Abstract:
Cross-linked polymer microspheres are carefully separated into fractions of equal size and density by first using sieves and then using hydraulic separation in a cone. Each fraction is separately plated with copper. The copper plated microspheres are again separated into fractions of equal size and density. Each fraction is then given an additional metal plating. The thus plated microspheres have uniformly thick plating 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 exhibit a marked improvement in the adsorption of hydrogen both quantitatively and in rapidity.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention relates generally to metal plating and more particularly to improved an process for the uniform plating of microspheres for use in catalytic processes and electrical applications. 
     2.Description of Related Art 
     In U.S. Pat. No. 3,577,324, I described a process and apparatus for plating particles which had as a preferred embodiment the plating of polymeric beads formed from polystyrene cross-linked with divinyl benzene. A solution for bonding copper atoms to such beads was disclosed. 
     In U.S. Pat. No. 3,787,718, I disclosed the use of plated spherical particles as electronic components. In this patent the forming of additional coatings or platings on the copper layer was also disclosed. 
     U.S. Pat. No. 2,915,406, Rhoda et al., entitled &#34;Palladium Plating by Chemical Reduction, discloses a number of baths for use in immersion plating of various metals. 
     The present invention discloses the preparation of resin microspheres having copper salts on the outer portion. These microspheres are separated into batches of substantially uniform sizes and are then plated. By plating microspheres of the same size and density (as determined by Stoke&#39;s law) a plating of uniform thickness can be achieved. This uniformly thick plating is essential when the plated microspheres are used in catalytic beds and/or with electric current flowing. Nonuniformly thick platings will result in hot spots which will cause the plating to spall off. 
     SUMMARY OF THE INVENTION 
     In a column exchange, a resin in hydrogen form is reacted with chlorosulfonic acid, the resulting microspheres have a sulfonate surface and hydrochloric acid is contained in the solution. The microspheres are washed with deionized water. The sulfonated microspheres are next placed in an aqueous copper chloride solution. The microspheres have copper salts on the surface and hydrochloric acid is contained in the solution. The microspheres are again washed with deionized water. The resulting resin when dried is in the form of microspheres having copper salts on the exterior. These microspheres are separated by passing them through meshes of progressively decreasing size beginning with U.S. sieve cut 16-18 and ending with U.S. sieve cut 25-30. Each such separated group of microspheres is further hydraulically separated to obtain microspheres of sizes identical to ±0.005 g/cm 3 . These microspheres are then plated with the electroless copper plating solution described in U.S. Pat. No. 3,577,324 with the required good agitation. After drying and further sorting, these microspheres are given an additional metal plating using the apparatus disclosed in the previously mentioned patent and solutions which will be described herein for various metal platings. Such plated microspheres are useful in electrical applications and in catalytic processes. For example, microspheres having a palladium outer plate have been found to occlude hydrogen in increased quantities and at faster rates than pure palladium wire or palladium plated wire. 
     It is therefore an object of this invention to provide a process for producing microspheres which have a plating of uniform thickness. 
     It is also an object of this invention to provide solutions and processes for achieving the metal plating. 
     In accordance with these and other objects, which will become apparent hereafter, the instant invention will now be described with reference to the accompanying drawings. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 1 depicts the reaction to produce sulfonated cross-linked polymer microspheres. 
     FIG. 2 depicts the reaction to produce cross-linked polymer microspheres having surface copper salts. 
     FIG. 3 is a graph showing relative times for total adsorption of hydrogen by palladium coated microspheres and palladium wire. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Polystyrene resin is reacted in a column exchange with chlorosulfonic acid yielding sulfonated polystyrene microspheres having hydrogen ions on the outer layer and hydrochloric acid, as shown in FIG. 1. This sulfonation should be limited to a 100 molecular layer depth. If sulfonation is excessive it will be found that the diameter of the microspheres will change when dry microspheres are hydrated. Following this reaction, the sulfonated polystyrene microspheres are washed with deionized water. Next aqueous copper chloride is added to the solution and substitutes for the hydrogen ions in the outer layer, as shown in FIG. 2. The microspheres are again washed with deionized water and dried. The resulting microspheres have copper salts on the exterior. The microspheres are passed through sieves to separate them into batches with each batch containing microspheres of substantially the same size. The largest cut is U.S. Sieve 16-18, followed by 18-20, 20-25 and 25-30 mesh. Each cut is then individually hydraulically separated in a cone having an upwardly laminar water flow. As is well known, in accordance with Stoke&#39;s law, microspheres of different densities and size will be found in different layers or zones . The microspheres in each zone are carefully removed separately and are now in fractions which are identical to +0.005 grams/cm 3 . These fractions are then copper coated using the process disclosed in U.S. Pat. No. 3,577,324. The resulting copper coated microspheres perform superiorly as electronic components and in catalytic functions because they do not develop hot spots as occurred with microspheres formed by the previous process. Such hot spots would cause the metal coating to pop off the microspheres. 
     For many applications a second metal coating is desired. To assure uniformity of coating, the copper coated microspheres are again hydraulically separated to an accuracy of ±0.0075 grams/cm 3   
     Second metal platings of various metals have been performed using the apparatus disclosed in U.S. Pat. No. 3,577,324 and the solutions which will now be described. 
     
