US3342710A - Method of rust proofing treatment of metals - Google Patents

Method of rust proofing treatment of metals Download PDF

Info

Publication number
US3342710A
US3342710A US297513A US29751363A US3342710A US 3342710 A US3342710 A US 3342710A US 297513 A US297513 A US 297513A US 29751363 A US29751363 A US 29751363A US 3342710 A US3342710 A US 3342710A
Authority
US
United States
Prior art keywords
beryllium
lit
metal
solution
group
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.)
Expired - Lifetime
Application number
US297513A
Other languages
English (en)
Inventor
Nishigaki Susumu
Nakamura Takao
Kusaka Takeshi
Yano Takeshi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NGK Insulators Ltd
Original Assignee
NGK Insulators Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Application granted granted Critical
Publication of US3342710A publication Critical patent/US3342710A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/38—Chromatising

Definitions

  • the present invention relates to the surface treatment for providing corrosion resistance to the surface of metals.
  • a transparent and compact anti-corrosive and refractory coating can be easily provided on the surface of a desired metal without spoiling appearance of the base metal by wetting with the solution, more particularly, dipping the metal to be treated into the solution and, if necessary, by applying electrolytic treatment in parallel thereto so that it has a novel characteristic as the rust prevention of metals.
  • the specific results of the invention can be obtained by using a special treating solution which consists of a 3,342,710 iatented Sept. 19, 1957 beryllium salt added with one or more of chromates or bichromates to prepare a mixed aqueous solution having a suitable pH value by adjusting its acidity and after the surface of the metal to be treated is removed from oil and fat and cleaned by washing with acid the metal is dipped into the aqueous solution or the metal is wiped with the aqueous solution or wetted by spraying the solution, then the liquid on the surface is wiped off by rubber rolls and dried at a temperature from room temperature to 200 C.
  • a special treating solution which consists of a 3,342,710 iatented Sept. 19, 1957 beryllium salt added with one or more of chromates or bichromates to prepare a mixed aqueous solution having a suitable pH value by adjusting its acidity and after the surface of the metal to be treated is removed from oil and fat and cleaned by washing with acid the
  • FIG. 3 is a diagram showing the relation between pH of the treating solution and the rate of rust generation
  • FIG. 4 illustrates curves showing the relation between the salt water spraying time and the rate of rust generation similar to FIG. 1 when the temperature of the treating solution is taken as parameter;
  • FIG. 5 shows curves illustrating the comparative test results of conventional rust proof treating process.
  • the curves A, B, C, D and E illustrate characteristic curves showing the relation between the salt water spraying period and the rate of white rust created as the results of exepriments treated by each aqueous solution prepared according to the following compositions:
  • wetting agent or reducing agent By adding to the treating solutions of the above described compositions less than 5% of Wetting agent or reducing agent further improved uniform coating can be obtained.
  • wetting agent triethanolamine, coconut amine or stearyl propylene diarnine and their ethylene oxide added derivatives, alkanol or phenol ether type derivatives are effective since such agents improve the quality of the coating by elfecting both catalytic and surface active agents on the surface of metals.
  • reducing agents use is made of an organic reducing agent having an aldehyde group or that producing aldehyde during the reaction such as can sugar, glucose, vanillin, hexamethylenetetramine, or inorganic reducing agent such as sodium hypophosphate which gives no detrimental results even when it remains in the coating.
  • FIG. 2-(a) illustrates the effects of the addition agents, wherein The curve B illustrates the experimental results with the composition of BeSO -4H O; 6.0 g./lit. CrO 6.0 g./lit.,
  • F illustrates the result when 0.6% of hexamethylene tetramine is added to the composition of E,
  • composition E shows that when 0.6% of sodium hypophosphate is added to the composition E,
  • J is that when 0.6% of cane sugar is added similarly.
  • curves are characteristic curves illustrating the relation between the time of spraying the above salt water and the rate of creating white rust.
  • FIG. 2-(b) illustrates the relation between the addition percent and the rust creating rate checked after the lapse of time of 120 hrs. of the salt water spray test specified by I IS rule
  • I IS rule When triethanolamine and cane sugar are added respectively to the standard treating solution having the composition of BeSO -4H O 6.0 g./lit., CrO 6.0 g./lit. expressed by K and L respectively.
  • trivalent chromium may be previously added to the treating solution to provide the coating having improved rust proof nature similarly.
  • trivalent chromium salts chromium alum, chromium hydroxide, chromium sulphate and chromium nitrate, etc. may be used.
  • concentration of the trivalent chromium is taken preferably within the range of 0.1 to 10 g./lit of Cr element. Below the above range anti-corrosion property becomes poor and at a higher rate the product is colored and no transparent coating is obtained and also the anti-corrosion effect is not improved.
  • FIG. 3 illustrates the results of salt water spray tests according to 118 after the lapse of 72 hrs. when the composition of the treating solution is BeSO -4H O 6.0 g./lit., CrO 6.0 g./ lit. with different values of pH.
  • the treating solution may be used at room temperature, but when it is heated to a temperature of 40 to 70 C. it provides a coating having superior anti-corrosive property.
