nitrate, and the solvent of iron salt solutions is one or more in water, methyl alcohol, ethanol, acetone, toluene; Described reductive agent is one or more in sodium borohydride, POTASSIUM BOROHYDRIDE, sodium hypophosphite, hydrazine hydrate.
Preferably, molysite used is iron nitrate, and organic solvent used is ethanol, and reductive agent used is sodium borohydride.
Wherein, in step 2) in, also comprise and pretreated step carried out to reductive agent used, namely first reductive agent is joined in solvent and dissolve, described solvent to be solvent be in water, methyl alcohol, ethanol, acetone, toluene one or more.
Preferably, solvent for use is ethanol.
Experiment that applicant carries out display, after above-mentioned activation treatment in silicon carbide powder surface adsorption iron particle, carry out copper-plating technique on this basis, carborundum powder surface complete packet is covered with metallic copper, has good consistency.
In the present invention, do not limit the relative usage of molysite specifically used, solvent, reductive agent, usually molysite being joined the later concentration of solvent is 0.4-10g/L, the consumption of reductive agent with final concentration in a solvent for 0.4-5g/L.
In the preferred case, when employing molysite is iron nitrate, organic solvent is ethanol, when reductive agent is sodium borohydride, iron nitrate concentration is in ethanol preferably 0.5-1g/L, and sodium borohydride concentration is in ethanol preferably 0.8-2g/L, can realize 100% and activate completely in this concentration range.
In the present invention, soak time is not restricted, and in usual 1min-4h, usually can realize activating completely at 5min.
By above-mentioned improvement, technical scheme of the present invention adopts molysite as activation solution main component, and achieve the activation of silicon-carbide particle, not only activation effect is good, and activation solution stable performance, cost are low, pollution-free.
Accompanying drawing explanation
Fig. 1 is the SEM figure before silicon carbide powder plating.
Fig. 2 is the SEM figure after silicon carbide powder plating.
Fig. 3 is the XRD figure after silicon carbide powder activation.
Fig. 4 is the XRD figure after silicon carbide powder copper facing.
Embodiment
In order to the specific implementation of technical solution of the present invention is described, applicant provide following some concrete enforcement.The present invention is not limited to this, and all amendment, replacement, changes made within the scope of the claims in the present invention all belong to protection scope of the present invention.
Embodiment 1
(1) pre-treatment: 50 object silicon carbide powder priority acetone and deionized water are carried out ultrasonic cleaning, with 5wt%NaOH solution ultrasonic cleaning 5min after filtering, again with 10v/v%HCl cleaning after filtration, filter rear distilled water flushing, be placed on 80 DEG C of oven dry in loft drier.
(2) preparation of activation solution: under room temperature condition, adds iron nitrate in dehydrated alcohol, is configured to the alcoholic solution 1g/L of molysite, fully dissolves; Sodium borohydride 3.5g/L is added in dehydrated alcohol, and hydro-oxidation sodium adjust ph 8.5 ~ 12, fully dissolve.
(3) activate: first the carborundum powder that step (1) is handled well is joined in the iron nitrate ethanolic soln in step (2), again the ethanolic soln of sodium borohydride in step (2) is slowly poured in iron nitrate ethanolic soln and carry out activating (total consumption of solution at least can hold whole silicon carbide powder), activation is carried out at ambient temperature, soak time is 5min, decantation is adopted to be separated the silicon carbide powder after activation, ageing certain hour.
(4) electroless plating: the silicon carbide powder after above-mentioned activation treatment is carried out electroless copper process.
The coated layers of copper of embodiment 1 gained silicon carbide powder, scanning electronic microscope (SEM) is used to observe apparent form, silicon carbide powder apparent form before and after acquisition plating is as Fig. 1, shown in Fig. 2, can find out that before and after plating, the apparent of silicon carbide powder there occurs obvious change, the coating even compact that powder is coated; X-ray diffractometer (XRD) composition to silicon carbide powder is used to test, the spectrogram obtained is as Fig. 3, shown in Fig. 4, iron particle obviously can have been found out after activation in silicon carbide powder surface adsorption by Fig. 3, Fig. 4 has shown on silicon carbide powder Surface coating metallic copper, and test result shows that this activation method is respond well.
Embodiment 2
Changing molysite in embodiment 1 step (2) is ferrous sulfate, and all the other conditions are with embodiment 1.The coated layers of copper of gained silicon carbide powder, coating even compact, this activation method is respond well.