         ______________________________________ELECTROPLATINGGOLD PLATING______________________________________Solution:   potassium gold cyanide KAu(CN).sub.2                        8-16    g/l   fluid potassium cyanide KCN                        23-39   ml/l   potassium carbonate K.sub.2 CO.sub.3                        31-94   ml/l   hydropotassium cyanide HKCO.sub.3                        23-39   ml/l______________________________________ This solution is used at a temperature of 130-160 degrees F. with a voltage of 2-5 volts DC and a current density 1-5 amp/ft.sup.2 with a good upflow and agitation. The resulting plated microspheres have a smooth surface. If a heavy porous surface is desired, the polarity shown in the previously referred to patent is reversed and carbon electrodes in nylon bag covers are used with a current density of 10 amp/ft.sup.2. 
    
     
         ______________________________________SILVER PLATING______________________________________Solution:  silver cyanide AgCN                        4-5.5 ml/l      potassium cyanide KCN                        78-94 ml/l______________________________________ 
    
     This solution is used at a temperature of 70-85 degrees voltage of 4-6 volts DC and a current density of 15-25 amp/ft 2 . The resulting plated microspheres have a smooth surface. 
     A heavy silver plate requires different parameters and solution. 
     
         ______________________________________Solution: silver cyanide AgCN                        37.5   ml/l     potassium cyanide KCN                        62.5   ml/l     potassium carbonate K.sub.2 CO.sub.3                        15.6   ml/l     silver metal Ag    27.3   g/l______________________________________ 
    
     This solution is used at a temperature of 70-80 degrees with a voltage of 4-6 volts DC and a current density of 5-15 amp/ft 2 . 
     
         ______________________________________PLATINUM PLATING______________________________________Solution:   chloroplatinic acid H.sub.2 PtCl.sub.6                          1-2 g/l   dibasic ammonia phosphate (NH.sub.4).sub.2 PO.sub.4                          20 g/l   dibasic sodium phosphate Na.sub.2 HPO.sub.4                          100 g/l______________________________________ 
    
     This solution is used at a temperature of 65-95 degrees F. with a rent density of 2-20 amp/ft 2 . A rate of deposition of 4.8 mg/amp/min is achieved or 0.0001 inches/30-60 min/ft 2 . The platinum may be plated over nickel. 
     
         ______________________________________PALLADIUM PLATING______________________________________Solution:  palladium chloride PdCl                        50 g/l      ammonium chloride NH.sub.4 Cl                        50 g/l______________________________________ 
    
     This solution is used at a temperature of 40-50 degrees C. with a current density of up to 10 amps/ft 2 . Note that the voltage should be kept below 1.8 volts DC which is below H 2  production so that the metal surface will not pre-adsorb or occlude hydrogen. A rate of deposition of 33 mg/amp min or 0.000 inches/15 min/ft 2 . The plated surface is a very active polymerization surface so that monomers should be kept away. One volume of palladium will adsorb up to 900 volumes of hydrogen. The palladium can be deposited over nickel. 
     
         ______________________________________NICKEL PLATING______________________________________Solution: nickel sulfate NiSO.sub.4                         156 ml/l     ammonium chloride NH.sub.4 Cl                         31 ml/l     boric acid H.sub.3 BO.sub.3                         31 ml/l______________________________________ 
    
     This is used at a temperature of 20-30 degrees C. with a voltage 6-8 volts DC, and a current density of 5-10 amp/ft 2 . 
     
         ______________________________________IMMERSION PLATINGPALLADIUM PLATING______________________________________Solution:  palladium chloride PdCl                        4.9    g/l      hydrochloric acid HCL                        250    ml/l______________________________________ 
    
     This solution is used at room temperature. This coating is porous and can be sealed by a solution of 1 part ammonia to two parts water. 
     