  • FIG. 4 shows the effect of the temperature of the treating solution by M when the temperature is room temperature and by N when the temperature is 40 C. and by P at 60 C. respectively and each rust creating rate when using the treating solution of BeSO -4H O 3.0 g./lit., CrO 3.0 g./lit.
  • dipping in the specification is to be understood to include the immersion into the solution, wiping, coating or spraying and the duration of dipping i preferably 2 to 60 seconds and the longer treatment time than this can not expect the further improved results.
  • the dipping method of the invention there is formed a coating having excellent rust proof and heat resistance on the surface of the metal to be treated containing essentially to 30% of BeO, mainly consisting of 2BeO-CrO or Cr O -2BeO-CrO and it is assumed that the coating is formed by the following reaction mechanisms
  • a treating solution having a strong acidity the coating containing a large amount of BeO can be obtained mainly according to the formula (1), and by the formula (2) when using a substantially neutral treating solution.
  • the wetting agent such as amines having the side chain of polyvalent alcohol or polyoxyethylene forms a stable chelate compound and at the same time the hydrophilic radical adheres to the surface of the treated metal to form an adherent uniform coating. Meanwhile hexavalent chromium is partly reduced to trivalent chrominum during the drying stage to provide a film having further superior anti-corrosive property.
  • a transparent and compact coating having 0.01 to 0.2;; thickness is produced without spoiling the appearance of the base metal and the rust proofing property of the film is exceedingly good and prevents rusting and decoloration of the base metal by corrosive gases and liquids, such as water vapour, sodium sulfide, hydrogen sulfide, ammonium and hydrogen chloride gases, caustic soda and the like.
  • gases and liquids such as water vapour, sodium sulfide, hydrogen sulfide, ammonium and hydrogen chloride gases, caustic soda and the like.
  • Q illustrates the result according to the treatments of chromic acid (1%), R is that of chromate treatment and S the treatment according to the invention.
  • the heat resisting (refractory) film up to 250 to 400 C. can be obtained and moreover it can be soldered, and the insulation resistance is considerably low so that it can be applied to various electrical purposes.
  • the treating solution of the invention is very dilute and the method of treatment can be simply carried out by dipping, wiping or spraying as above explained so that it has advantage from an economical point of view.
  • the rust proof treatment of the invention can be broadly applied to various purposes and it is effective in preventing rust, decoloration and improving the heat resistance for the metals such as zinc alloys, copper, copper alloys, aluminum, aluminum alloys, magnesium, magnesium alloys, cadmium, cadmium alloys, white metal, mild steel, stainless steel and the like iron and steel products, gold, silver, nickel and nickel alloys, chromium and the like metals and the plated products thereof and can be broadly and etfectively applied to general household utensils, electrical parts, machines and machine parts, gold and silver decorations, zinc plated iron plates and the like building construction materials, fixtures and the like.
  • the metals such as zinc alloys, copper, copper alloys, aluminum, aluminum alloys, magnesium, magnesium alloys, cadmium, cadmium alloys, white metal, mild steel, stainless steel and the like iron and steel products, gold, silver, nickel and nickel alloys, chromium and the like metals and the plated products thereof and can be broadly and et
  • the method of the invention can be carried out by using an aqueous solution mainly containing beryllium salts added with chromic acid, sodium bichromate, potassium bichrornate and the like chromium salts and by dipping the metal to be treated therein and by passing electric current therethrough under a definite condition with the treated metal as a cathode, thereby producing oxidized film containing anti-corrosive beryllium and chromium, which is transparent, compact and exhibits an anti-corrosive property.
  • the oxidized film coating is produced by electrolyzing an aqueous solution containing beryllium salts to discharge Be++ on the surface of the metal constituting a cathode and at a same time oxidized by the chromic acid, thereby forming the oxidized beryillium coating directly on the metal surface and its reaction is shown by the following formulas as for instance:
  • the transparent, compact and anti-corrosive coating having complex compositions such as BeO, Cr O CrO BeCrO BeCr O is formed on the surface of the metal.
  • beryllium beryllium sulfate, beryllium nitrate, beryllium halide, basic beryllium acetate, sodium tetrafluoro beryllate and the like beryllium salts are used.
  • chromate chromic acid, sodium chromate and as bichromate, sodium bichromate, potassium bichromate is added thereto to provide a mixed solution and the pH value of this solution is adjusted to 2 to 7 by using an alkali such as ammonia water or caustic soda or an acid such as sulfuric acid.
  • the metal to be treated is dipped into the aqueous solution to establish a cathode and using a lead plate, graphite plate or stainless plate and the like anti-corrosive conductive material or beryllium metal piece itself as an anode, the direct current is passed through these electrodes, then the metal thus treated is water washed and dried.
  • inorganic or organic salts of metals such as nickel, cobalt, titanium, zirconium, zinc, lead, chromium, tin, gold, silver, copper, rhodium, antimony, cadmium, aluminum, magnesium and the like is added to the above solution and electric current is passed in the similar manner as before more compact, and lustrous coating may be obtained and the anti-corrosive property can be further improved.