Embodiment 3
Changing molysite in embodiment 1 step (2) is ferric oxide, and all the other conditions are with embodiment 1.The coated layers of copper of gained silicon carbide powder, coating even compact, this activation method is respond well.
Embodiment 4
Changing molysite in embodiment 1 step (2) is Ferrox, and all the other conditions are with embodiment 1.The coated layers of copper of gained silicon carbide powder, coating even compact, this activation method is respond well.
Embodiment 5
Changing reductive agent in embodiment 1 step (2) is POTASSIUM BOROHYDRIDE, and all the other conditions are with embodiment 1.The coated layers of copper of gained silicon carbide powder, coating even compact, this activation method is respond well.
Embodiment 6
Changing reductive agent in embodiment 1 step (2) is sodium hypophosphite, and all the other conditions are with embodiment 1.The coated layers of copper of gained silicon carbide powder, coating even compact, this activation method is respond well.
Embodiment 7
Changing reductive agent in embodiment 1 step (2) is hydrazine hydrate, and all the other conditions are with embodiment 1.The coated layers of copper of gained silicon carbide powder, coating even compact, this activation method is respond well.
Embodiment 8
Changing dehydrated alcohol in embodiment 1 step (2) is water, and all the other conditions are with embodiment 1.The coated layers of copper of gained silicon carbide powder, coating even compact, this activation method is respond well.
Embodiment 9
Changing dehydrated alcohol in embodiment 1 step (2) is acetone, and all the other conditions are with embodiment 1.The coated layers of copper of gained silicon carbide powder, coating even compact, this activation method is respond well.
Embodiment 10
Changing dehydrated alcohol in embodiment 1 step (2) is methyl alcohol, and all the other conditions are with embodiment 1.The coated layers of copper of gained silicon carbide powder, coating even compact, this activation method is respond well.
Embodiment 11
Changing dehydrated alcohol in embodiment 1 step (2) is toluene, and all the other conditions are with embodiment 1.The coated layers of copper of gained silicon carbide powder, coating even compact, this activation method is respond well.
Comparative example
With organic nickel salt reduction method of the research in the early stage R&D process of applicant, activation treatment is carried out to SiC powder, concrete activating process parameter adopts nickelous acetate 1g/L, sodium borohydride 2g/L, activate under room temperature condition, when being less than 1h upon activation, after experimental result display activation, nickel is wrapped in particle surface preferably; But more than 1h upon activation, carry out copper facing with copper-plating technique on surface, it is coated that the SiC powder of process cannot carry out chemistry, illustrates that activation solution lost efficacy.
Claims (4)
1. the palladium-free activation process of a silicon carbide powder, it is characterized in that comprising the steps: 1) pre-treatment of silicon carbide powder raw material: the organic dirt settling utilizing organic solvent cleaning sic powder surface, utilizes the inorganic dirt settling of inorganic acid solution and/or alkaline solution cleaning sic powder surface; 2) activation of silicon carbide powder: the silicon carbide powder after cleaning is joined in the solution containing molysite, then adds reductive agent wherein and silicon carbide powder is activated; 3) be separated the silicon carbide powder of activation, carry out electroless plating process.
2. palladium-free activation process according to claim 1, it is characterized in that in step 1) in, adopt dehydrated alcohol or acetone to clean under ultrasound environments as organic solvent, then use the cleaning under ultrasound environments of NaOH solution, hydrochloric acid soln, final rinse water post-drying.
3. palladium-free activation process according to claim 1, it is characterized in that in step 2) in, described molysite is one or more in ferrous sulfate, Ferrox, ferric oxide, iron nitrate, and the solvent of iron salt solutions is one or more in water, methyl alcohol, ethanol, acetone, toluene; Described reductive agent is one or more in sodium borohydride, POTASSIUM BOROHYDRIDE, sodium hypophosphite, hydrazine hydrate.