         ______________________________________NICKEL PLATING______________________________________Solution:   nickel sulfate NiSO.sub.4                          62.5 ml/l   nickel ammonium sulfate Ni(NH.sub.4)SO.sub.4                          62.5 ml/l   sodium thiosulfate Na.sub.2 S.sub.2 O.sub.3                          62.5 ml/l______________________________________ 
    
     This solution was used at room temperature (20-30 degrees C.). 
     
         ______________________________________RHODIUM ON COPPER PLATING______________________________________Solution:  rhodium chloride RhCl                        4.9    g/l      hydrochloric acid HCl                        250    ml/l______________________________________ 
    
     This solution was used at room temperature in immersion plating. 
     
         ______________________________________TIN ON COPPER PLATING______________________________________Solution:  tin chloride SnCl 19.5 ml/l      sodium cyanide NaCN                        195 ml/l      sodium hydroxide NaOH                        23.4 ml/l______________________________________ 
    
     This solution was used at room temperature in immersion plating. 
     
         ______________________________________GOLD ON COPPER PLATING______________________________________Solution:   67% potassium gold cyanide KAuCN                          3.9 ml/l   sodium cyanide NaCN    31 ml/l   soda ash NaCO.sub.3    39 ml/l______________________________________ 
    
     This solution was used at 150-180 degrees F. in immersion plating. 
     
         ______________________________________SILVER ON COPPER PLATING______________________________________Solution: silver nitrate AgNO.sub.3                         7.8 ml/l     ammonia hydroxide NH.sub.4 OH                         78 ml/l     sodium thiosulfate Na.sub.2 S.sub.2 O.sub.3                         109 ml/l______________________________________ 
    
     This solution was used at room temperature in immersion plating. 
     
         ______________________________________PLATINUM ON COPPER PLATING______________________________________Solution:  platinum chloride PtCl                        4.9    g/l      hydrochloric acid HCl                        250    ml/l______________________________________ 
    
     This solution was used at 150 degrees F. in immersion plating. 
     ELECTROLESS PLATING 
     Electroless plating in accordance with the teachings of U.S. Pat. No. 2,874,072 has been performed as will now be described. 
     
         ______________________________________COPPER PLATING______________________________________Solution: copper nitrate Cu(NO.sub.3).sub.2                        15     g/l     sodium carbonate NaCO.sub.3                        10     g/l     rochelle salts     30     g/l     sodium hydroxide NaOH                        20     g/l     37% formaldehyde   100    ml/l______________________________________ 
    
     PH 11.5, temperature 75 degrees F., 0.1 mil/hr 
     A high speed, one shot bath coating of copper has been performed. 
     
         ______________________________________Solution:  copper sulfate CuSO.sub.4                         29 g/l      sodium carbonate Na.sub.2 CO.sub.3                         25 g/l      rochelle salts     140 g/l      versene &#34;T&#34;        17 g/l      sodium hydroxide NaOH                         40 g/l      37% formaldehyde   150 g/l______________________________________ 
    
     PH 11.5, Temperature 70 degrees C., 0.8 mil/hour 
     
         ______________________________________NICKEL PLATING______________________________________Solution: nickel chloride NiCl 30 g/l     ammonium chloride NH.sub.4 Cl                          50 g/l     sodium citrate Na Cit                          100 g/l     sodium hydrophosphate NaHPO.sub.4                          10 g/l______________________________________ 
    
     PH 10, Temperature 190 degrees F. adjust PH with NH OH constantly, 0.3 mil/hr. 
     
         ______________________________________PALLADIUM PLATING                Still Moving______________________________________Solution:   tetramine palladium chloride                      5.4     7.5 g/l   disodium EDTA      33.6    8.0 g/l   hydrazine          0.3   ammonium hydroxide NH.sub.4 OH                      350     280 g/l   temperature        175     95° F.______________________________________ 
    