  • an electrolyte which does not spoil the characteristics of coating such as, sodium sulfate, and boric acid may be added, then the conductivity of the treating solution is improved and the film can be well coated.
  • the conductivity of the treating solution is improved and the film can be well coated.
  • the lustre and anti-corrosion improving agents of inorganic or organic material such as compounds of arsenic, selenium, tellurium and sulfur, gelatin, saccharin, quinoline and the like further effect can be produced and also by adding less than of wetting agent or reducing agent it enables to obtain more homogeneous coating of better quality.
  • the wetting agents are preferably coconut amine, stearyl propylene diamine and their derivatives and the like amine system and also alkanol or phenol ether type derivatives.
  • the solution is preliminary added with trivalent chromium for the purpose of electrolytic treatment, then the coating having better anti-corrosive nature can be obtained.
  • the trivalent chromium chromium alum, chromium hydroxide, chromium sulfate, chromium nitrate can be used and the concentration of the trivalent chromium is preferably 0.1 to 10 g./lit. of Cr component.
  • Arsenic, selenium, tellurium and sulfur compounds make the surface coating compact and hard and provide lustre and improve anti-corrosive nature, but more than 20% has no more improvement than that of less than 20% so that 20% is taken as a limit.
  • Gelatin, saccharin and quinoline make the surface specially smooth and increase the corrosion resistance, but more than 20% has no effect of improving further so that it was taken as a limit.
  • the prodllcts should be well washed with water and dried. The coating thus obtained increases the lustre above that of the case when beryllium salts only are used in the solution and also the corrosion resistance is superior.
  • the treating solution of the invention is deteriorated during use by the metal to be treated. Since the treating solution is deteriorated as it is used it should be always maintained within the following range of composition in order to obtain a good coating.
  • the current density of the cathode for obtaining the best coating is 0.05 ma./cm. to 10 ma./cm. and with the current density less than that a homogeneous coating can not be obtained and with the larger current density the treated surface becomes coarse so that the compact coating is diflicult to obtain.
  • the concentration of beryllium in the electrolytic treating solution is preferably 0.05 g./l. to 1.0 g./l. and with a lower concentration than this range the transparent and compact coating can not be produced so that it is not suitable and with a higher concentration the treated surface becomes rough and loses lustre.
  • the pH of the solution is best at 2 to 7 and if the pH is larger than 7 beryllium hydroxide precipitates in the treating solution so that the concentration of beryllium ion necessary in the solution can not be obtained and moreover colloidal beryllium hydroxide precipitates on the surface of the cathode. If the pH of the solution is less than 2 the metal to be treated is attacked before electric current is passed and the treating solution is deteriorated so that a good coating can not be obtained.
  • the time necessary for electrolysis depends upon the use of the articles to be treated, yet in order to improve the lustre, resistance to decoloration and corrosion the duration of 1 second to 20 minutes is preferable and more particularly in order to improve the corrosion resistance 2 to 20 minutes are preferable, yet if the electrolysis is continued longer than the above the beryllium discharged on the surface of cathode will become beryllium hydroxide to precipitate as the corroidal tate on the surface of the transparent and compact oxidized film initiary formed on' the surface, thereby disturbing the effective utilization of beryllium so that it is unsuitable.
  • the coated film showed good corrosion resistance and maintained good condition in water vapour, sodium sulfide, hydrogen sulfide, ammonia, hydrogen chloride and the like corrosive gases and moreover, it has a large advantage in that a very dilute solution of beryllium is used for the treatment at a low current density for a very short time so that the cost of treatment is very low.
  • the present anti-corrosion surface treatment is particularly effective for all articles made by zinc die-casting or galvanized iron plates and also zinc plated articles, moreover, it shows effective results which can never be attained by the other plating solution for the improvement of discoloration and corrosion resistance for all metals such as light alloy products, copper and copper alloy products, white metal, iron and steel products, copper, chromium, nickel, rhodium, gold, silver, cadmium, antimony, tin, lead and the like various plated products.
  • the beryllium may be used as a very dilute solution and chromium is sufiicient with a much less quantity than that for the chromate treating solution so that the cost is very inexpensive.
  • Example 1 Beryllium sulfate g./lit. 6.0 Chromic acid g./lit. 6.0 pH (controlled by ammonia water) .8 Temperature of the solution, C 60 Into the above mentioned treating solution were dipped a zinc plate and a cadmium plate for 5 seconds respectively, then the solution attached to the plates was squeezed by means of rubber rolls and dried at 120 C. for 5 minutes, a transparent surface coating having thickness of 0.05 was obtained. According to the salt water spray test under the specification of HS Z 2371 each of the test pieces when untreated formed rust in 5 hrs., but using that subjected to the treatment of the invention no rust was recognized after the lapse of 60 hrs.
