CN1187222A - Improved uniformly plated microsphere catalyst - Google Patents
Improved uniformly plated microsphere catalyst Download PDFInfo
- Publication number
- CN1187222A CN1187222A CN96194463A CN96194463A CN1187222A CN 1187222 A CN1187222 A CN 1187222A CN 96194463 A CN96194463 A CN 96194463A CN 96194463 A CN96194463 A CN 96194463A CN 1187222 A CN1187222 A CN 1187222A
- Authority
- CN
- China
- Prior art keywords
- layer
- metal
- palladium
- catalyzer
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Chemically Coating (AREA)
- Catalysts (AREA)
Abstract
Cross-linked polymer non-conductive cores (12) having a sulfonated cation exchange surface are carefully separated into fractions of equal size and density. Each fraction is separately plated preferably with a copper, palladium, nickel, titanium or any metal cation which will reduce with hydrazine to form a conductive metal flash coating (14 or 24). The flash coat plated microspheres are again separated into fractions of equal size and density. Each fraction is then given additional metal platings first of nickel (16 or 26), then preferably palladium (18 or 28), then a support layer for the palladium, followed preferably by a stabilizing metal layer (32) such as chromium. The thus plated microspheres (10 or 22) have uniformly thick platings and have a maximized surface area for the amount of metal plated making them particularly useful as catalysts or in electrical products or processes. Microspheres having a plating of palladium (18 or 28) exhibit a marked improvement in the adsorption of hydrogen both quantitatively and in rapidity. An inner nickel layer (16 or 26) between the copper flash coat (14 or 24) and palladium layer (18 or 28) and an outer nickel layer (20 or 30) atop the palladium layer serve to structurally stabilize the palladium layer during a heat production duty cycle without inhibiting hydrogen adsorption by the palladium layer.
Description
The present invention relates in general to metal deposition, particularly relates to the improved uniformly plated microsphere of the improvement that is used for catalytic treatment and electronic application aspect.
At United States Patent (USP) 3,577, in 324, as most preferred embodiment, I disclose a kind of method and device thereof of plating grain, this plating grain from the Vinylstyrene plating of the polymer beads that forms of the polystyrene of commissure mutually.The bonded copper atom is disclosed to a kind of solution of this particulate.
At United States Patent (USP) 3,787, in 718, I disclose use plating spherolite as the electronics component.In this patent, also disclose and on the copper layer, formed additional coating or coating.
The United States Patent (USP) of " through the palladium plating of chemical reduction " by name of people such as Rhoda invention discloses many body lotions that are used to immerse various metal depositions.
The early stage patent of my another, United States Patent (USP) 5,036,031 discloses a kind of metal deposition microspheroidal catalyst, and this is disclosed in, and this is for referencial use.This early stage patent disclosure on palladium coating, use the copper coating of uniform thickness, on the formed microsphere of commissure polystyrene, use copper coating ' 324 patent that is similar to mine.
' 031 patent battery in my early stage United States Patent (USP) 5,372,688 discloses the application microspheroidal catalyst.I have observed a kind of black residue that forms in the liquid electrolyte of this battery.I also find to have shortened desired battery life.Further research, I think that this black residue is the palladium that goes out from the microspheroidal catalyst particle separation under the Circulation of heat and electric current.
The invention discloses the preparation that has the copolymer microsphere body of mantoquita at outer position.These microspheres are separated on each evenly big or small basically in batches, then plating.By plating size and the identical microsphere of density (as determining) with the Stoke rule, can obtain the coating of uniform thickness, when plated microsphere is used for catalytic bed and/or electric current when mobile, the coating of this homogeneous thickness is necessary.The coating of non-homogeneous thickness can cause generation the showing tremendous enthusiasm flower of plating exfoliation.A kind of modified form coating layer that is coated with one deck nickel on palladium also is disclosed, and this is used for stablizing palladium from structure, and does not suppress the diffusion of hydrogen to palladium.