4. palladium-free activation process according to claim 1, it is characterized in that in step 2) in, also comprise and pretreated step is carried out to reductive agent used, namely first reductive agent is joined in solvent and dissolves, described solvent to be solvent be in water, methyl alcohol, ethanol, acetone, toluene one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410815056.2A CN104561942B (en) | 2014-12-24 | 2014-12-24 | Palladium-free activation method of silicon carbide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410815056.2A CN104561942B (en) | 2014-12-24 | 2014-12-24 | Palladium-free activation method of silicon carbide powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104561942A true CN104561942A (en) | 2015-04-29 |
| CN104561942B CN104561942B (en) | 2017-02-22 |
Family
ID=53078997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410815056.2A Expired - Fee Related CN104561942B (en) | 2014-12-24 | 2014-12-24 | Palladium-free activation method of silicon carbide powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104561942B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105195737A (en) * | 2015-10-14 | 2015-12-30 | 东南大学 | Method for covering surfaces of SiC particles with nickel |
| CN106698435A (en) * | 2016-12-16 | 2017-05-24 | 苏州金仓合金新材料有限公司 | Silicon carbide particle and preparation method thereof |
| CN110499502A (en) * | 2019-09-24 | 2019-11-26 | 青岛科技大学 | A kind of preparation method of plating iron graphene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1740382A (en) * | 2005-09-22 | 2006-03-01 | 上海交通大学 | Chemical copper plating process for the surface of SiC ceramic grain |
-
2014
- 2014-12-24 CN CN201410815056.2A patent/CN104561942B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1740382A (en) * | 2005-09-22 | 2006-03-01 | 上海交通大学 | Chemical copper plating process for the surface of SiC ceramic grain |
Non-Patent Citations (2)
| Title |
|---|
| LAI-MA LUO ET AL.: "Electroless copper plating on PC engineering plastic with a novel palladium-free surface activation process", 《SURFACE & COATINGS TECHNOLOGY》 * |
| 邹忠利等: "碳化硅粉体化学镀镍前无钯活化工艺", 《电镀与涂饰》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105195737A (en) * | 2015-10-14 | 2015-12-30 | 东南大学 | Method for covering surfaces of SiC particles with nickel |
| CN105195737B (en) * | 2015-10-14 | 2017-07-18 | 东南大学 | A kind of method of SiC particulate surface cladded with nickel |
| CN106698435A (en) * | 2016-12-16 | 2017-05-24 | 苏州金仓合金新材料有限公司 | Silicon carbide particle and preparation method thereof |
| CN110499502A (en) * | 2019-09-24 | 2019-11-26 | 青岛科技大学 | A kind of preparation method of plating iron graphene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104561942B (en) | 2017-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105195737B (en) | A kind of method of SiC particulate surface cladded with nickel | |
| CN102002747B (en) | Method for preparing metal surface fullerene film by electrophoresis | |
| CN100451166C (en) | Chemical plating activating process and metal depositing process therewith | |
| CN100348778C (en) | Chemical copper plating process for the surface of SiC ceramic grain | |
| CN104561942A (en) | Palladium-free activation method of silicon carbide powder | |
| CN106148926A (en) | Silver-coated copper powder and preparation method thereof | |
| JP2020045574A (en) | Composition and method for metallizing non-conductive plastic surface | |
| CN104862676A (en) | Graphene oxide nickel-phosphorus composite plating solution, preparation method and applications thereof | |
| CN102978667B (en) | A kind of method of preparing nano-bronze powder using electric deposition | |
| WO2006072943A3 (en) | Nano- and mesosized particles comprising an inorganic core, process and applications thereof | |
| JP2012532253A5 (en) | ||
| CN101818337A (en) | Coating method of high-density Ni layer of carbon nano tube | |
| CN101942689A (en) | Micro-arc oxidation treatment method of magnesium alloy | |
| EP3255176B1 (en) | Method of plating particulate matter | |
| CN114870823A (en) | Lanthanum-based metal organic framework dephosphorization composite material and preparation method and application thereof | |
| CN100469699C (en) | Method for the treatment of aluminum oxide powder | |
| CN106835086A (en) | A kind of plating nickel on surface method of artificial diamond | |
| CN104988476A (en) | Method for plating nano-silver on surface of diamond micro-powder | |
| CN1831048A (en) | Siliver-carried micron kaolin and its prepn. method | |
| CN101302080B (en) | Pretreatment method of chemical plating conductive magneto-conductive glass fibre | |
| CN100348777C (en) | Tangsten plating process for the surface of SiC ceramic grain | |
| CN102776494A (en) | Peptizing solution for metalized modification on surface of macromolecule material | |
| CN104694910A (en) | Preparation process for bionic self-cleaning metal fiber filtering material | |
| CN104325137B (en) | A kind of preparation method of silvered aluminum powder | |
| CN104294243B (en) | A kind of aluminum pipe nickel plating process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170222 Termination date: 20171224 |