  • Example 4 Beryllium nitrate g./lit. 4.0 Chromic acid g./lit. 6.0 Chromium alum g./lit. 4.0 pH 3.5 Temperature of the solution, C 60 Into the above mentioned treating solution was dipped a zinc plate for 5 seconds, then the liquid on the plate was shaken off and dried at 120 C. for 2 minutes, then water washed and left at room temperature. The zinc plate thus treated was applied to the salt water test of JIS Z 2371 and ascertained that entirely no white rust was created after the lapse of 120 hrs. Further the reduction of weight by dipping the sample into water for 3 months was measured and it showed that the reduction was only A; of the chromate treated zinc plate and the surface appearance has entirely no change from that before the test.
  • the sample thu treated showed no discoloration by placing in hydrogen sulfide gas for 2 hrs. or exposing it in ammonia gas for 5 hours and dipping in (5%) sodium sulfide solution for 10 minutes or, by subjecting it to the heat treatment at 300 C. for 30 minutes.
  • Example 6 Beryllium sulfate g./lit l5 Chromic acid g./lit 10 Chromium hydroxide g./lit 3 pH 3.5
  • Example 7 3.0 g. of beryllium sulfate tetrahydrate crystal, 1.0 g. of chormic acid and 3.0 g. of nickel sulfate heptahydrate crystal were dissolved in 1 lit. of water and it pH was adjusted to 5.5 with ammonia water. Into this solution was dipped a copper plate of 2.5 cm. x 4 cm. x 0.1 cm. after being defatted and washed with acid and water and electrolyzed as a cathode using lead plates as an anode with the current density of 0.2 ma./cm. for 7 minutes and after completion the plate was dried.
  • Example 8 3.0 g. beryllium sulfate tetrahydrate crystal and 2.0 g. of chromic acid were dissolved in 1 lit. of water and its pH was adjusted to 5.8 by means of ammonia water. Into this solution were dipped a sufficiently defatted, acid and water washed copper plate, brass plate and iron plate as cathodes and electrolyzed by using a lead plate as an anode with current density of 0.5 ma./cm. for 5 minutes. After the completion of the electrolysis the plates were thoroughly water washed and dried at C. for 10 minutes to yield coatings on the metal surfaces. Each sample thus treated was suspended into conc.
  • the similarly treated copper plate was heat treated in the atmosphere at 230 C. for 2 hours, then the untreated sample changed to dark brown color but the treated sample showed no change.
  • Example 9 3.0 g. of beryllium sulfate tetrahydrate crystal, 3.0 g. of sodium bichromate and 2.0 g. of nickel sulfate heptahydrate crystal were dissolved in I lit. of water and its pH was adjusted to 5.5 with ammonia water. Into this solution were dipped a thoroughly defatted, acid and water washed copper plate and a lead plate to be used as an anode and electrolytic plating was effected with current density of 0.3 ma./cm. for 7 minutes and after completion the samples were dried in the similar manner as in Example 8. The samples were dipped into sodium sulfide aqueous solution for 1 minute, then the untreated sample was changed to dark brown color, but the treated sample showed no change.
  • a method of forming a corrosion resistant coating on metal surfaces selected from the group consisting of zinc, cadmium, silver, copper, iron metal and their base metal alloys which comprises applying on the metal surface an aqueous solution consisting essentially of a beryllium salt selected from the group consisting of beryllium sulphate, beryllium nitrate, beryllium halide, basic beryllium acetate, beryllium citrate, beryllium tartrate, beryllium oxalate and sodium tetrafluoro beryllate having a beryllium ion concentration in the range of from 0.5 to 5 g./lit., at least one compound selected from the group consisting of chromic acid, chromates and bichromates having a chromium ion concentration in the range of from 0.5 to 30 g./lit., and a reducing agent selected from the group consisting of cane sugar, glucose, vanillin, hexamethylene tetramine and
  • a method of forming a corrosion resistant coating on metal surfaces selected from the group consisting of aluminum, magnesium, zinc, cadmium, silver, copper, iron metal and their base metal alloys which comprises dipping said metal into an aqueous solution consisting essentially of a beryllium salt selected from the group consisting of beryllium sulphate, beryllium nitrate, beryllium halide, basic beryllium sulphate, beryllium citrate, beryllium tartrate, beryllium oxalate and sodium tetrafiuoro beryllate having a beryllium ion concentration in the range of from 0.05 to 1.0 g./lit., at least one compound selected from the group consisting of chromic acid, chromates and bichromates having a chromium ion concentration in the range of from 0.5 to 30 g./lit., and a wetting agent selected from the group consisting of coconut amine, .triethanol amine, steary
  • aqueous solution for forming a corrosion resistant coating on metal surfaces by electrolyzing the aqueous solution which consists essentially of water, a beryllium salt selected from the group consisting of beryllium sulphate, beryllium nitrate, beryllium halide, basic beryllium acetate, beryllium citrate, beryllium tartrate, berylllll lium oxalate and sodium tetrafluoro beryllate having a beryllium ion concentration in the range of from 0.
  • aqueous solution for forming a corrosion resistant coating on metal surfaces by electrolyzing the aqueous solution which consists essentially of water, beryllium salt selected from the group consisting of beryllium sulphate, beryllium nitrate, beryllium halide, basic beryllium acetate, beryllium citrate, beryllium tartrate, beryllium oxalate and sodium tetrafiuoro beryllate having a beryllium ion concentration in the range of from 0.05 to 5 g./lit., and at least one compound selected from the group consisting of chromic acid, chromates and bichromates having a chromium ion concentration in the range of from 0.5 to g./lit., and a reducing agent selected from the group consisting of cane sugar, glucose, vanillin, hexamethylene tetramine and sodium hypophosphate present in an amount of less than 5% by weight based on the total amount of