As United States Patent (USP) 5,036,031 and 4,943,355 is disclosed, in a post exchange, a kind of multipolymer in the Hydrogen and chlorsulfonic acid reaction, result's microsphere in Hydrogen has the sulfonation surface.This microsphere with deionized water towards Xian.Then the sulfonated microsphere is put into the hydration Cupric Chloride Solution.There is mantoquita on this microsphere surface, and contains hydrochloric acid in ion exchanged soln.Once more with deionized water towards Xian's microsphere.The multipolymer that produces when dry is the microsphere of appearance with mantoquita.These microspheres are progressively by being divided into the 16-18 order to being divided into the 25-30 order by sieve at last from initial sieve.The further hydraulic pressure of separated group of every kind of this class microsphere separates, and obtains ideal microsphere size to ± 0.005g/cm
3
Then, these microspheres United States Patent (USP) 3,577,324 disclosed no electronics copper plating liquids, cover down plating having desired good stirring or have the scumbling that is formed by a kind of metallic cation, used metallic cation will be with hydrogen or hydrazine chemical reduction, as copper, nickel, palladium, titanium.Dry and further after the classification, these microspheres use the device of ' 324 patent disclosure of originally mentioning and carry out additional metal deposition at the solution of these the various metal plating that will describe.The microsphere of this plating is useful in electronic application and catalytic treatment.As the microsphere with the outer plating of palladium is used for occlude hydrogen aspect improving the quality, and than pure palladium line or plating palladium linear rate height.Further improve being included in and use additional nickel serving on the palladium coating, and the copper coating at it under or scumbling are covered with to palladium coating increase structural integrity.
Therefore, first purpose of the present invention provides the modified form catalysis microsphere that has homogeneous thickness coating on the homogeneous non-metallic particle, granular layer comprise various in nickel coatings and the combination of palladium or similar coating thereon, and on palladium coating, scribble another kind of coating during cycle period to gain in strength when microsphere is used for catalyzed reaction hydrogen (or isotropic substance of hydrogen).
For these with hereinafter with conspicuous other purpose, the present invention describes with reference to the accompanying drawings.
Fig. 1 represents the part of one embodiment of the invention integral body.
Fig. 2 represents the part figure of another embodiment of the present invention.
My United States Patent (USP) 5,036,031 (U.S. ' 031) all is incorporated herein by reference at this.
Crosslinked polystyrene copolymer is chlorsulfonic acid and the hydrochloric acid reaction that has the crosslinked polystyrene copolymer microsphere of hydrionic sulfonated in the post exchange with the generation skin, and ' 031 is shown in Figure 1 as my United States Patent (USP).This sulfonation should be limited in 100 molecular layer degree of depth.If sulfonation is excessive, dried microsphere during by hydration the diameter of microsphere will change.Then after this reaction, with deionized water towards Xian's sulfonated polystyrene microsphere body.Next step, the hydration cupric chloride is added in this solution, and replaces hydrogen ion at skin, and ' 031 is shown in Figure 2 as my United States Patent (USP).This microsphere is also dry towards Xian with deionized water once more.The microsphere that produces has mantoquita in most external.This microsphere is divided into every batch of each batch with substantially the same size through sifting out.By the maximum fractionation after 18-20,20-25 and the screening of 25-30 purpose sieve is U.S. sieve 16-18 order.So, cut apart the oriented independent hydraulic pressure of cone of going up the stratiform current of apparatus for every kind and separate.This is known, and according to the Stoke rule, the microsphere of different densities and size can be at different layers or band.Carefully the microsphere in each band is removed respectively, formed each several part, and their density is corresponding to ± 0.005g/cm
3Then, with being coated with the copper clothing on the particle of United States Patent (USP) 3,577,324 disclosed methods with these parts.The microsphere that obtains being coated with copper as electronic component and on catalysis performance good do not produce showing tremendous enthusiasm flower when forming microsphere because they were handled in the preceding step.This showing tremendous enthusiasm spending may cause that washing loses suddenly from microsphere.