     CATALYTIC SUPPORTED METALS 
     Only thin metal films are required for catalytic activity. One of the active metal groups for producing surface catalytic reactions is the nickel (58.69), palladium (106.70), white gold (197.20), platinum (195.23) with specific gravities of 8.9, 12.02, 21.45 g/cm 3 , respectively. For example, palladium (Pd) surface will adsorb hydrogen gas. This adsorption will be used as an example to show an improvement in surface activity of metals coated on small stable plastic spheres. 
     PALLADIUM COATING OF PLASTIC SPHERES 
     100.000 grams of plastic microspheres were treated as described to produce a flash copper coating. The copper coated microspheres when dry exhibit a static surface charge. Density of microspheres as determined by S.V.S., U.S. Pat. No. 4,196,618 was 1.0550+/-0.0005 gm/cm 3  dry. A 0.1000 gm 3  tube was used in S.V.S. in conjunction with a Metler analytical balance. The microspheres were coated with palladium using three coating techniques, electroplating, immersion plating and electroless plating. In addition, coils of 100.000 gm, 0.05 mm diameter copper wire were coated using the same technique as the microspheres. All microspheres and wire were coated to give a weight of 20.000 grams of palladium. 
     
                       TABLE OF RESULTS______________________________________PALLADIUM COATING______________________________________         BEADS      WIRE______________________________________WEIGHT        100.00 grams                    100.00 gramsWEIGHT Pd      20.00 grams                     20.00 grams______________________________________SPECIFIC GRAVITY OF Pd COATING IN GRAMS/CM.sup.3PLATING  E       I       EL    E     I     EL______________________________________    11.99   11.40   11.1  12.00 11.95 11.85    11.85   11.00   10.75______________________________________ E = ELECTRODEPOSITION I = IMMERSION EL = ELECTROLESS 
    
     HYDROGEN LOADING OR Pd SURFACES 
     As is well known, palladium in noted for its tendency to absorb hydrogen. When finely divided, it takes up about 800 its own volume. See Smith&#39;s College Chemistry by James Kendall, The Century Co., 1926, at page 630. Given below are comparative results of adsorption of hydrogen by palladium plated cross-linked polymer microspheres, palladium plated wire and pure palladium wire. 
     
         ______________________________________VOLUMES OF HYDROGEN/VOLUME OF PdMICROSPHERES Pd PLATED WIRE PURE Pd WIREE     I      EL      E     I    EL    E    I    EL______________________________________900   910     950    580   590  610        570950   975    1050______________________________________ 
    
     1 volume Pd to × volumes hydrogen 
     Using specific gravity of Pd at 12.02 gm/cm 3  and coating weight for Pd volume and standard gas conditions for hydrogen, a volume of metal to volume of hydrogen is given as loading, i.e. where the Pd coating on the beads range from 1.962 to 1.760% of the microsphere volume. 
     Microspheres range in size from 2 mm to 10 microns. 
     It is seen that the plated microspheres take up a large volume of hydrogen per unit volume of Pd than either plated wire or pure Pd wire. This shows the improved catalytic nature of metal coated microspheres over plated or pure metal wire. The volume of metal on plated microspheres shows that considerably less metal is required on the microsphere to give improved reactions over the pure metal. Using the Pd - hydrogen up take as the example. 
     Extension of the metal coating bead catalytic effects can be extended to cover the isotopes of the reactions shown. See U.S. Pat. No. 3,632,496, where the reactor of FIG. 2 has isolated contact electrodes with an applied electrical potential across the catalyst. Bead bed is Pd/ Hydrogen. 
     A remarkable result relating to the adsorption of hydrogen by palladium is depicted in FIG. 3. Palladium plated cross-linked polymer microspheres having an outside diameter of essentially 0.8 mm and palladium wire were exposed to hydrogen under standard conditions of temperature and pressure. In unit periods of time as shown in FIG. 3, the microspheres are found to reach maximum uptake in a much shorter period than the wire. It is believed that the adsorption occurs more rapidly on the surface and the beads present a much higher surface area. In addition, it appears that the thinner the metal plate on the beads, the more rapidly the adsorption occurs, since the hydrogen does not have to penetrate deeply. Moreover, this thin coating does not adversely effect the electrical conduction properties when these microspheres are used as a catalyst in electrochemical or electro induced reactions. Consequently, the shell metal not only produces a greater product yield, but also produces it faster. 
     Based on the foregoing, the palladium coated microspheres represent an ideal adsorber for hydrogen and its isotopes. Other uses for the plated microspheres of the various metals described above will be apparent to those who typically use such metals as catalysts. The plated microspheres provide enhanced catalytic activity because the surface area is maximized for the weight and volume of the metal. 
     While the instant invention has been shown and described herein in what is conceived to be the most practical and preferred embodiment, it is recognized that departures may be made therefrom within the scope of the invention, which is therefore not to be limited to the details disclosed herein, but is too be afforded the full scope of the claims so as to embrace any and all equivalent apparatus and articles.