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
US297513A 1962-07-27 1963-07-25 Method of rust proofing treatment of metals Expired - Lifetime US3342710A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP3128462 1962-07-27
JP3738362 1962-09-04
JP1553163 1963-03-27
JP2921563 1963-06-05
JP3147763 1963-06-13

Publications (1)

Publication Number Publication Date
US3342710A true US3342710A (en) 1967-09-19

Family

ID=27519720

Family Applications (1)

Application Number Title Priority Date Filing Date
US297513A Expired - Lifetime US3342710A (en) 1962-07-27 1963-07-25 Method of rust proofing treatment of metals

Country Status (3)

Country Link
US (1) US3342710A (de)
DE (1) DE1521892B1 (de)
FR (1) FR1439830A (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3484343A (en) * 1964-07-13 1969-12-16 Toyo Kohan Co Ltd Amine solution treatment of cathodically chromated metal surfaces
JPS5010736A (de) * 1973-06-05 1975-02-04
US20070023104A1 (en) * 2004-03-03 2007-02-01 Dipsol Chemicals Co., Ltd. Agent for reducing conversion film overall friction coefficient for trivalent chromate treating solution, trivalent chromate treating solution and method for production thereof, and trivalent chromate conversion film reduced in overall friction coefficient and method for production thereof
US20120020047A1 (en) * 2008-10-13 2012-01-26 Christian Wunderlich Method for improving the adhesion between silver surfaces and resin materials
US20160298330A1 (en) * 2015-04-10 2016-10-13 Kenneth Kyle Friesen Preventing corrosion in a greenhouse