Concerning many application, second kind of washing is necessary.In order to ensure the homogeneity that applies, copper be coated with microsphere once more hydraulic pressure be separated into precision ± 0.0075g/cm
3
With United States Patent (USP) 3,577,324 disclosed devices and on copper applies, carried out second metal deposition of various metals at the solution of United States Patent (USP) ' 031 of following detailed description:
Used plating:
Gold-plated;
Silver-plated;
Platinum plating;
The plating palladium;
Nickel plating;
Used immersion plating:
The plating palladium;
Nickel plating;
Rhodanizing on copper coating;
Zinc-plated on copper coating;
Gold-plated on copper coating;
Silver-plated on copper coating;
Platinum plating on copper coating;
Used electroless plating:
Copper facing;
Nickel plating;
The plating palladium.
Except for the above-mentioned processing that forms the coating of wanting, use little electroplating method of these coating can comprise the method for vacuum-evaporation, ion plating and sputter.These additional platings are handled and all are described in fully in 365 to 375 pages " the vacuum metal sputter " that Paul R.Forant shows " metal finishing instruction and dictionary " (publication in 84 years).
The metal of catalyst cupport
Have only thin-layer metal membrane to need catalytic activity.The one group of reactive metal that produces surface-catalyzed reactions is to have that specific gravity respectively does for oneself 8.9,12,02,21.45,4.5g/cm
3Nickel (58.68), palladium (106.70), platinum (197.20), platinum (185.23), titanium (47.9).Can absorb hydrogen as palladium (Pd) surface.This absorption meeting is used as an example, to show the active improvement of metallic-coated surface on compact stabilized interpolymer microsphere.
Being coated with the palladium microsphere absorbs best to hydrogen (or isotropic substance hydrogen).But palladium also can replace with other transition metal, alkaline-earth metal and uranium.In general, can combine any metal that forms metal hydride with a large amount of hydrogen all can accept.The applicant known will be instead or with these metals of palladium bonded be lanthanum, praseodymium, cerium, titanium, zirconium, vanadium, tantalum, uranium, hafnium and thorium.The authoritative conclusion of these elements in this group is seen that B.L.Shaw institute that Pergamon distribution society in 1967 publishes is famous be " inorganic hydride " book.But, palladium is the metal hydride and the metallic hydrogen isotropic substance thing thereof of the most well known and broad research, and the patent that has been used for my reference in early stage absorbs microsphere to form conductor hydrogen.Even in more common general knowledge, providing the surface of a kind of " metal hydride " (and isotropic substance) in this topmost requirement, manufacturing of microsphere awl is will consider in second step.
The palladium of plastic microsphere applies
The copolymer microsphere body of processing 100.00 grams as described applies to produce a kind of thin copper.Show stable surface charge when being coated with copper microsphere drying.With the dry state density of United States Patent (USP) 4,196, the 618 determined microspheres of S.V.S. be 1.0550+/-0.0005g/cm
3Being used in pipe relevant with metal balance among the S.V.S. is 0.1000cm
3This microsphere is to adopt the palladium of plating, immersion plating and three kinds of paint-on techniques of electroless plating to apply.In addition, with applying for the copper coil of 100.000gm, diameter 0.05mm as the technology of microsphere equally.All microspheres and electric wire are coated with reaching the palladium that weight is 20.000 grams.
Table as a result
Palladium applies
The particle electric wire
Weight 100.00 grams 100.00 grams
Palladium weighs 20.00 grams, 20.00 grams
With g/cm
3The specific gravity that applies for the palladium of unit
Plating method E I EL
11.00 11.40 11.1
11.85 11.00 10.75
12.00 11.95 11.85
E=electroplates
I=immersion plating
The EL=electroless plating
The hydrogen load on palladium surface
As everyone knows, palladium is famous to have the hydrogen of absorption and isotopic tendency thereof.Its absorbed dose is about 800 times of itself volume when subfractionation.The Century Co.630 page or leaf referring to nineteen twenty-six James Smith that Kendall shows chemistry institute.It is following that what give is by the hydrogen of plating palladium commissure polymeric microspheres, plating palladium line and pure palladium line and the comparative result that isotropic substance absorbs thereof.
The volume of the volume/Pd of hydrogen
The pure Pd line of microsphere plating Pd line
E I EL E I EL E I EL
900 910 950 580 590 610 570
950 975 1050
The Pd of 1 volume is to the hydrogen of X volume
The special proportion that uses Pd is at 12.02gm/cm
3With the coat weight of Pd volume and the standard gas condition of hydrogen, metal volume is given with load to hydrogen volume, promptly applies Pd on the particle that accounts for microsphere volume 1.962% to 1.760%.The microsphere magnitude range is from 2mm to 10 micron.
This shows big than plating Pd line of amount that plating microsphere per unit volume Pd absorbs hydrogen, also big than pure Pd line.This improvement catalytic property that shows the washing microsphere is better than metallizing or pure metal line.Amount of metal explanation on the coating microsphere needs little metal so that the improvement that is better than pure metal reaction to be provided on microsphere, absorbs as using palladium/hydrogen in the example.
Show among Fig. 3 of relevant remarkable result ' 031 that absorbs hydrogen by palladium at United States Patent (USP).Having external diameter and be substantially the plating palladium microsphere of cross-linked polymer of 0.88mm and palladium line is placed in the hydrogen under the standard temperature and pressure (STP) condition.In the unit time shown in Figure 3 of ' 031, find that microsphere reaches maximum absorption than electric wire at United States Patent (USP) in the shorter time.Can think that the absorption that occurs in the surface is faster, and the particulate surface-area is bigger.In addition, show on particle metal plating more small property give birth to absorb fast more because hydrogen needn't deeply permeate.But, lead when being used as catalyzer in the reaction at electrochemistry or electricity when these microspheres, this scumbling is not covered electronic conductor character is had a negative impact.On the contrary, this shell metal not only makes production output improve, and has accelerated production.
Furthermore, plating palladium microsphere shows ideal hydrogen and its isotopic absorption.Other purposes of above-mentioned described various metal plating microspheres is conspicuous to using this metalloid as the people of catalyzer.Because the metal surface area to given weight and volume has reached maximum, the coating microsphere has been strengthened catalytic activity.
Referring to Fig. 1 of the application, the present invention totally is expressed as label 10.Core 12 is nonmetal and is preferably formed by my the described cross-linked styrene Vinylstyrene in United States Patent (USP) ' 031.Being determined by experiment described 16 top equal affix nickel dams following and 18 in the above provides further hydrogen to absorb catalytic effect.Use the aforementioned palladium plating microsphere that does not have plating nickel outside in experiment, these experimental results are disclosed in my the early stage United States Patent (USP) 5,318,675 and 5,372,688, the black residue that analysis is producing in liquid electrolyte, and to determine be palladium.This palladium only has a source, the palladium plating on ' the 031 microsphere particle that is United States Patent (USP).The further analysis revealed of this black residue because of charging and in the electric current of ionogen and my He ' 675, ' 688 patent battery interaction the time be applied to a kind of result of the own round-robin of heat/electric current on the palladium coating of each microsphere.This itself circulating in obviously produces tiny crackle, delaminates and/or peels off on the palladium coating.
Shown in Figure 1 the invention provides a kind of on prior to the copper plating of using the palladium plating or flash plating 14 additional in nickel plate 16.Afterwards, additional nickel plating 20 is used in the palladium plating 18, thereby has prepared the preferred embodiments of the present invention 10.