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2733199A (en) * 1956-01-31 Electrolytic treatment of metal
US2746915A (en) * 1951-10-15 1956-05-22 Autoyre Co Inc Electrolytic metal treatment and article
US2868679A (en) * 1955-12-05 1959-01-13 Turco Products Inc Process and compositions for producing aluminum surface conversion coatings
US2998361A (en) * 1958-06-11 1961-08-29 Toyo Kohan Co Ltd Electrochemical treatment of metal surfaces and the products thereof
US3084111A (en) * 1958-04-24 1963-04-02 Dehydag Gmbh Wetting agents for electroplating baths

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2733199A (en) * 1956-01-31 Electrolytic treatment of metal
US2746915A (en) * 1951-10-15 1956-05-22 Autoyre Co Inc Electrolytic metal treatment and article
US2868679A (en) * 1955-12-05 1959-01-13 Turco Products Inc Process and compositions for producing aluminum surface conversion coatings
US3084111A (en) * 1958-04-24 1963-04-02 Dehydag Gmbh Wetting agents for electroplating baths
US2998361A (en) * 1958-06-11 1961-08-29 Toyo Kohan Co Ltd Electrochemical treatment of metal surfaces and the products thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3484343A (en) * 1964-07-13 1969-12-16 Toyo Kohan Co Ltd Amine solution treatment of cathodically chromated metal surfaces
JPS5010736A (de) * 1973-06-05 1975-02-04
JPS5332350B2 (de) * 1973-06-05 1978-09-07
US20070023104A1 (en) * 2004-03-03 2007-02-01 Dipsol Chemicals Co., Ltd. Agent for reducing conversion film overall friction coefficient for trivalent chromate treating solution, trivalent chromate treating solution and method for production thereof, and trivalent chromate conversion film reduced in overall friction coefficient and method for production thereof
US20120020047A1 (en) * 2008-10-13 2012-01-26 Christian Wunderlich Method for improving the adhesion between silver surfaces and resin materials
US8819930B2 (en) * 2008-10-13 2014-09-02 Atotech Deutschland Gmbh Method for improving the adhesion between silver surfaces and resin materials
US20160298330A1 (en) * 2015-04-10 2016-10-13 Kenneth Kyle Friesen Preventing corrosion in a greenhouse
US10718109B2 (en) * 2015-04-10 2020-07-21 Kenneth Kyle Friesen Preventing corrosion in a greenhouse

Also Published As

Publication number Publication date
FR1439830A (fr) 1966-05-27
DE1521892B1 (de) 1970-10-01

Similar Documents

Publication Publication Date Title
US4419199A (en) Process for phosphatizing metals
US4062737A (en) Electrodeposition of chromium
BR112013027921B1 (pt) Banho de galvanização e método eletrodeposição de uma camada de cromo escuro em uma peça de trabalho
DE2638305A1 (de) Verfahren und mittel zur chemischen oberflaechenausruestung von metallen
JP2604387B2 (ja) 金属表面にリン酸塩皮膜を形成する方法
US2121574A (en) Art of coating zinc
EP0140564A2 (de) Elektroplattierte Produkte und Verfahren zu deren Herstellung
US2159510A (en) Method of coating copper or its alloys with tin
US3342710A (en) Method of rust proofing treatment of metals
US4935111A (en) Method for producing black colored steel strip
US1827204A (en) Method of protecting metal surfaces
US3843430A (en) Chromate-free bright dip for zinc and cadmium surfaces
US3511759A (en) Method and electrolytes for electro-depositing black chromium
US1798218A (en) Coating and coloring metals
US3449222A (en) Metal coating process
US2499231A (en) Method of producing surface conversion coatings on zinc
JPS60190588A (ja) 亜鉛または亜鉛合金めつき鋼板の黒色処理方法
US4591416A (en) Chromate composition and process for treating zinc-nickel alloys
US3729392A (en) Plating of titanium with chromium
US2769774A (en) Electrodeposition method
US2437441A (en) Coloring metal surfaces
US2762731A (en) Method of and materials for producing paint bonding films on ferriferous metal surfaces
US3257295A (en) Method of chemically treating metals
US3647650A (en) Method of treating tin plate or galvanized sheet
US3346404A (en) Chemical plating process