Below palladium plating 18 and above stablize palladium from structure when all having the principal benefits of additional nickel plating 16 and 20 to be to allow hydrogen freely be diffused into palladium coating 18.In He ' 675, ' 688 patent described itself, the sizable heat that produces in the palladium layer causes and expands and dwindling thereafter cycle period.For the crackle that stops the palladium layer, delaminate and/or peel off, below the palladium layer and above nickel dam increase structural integrity, and under the situation of not restraining the hydrogen diffusion, stop this injury and deterioration.
The scope of preferred layer thickness is, copper flash plating 14 is 1 to 10 dust, and interior nickel coating 16 is 10 dusts to 1 micron, and palladium coating 18 is 10 dusts to 2 micron, and the outer nickel coating 20 on palladium coating 18 is 10 dusts to 1/2 micron.
With reference to figure 2, total the representing of another overall embodiment of the present invention with label 22, and comprise the aforementioned ball-type non-metallic core 12 relevant with Fig. 1.The flash plating 24 that the conductor metal of uniform thickness applies is to be formed by meeting and the metallic cation that hydrogen carries out chemical reduction.This flash plating 24 thickness ranges are 1 to 10 dust.This flash plating 24 is to be formed by copper, palladium, nickel and titanium, is preferably copper.
On this flash plating 24, use then by nickel and form and have a second layer 26 that homogeneous thickness is 10 dusts to 1 micron.Re-use palladium coating 28 on nickel coating 26, the thickness range of palladium coating 28 is 10 dusts to 2 micron.Furthermore, this coating 28 can be formed by the metal hydride that combines with a kind of isotropic substance of aforesaid hydrogen or hydrogen easily.This metal hydride coating 28 can adopt palladium, lanthanum, praseodymium, cerium, titanium, zirconium, vanadium, tantalum, uranium, hafnium and thorium, any other a kind of combination the in preferably adopting independent palladium or palladium and this organizing.
Form the fixing coating 30 of metal that forms homogeneous thickness on the coating 28 at metal hydride again, selected this metal has high hydrogen diffusivity and low hydride rate of formation.Can being used to form fixedly, the material of coating 30 is selected from nickel, Jin Heyin, preferably nickel.Acceptable hydrogen diffusion two-forty scope is to 1 mole of about 0.85 moles of hydrogen of palladium.The molar ratio that acceptable low hydride rate of formation is metal and hydride or denteride is for less than 10: 1, or 1 mole metal is to less than 0.1 mole of hydride or denteride (reduzate).
Fixedly form the stabilized metal coating 32 of homogeneous thickness again on the coating 30 at metal.Stablizing coating 32 is to be formed by one of transition metal with two-forty hydrogen diffusibility, and can be selected from chromium, iron, cobalt and nickel, preferably chromium.Thickness is in 1 to 60 dust scope.
One or more pairs of extra plays 34/36 of palladium, or the metal hydride widely after nickel coating 36 forms coating 34, or the metal widely that has the diffusion of two-forty hydrogen and hang down the hydride rate of formation fixedly coating can supply with every kind of required special catalytic environment.Many this paired layers 34/36 can one build on another to nearly 5 to 10 pairs increase structural integrities and strengthen the extra plays that hydrogen absorbs.
Shown here and described example invention is acceptable most realistic and most preferred embodiment, simultaneously can recognize within the scope of the present invention and can change to some extent thus, this is not subjected to placing restrictions on of disclosed details, but in all scopes of claim, comprise any one and whole plant and instrument and part.
Claims (25)
1, a kind of catalyzer, it comprises:
The microsphere of a plurality of property led, each all has first nickel dam that is formed on the homogeneous thickness on the homogeneous thickness copper layer, and described copper layer forms on the non-property a led core;
The palladium layer of a homogeneous thickness that on described first nickel dam, forms, described palladium layer has high hydrogen receptivity; With
Homogeneous thickness second nickel dam that on described palladium layer, forms.
2, catalyzer as claimed in claim 1 is characterized in that:
The described non-property led core is crosslinked polystyrene.
3, catalyzer as claimed in claim 1 is characterized in that:
At least one described layer forms by electroplating.
4, catalyzer as claimed in claim 1 is characterized in that:
At least one described layer is formed by immersion plating.
5, catalyzer as claimed in claim 1 is characterized in that:
At least one described layer is formed by electroless plating.
6, catalyzer as claimed in claim 1 is characterized in that:
At least one described layer is formed by vacuum-evaporation.
7, catalyzer as claimed in claim 1 is characterized in that:
At least one described layer is formed by ion plating.
8, catalyzer as claimed in claim 1 is characterized in that:
At least one described layer is formed by splash.
9, a kind of palladium-plating catalyst with high hydrogen receptivity, it comprises:
The microsphere of a plurality of property led, diameter is unified and have the copper layer basically for each, and one first nickel dam is arranged on this copper layer again, and a palladium layer is arranged on described first nickel dam again, on described palladium layer second nickel dam is arranged again, described every layer thickness homogeneous;
Described palladium layer can absorb a large amount of hydrogen by described second nickel dam.
10, catalyzer as claimed in claim 9 is characterized in that:
Each described microsphere has the non-property a led core that is formed by crosslinked polystyrene.
11, catalyzer as claimed in claim 9 is characterized in that:
At least one outer described layer forms by electroplating.
12, catalyzer as claimed in claim 9 is characterized in that:
At least one described layer is formed by immersion plating.
13, catalyzer as claimed in claim 9 is characterized in that:
At least one described layer is formed by electroless plating.
14, catalyzer as claimed in claim 9 is characterized in that:
At least one described layer is formed by vacuum-evaporation.
15, catalyzer as claimed in claim 9 is characterized in that:
At least one described layer is formed by ion plating.
16, catalyzer as claimed in claim 9 is characterized in that:
At least one described layer is formed by splash.
17, a kind of catalyzer, it comprises:
The non-property the led core of a plurality of homogeneous, each all has the property the led metal foil coating that combines formation homogeneous thickness with the cationic chemical of the described non-property led core surfaces exchange, and described metallic cation will be used the hydrazine chemical reduction;
The nickel dam of a homogeneous thickness that on described flash plating, forms;
The metal hydride form layers of a homogeneous thickness that on described nickel dam, forms, described metal hydride form layers combines with the isotropic substance of hydrogen or hydrogen easily;
The metal immovable bed of a homogeneous thickness that on described metal hydride form layers, forms.
18, catalyzer as claimed in claim 17 further comprises:
The stabilized metal layer of a homogeneous thickness that forms on described metal immovable bed, described stabilized metal layer is a kind of transition metal.
19, catalyzer as claimed in claim 17 is characterized in that:
Described flash plating thickness range is 1 to 10 dust;
Described nickel dam and the every layer thickness scope of described metal immovable bed are 10 dusts to 1 micron;
Described metal hydride form layers thickness range is 10 dusts to 2 micron.
20, catalyzer as claimed in claim 18 is characterized in that:
Described flash plating thickness range is 1 to 10 dust;
Described nickel dam and the every layer thickness scope of described metal immovable bed are 10 dusts to 1 micron;
Described metal hydride form layers thickness range is 10 dusts to 2 micron;
Described stabilized metal layer thickness scope is 1 to 60 dust.
21, catalyzer as claimed in claim 17, it is characterized in that described flash plating by under organize metal and obtain:
Copper, palladium, nickel and titanium.
22, catalyzer as claimed in claim 17, it is characterized in that described metal hydride form layers by under organize metal and obtain:
Palladium, lanthanum, praseodymium, cerium, titanium, zirconium, vanadium, tantalum, uranium, hafnium and thorium.
23, catalyzer as claimed in claim 17, it is characterized in that described metal immovable bed by under organize metal and obtain:
Nickel, gold and silver and titanium.
24, catalyzer as claimed in claim 18, it is characterized in that described stabilized metal layer by under organize metal and obtain:
Chromium, iron, cobalt and nickel.
25, catalyzer as claimed in claim 18 is characterized in that:
Described flash plating by under organize metal and obtain:
Copper, palladium, nickel and titanium;
Described metal hydride form layers by under organize metal and obtain:
Palladium, lanthanum, praseodymium, cerium, titanium, zirconium, vanadium, tantalum, uranium, hafnium and thorium;
Described metal immovable bed by under organize metal and obtain:
Nickel, gold and silver and titanium; And
Described stabilized metal layer by under organize metal and obtain:
Chromium, iron, cobalt and nickel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96194463A CN1187222A (en) | 1995-06-05 | 1996-06-03 | Improved uniformly plated microsphere catalyst |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/462,005 | 1995-06-05 | ||
| CN96194463A CN1187222A (en) | 1995-06-05 | 1996-06-03 | Improved uniformly plated microsphere catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1187222A true CN1187222A (en) | 1998-07-08 |
Family
ID=5128650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96194463A Pending CN1187222A (en) | 1995-06-05 | 1996-06-03 | Improved uniformly plated microsphere catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1187222A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334254C (en) * | 2004-12-16 | 2007-08-29 | 四川材料与工艺研究所 | Surface treatment method for improving gas impurity poisoning resistance of lanthanide alloy |
-
1996
- 1996-06-03 CN CN96194463A patent/CN1187222A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334254C (en) * | 2004-12-16 | 2007-08-29 | 四川材料与工艺研究所 | Surface treatment method for improving gas impurity poisoning resistance of lanthanide alloy |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU697004B2 (en) | Improved uniformly plated microsphere catalyst | |
| Li et al. | Electrochemical growth of two-dimensional gold nanostructures on a thin polypyrrole film modified ITO electrode | |
| CN104691046B (en) | Surface carries metal foam body, the preparation method and use of controlled in size crystal grain | |
| US20090166209A1 (en) | Porous Battery Components Comprising Electrochemically Created Nanocatalysts | |
| JP3077113B2 (en) | Microporous fluororesin material plated with platinum group or platinum group alloy and method for producing the same | |
| US5036031A (en) | Metal plated microsphere catalyst | |
| CN1740390A (en) | Chemical plating activating process and metal depositing process therewith | |
| US9849445B2 (en) | Subnanometer to nanometer transition metal CO oxidation catalysts | |
| CN103165908A (en) | Preparation method of ordered electrode | |
| JP2007184278A (en) | Method of manufacturing conductive metal-coated particulate and its manufactured product | |
| CN110813322A (en) | Method for reversely preparing monolithic catalyst | |
| CN113274993A (en) | Preparation method of silica gel matrix chromatographic packing for separating strong-polarity drugs | |
| CN109053963A (en) | A kind of preparation method of cation polystyrene resin | |
| CN1187222A (en) | Improved uniformly plated microsphere catalyst | |
| CN108461172A (en) | Conductive particle and preparation method and application thereof | |
| CN1311104C (en) | Process for preparing nickel hydroxide material using electric deposition method | |
| CN1194031C (en) | Method for mfg. controllable structure inorganic nanoparticle/polymer composite superthin film | |
| CN102974395A (en) | Eggshell noble metal-polymer ligand catalyst and preparation method thereof | |
| CN1637169A (en) | Electroplating method for a semiconductor device | |
| CN107405604B (en) | Method for producing catalyst supporting core/shell structured catalyst particles | |
| CN1186820A (en) | High molecular composite conductive micro-balloons | |
| JP2004119072A (en) | Electrode for fuel cell | |
| EP3846599A1 (en) | Method for forming conductive thin wire, method for producing transparent conductor, method for producing device, and set of conductive ink and base material | |
| JPH02144154A (en) | Heat conductive catalytic body and production thereof | |
| JP4842025B2 (en) | Method for forming metal oxide fine particle layer on conductive substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |