US3645895A - Sodium chlorate compositions of reduced fire hazard containing an alkali metal silicate fire retardant - Google Patents

Sodium chlorate compositions of reduced fire hazard containing an alkali metal silicate fire retardant Download PDF

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Publication number
US3645895A
US3645895A US697637A US3645895DA US3645895A US 3645895 A US3645895 A US 3645895A US 697637 A US697637 A US 697637A US 3645895D A US3645895D A US 3645895DA US 3645895 A US3645895 A US 3645895A
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Prior art keywords
chlorate
sodium
alkali metal
additive
silicate
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US697637A
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English (en)
Inventor
John A Peterson
Albert H Ross
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Occidental Chemical Corp
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Hooker Chemical Corp
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Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE APRIL 1, 1982. Assignors: HOOKER CHEMICALS & PLASTICS CORP.
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23H—WORKING OF METAL BY THE ACTION OF A HIGH CONCENTRATION OF ELECTRIC CURRENT ON A WORKPIECE USING AN ELECTRODE WHICH TAKES THE PLACE OF A TOOL; SUCH WORKING COMBINED WITH OTHER FORMS OF WORKING OF METAL
    • B23H3/00—Electrochemical machining, i.e. removing metal by passing current between an electrode and a workpiece in the presence of an electrolyte
    • B23H3/08—Working media

Definitions

  • compositions of matter containing an alkali metal or ammonium chlorate (preferably sodium chlorate), an alkali metal silicate and optionally other inorganic compounds.
  • alkali metal or ammonium chlorate preferably sodium chlorate
  • alkali metal silicate preferably sodium chlorate
  • optionally other inorganic compounds preferably organic compounds
  • These compositions find utility in the field of agricultural chemistry as soil sterilizers, defoliants, and weed killers.
  • These compositions also have utility as electrolytes for use in electrochemical machining and grinding operations.
  • the compositions are especially useful because of their flame retardant properties.
  • Alkali metal and ammonium chlorates are ideal electrolytes for use in electrochemical machining operations.
  • the major problem attending their use resides in their tendency to rapidly oxidize combustible materials.
  • the advantages and problems residing in the use of chlorates as the electrolyte in electrochemical machining operations are summarized in the article appearing in Metal Progress, March 1967, pp. 81-84. For example, when some of the chlorate containing electrolyte comes into contact with the clothing of the operator, or any combustible material near an electrochemical machining operation, the tendency to initiate fire is great after the wetted material has dried.
  • electrochemical machining operations it is intended to include those operations by which a workpiece is machined, milled, or ground so that the metal is removed by an electrochemical process to produce shaped or curved structures. These operations also include the production of smooth flat surfaces and the formation of holes in a workpiece.
  • the workpiece to be shaped functions as the anode in electrically conducting relationship with the cathode die through a suitable electrolyte. Metal is dissolved from the workpiece anode.
  • the selection of the electrolyte is based upon its conducting properties, its tendency to attack the electrodes, its performance in electrochemical machining operations and its cost.
  • Comstock mentions the rusting of a workpiece and its prevention through the use of a rust inhibiting agent as the electrolyte.
  • Sodium chlorate is an excellent electrolyte for electrochemical machining operations.
  • Sodium chlorate solutions used as the electrolyte in electrochemical machining are typically aqueous solutions containing about 350 g./1 .NaClO Solutions containing from about 300 to 400 grams per liter NaClO are typical examples of efficient electrolytic solutions.
  • the used electrolyte solutions usually of pH above about 6 to 7, contain precipitated hydroxides of the metal removed from the workpiece. For example, where the workpiece contains iron, nickel or chromium, the corresponding iron, nickel or chromium hydroxides are formed.
  • any flame retardant additive will have to function in the presence of at least low concentrations of dissolved CrO; ions. It is also important that any additive must not change the characteristics of sodium chlorate in its operation as an electrolyte. However, it is most desirable that an additive both act as a flame retardant and improve the properties of sodium chlorate as an electrolyte.
  • alkali metal chlorates have been used as defoliauts (especially for cotton), Weed killers, soil sterilizers, insecticides and as seed disinfectants.
  • One of the major drawbacks to the use of chlorates as agricultural chemicals resides in the problem of its flammability when dried in contact with organic matter such as the workers clothing.
  • additives such as an alkali metal silicate alone or in conjunction with a co-additive for the chlorate solutions used in agricultural applications obviates this objection to the use of chlorates and broadens the field for uses of chlorates at concentrations heretofore considered too dangerous for handling by the layman.
  • compositions of matter containing a major proportion alkali metal chlorate in combination with one or more additives the latter functioning as flame retarding agents when said compositions are deposited in a dry state upon combustible organic materials.
  • an alkali metal silicate when dissolved in a solution with an alkali metal or ammonium chlorate, will act as a flame retardant when the solution is dried on a combustible material.
  • the ratio of Si0 to chlorate may vary from 1:4 to about 1:40 on a dry weight basis.
  • the preferred ratio of Na SiO to NaClO is between 1:4 and 1:10 on a dry weight basis. In an electrolytic solution, this ratio represents, for a solution containing between about 300 to 400 grams per liter NaClO from about 7-75 grams of SiO (as a soluble silicate) per liter and preferably between about 15 to 50 grams Si0 per liter.
  • the preferred silicate additive for chlorate containing solutions employed as electrochemical machining or grinding electrolytes is sodium metasilicate (Na SiO which may be added either as the anhydrous salt or as a hydrate such as the nona-hydrate (Na SiO .9H O).
  • silicates such as the disilicate (Na Si O and tetrasilicate (Na Si O commonly referred to as water glass may be employed as the fire retardant additive for various chlorate containing compositions.
  • sodium metasilicate is preferred to silicates of lower Na/Si ratios such as water glass because the tendency of the latter silicates is to deposit hydrous SiO from solution in the presence of chlorate.
  • Co-additives which may be advantageously employed in conjunction with the silicate additive are alkali metal or ammonium chromates, carbonates hydroxides, phosphates, sulfates, and borates. These co-additives are effectively present in an amount between 10 and 80 grams per liter of solution in the use of chlorate-silicate solutions as the electrolyte for electrochemical machining and grinding operations.
  • the ratio of silicate, expressed as SiO and independently the coadditive to chlorate may be 1:440, while a more preferred ratio is about l025 parts of sodium metasilicate to from about 4l0 parts of sodium metaborate for every 100 parts of sodium chlorate and the most preferred ratio is 2:1:16 sodium metasilicate to sodium metaborate to sodium chlorate.
  • Exemplary mixtures containing sodium chromate as the co-additive are those containing on a dry weight basis a mixture of about l0-25 parts of sodium metasilicate and from about 10 to parts of sodium chromate for every 100 parts of sodium chlorate.
  • the most preferred mixture containing sodium chromate as the co-additive is 12118 sodium metasilicate to sodium chromate to sodium chlorate.
  • the most preferred aqueous solutions of electrolyte for electrochemical machining operations are those containing from 300 to 400 grams sodium chlorate per liter and from to 100 grams sodium metasilicate per liter; or 30 to 100 grams sodium metasilicate per liter in combination with from about 12-40 grams per liter sodium metaborate; or from about 30-100 grams per liter sodium metasilicate in combination with about 30-80 grams per liter sodium chromate.
  • an aqueous solution containing between about 300 to 400 grams per liter of sodium chlorate and up to about 100 grams per liter of sodium metasilicate is alkaline in pH, it is desirable to include an appropriate amount of NaOH whenever an acidic co-additive such as borax (Na B O sodium pentaborate (Na B O or Na HPO is used. If NaOH is not employed in conjunction with acidic co-additives, the pH drop of the electrolyte solution causes hydrolysis of the silicate and precipitation of hydrous SiO-
  • the alkali metal silicate additives alone are very effective flame retardant additives for chlorate induced combustion of organic materials in many applications.
  • the alkali metal silicates are extremely effective flame retardants for chlorate induced combustion. In the presence of trace amounts of chromate ions, the effectiveness of an alkali metal silicate as a flame retardant is somewhat diminished although it is still adequate to provide the degree of protection needed for the machine operator. However, the introduction of a co-additive in conjunction with the silicate, will produce a silicate based additive which is more effective than silicate alone under the conditions of low humidity, the presence of trace chromate and a large ignition source. The silicate based additives are superior to most other additive systems tested.
  • Such supporting electrolytes may be NaCl, NaBr, NaF, NaNO etc.
  • chromate is referred to in the specification as a co-additive, it is intended to include Na CrO or sodium dichromate or chromic acid in the presence of suflicient NaOH to produce chromate in situ via the reaction:
  • Examples I-XVI represents specific embodiments of this invention. They represent applicable additive concentration levels which will produce the desired result.
  • the minimum operable concentration of the flame retardant additives is desirable because excessive concentrations may cause inferior performance of the chlorate solution as electrolyte in an electrochemical machining or grinding operation.
  • the metal based silicate flame retardant additives of this in addition 0f both sodium metasilicate and sodium metavention when employed in conjunction with chlorate as horate exemplified in Examples 13 and 14 demonstrates an electrochemical grinding or machining electrolyte prefllfi higher degree of flame l'etafdallcy attending the use sent no deleterious efiect in the actual grinding or machinof a co-additive with the silicate.
  • alkali metal silicate based flame retardant additives of th1s Having disclosed the invention, it i be apparent to invention perform the Same function and may be used those skilled in the art that obvious modifications may be in substantially the same amounts as illustrated for chromade, For example, in any of the disclosed combinations mate and metaborate to achieve substantially the same f additives f c o the amount f silicate plus results. additive present may be increased without deleterious EXAMP XVII effects.
  • the minimum amount of the flame retardant additive or additives is the critical factor to be considered in The So described in EXtIIIlP16S 13 and 14 in the most applications because of possible deleterious effects preceding table was cha ged t the TESBIIVOiT of an f that may impair the function of the chlorate as an electrochemical gn'llding machine
  • the grinmflg wheel (1 F chemical machining electrolyte.
  • a composition of matter comprising a member se- The feed rate of the workpiece into the grinding wheel lected from the group consistlng of an alkali metal chlowas varied when necessary to maintain a light load on the rate, ammonium chlorate and mixtures thereof, and a grinding wheel drive motor.
  • the power input to the drive flame retardant proportion of a member selected from the motor was kept at about 10 percent of the load theoretigroup consisting of an alkali metal sihcate and hydrates cally needed to cut the metal workpiece by abrasion alone. thereof, in which the silicate, expressed as S10 to chlo- Therefore, practically all of the metal removal was due rate weight ratio is between about 1:4 to 1:40'.
  • composition of claim 1 in which sodium metasilicate and sodium chlorate appear in the weight ratio of about 1:4 to 1:10.
  • a composition of matter comprising a member selected from the group consisting of an alkali metal chlorate, ammonium chlorate and mixtures thereof; a flame retarding proportion of a member selected from the group consisting of an alkali metal silicate and hydrates thereof; and a flame retarding proportion of a co-additive selected from the group consisting of an alkali metal chromate, borate, carbonate, phosphate, sulfate, hydroxide, ammonium analogs thereof, hydrates thereof and mixtures thereof, in which the silicate, expressed as SiO co-additive and chlorate are in the weight ratio of 1:1:4-40.
  • composition of claim 3 comprising about 10-25 parts of sodium metasilicate, and about 4-10 parts of sodium metaborate to each 100 parts of sodium chlorate.
  • composition of claim 3 in which the weight ratio of sodium metasilicate to sodium metaborate to sodium chlorate is about 211216.
  • composition of claim 3' comprising about 10-25 parts of sodium metasilicate and about 10-20 parts of sodium chromate to each 100 parts of sodium chlorate.
  • composition of claim 3 in which the weight ratio of sodium metasilicate to sodium chromate to sodium chlorate is about 1:118.
  • aqueous solution of an electrolyte comprising from about 300 to about 400 grams per liter of a member selected from the group consisting of an alkali metal chlorate, ammonium chlorate and mixtures thereof; about 7 to about 75 grams per liter of an alkali metal silicate, expressed as SiO and from 10 to about 80 grams per liter of a co-additive selected from the group consisting of an alkali metal chromate, borate, carbonate, phosphate, sulfate, hydroxide, the ammonium analogs thereof and mixtures thereof.
  • the solution of claim 9 which contains from about 30-100 grams per liter of sodium metasilicate and from about 12-40 grams per liter of co-additive sodium metaborate.
  • a method of retarding chlorate induced combustion of organic material which comprises incorporating into aqueous solutions containing the chlorate ion, a flame retardant proportion of an alkali metal silicate and a flame retardant amount of a co-additive selected from the group consisting of an alkali metal chromate, carbonate, borate, phosphate, sulfate, hydroxide, ammonium analogs thereof and mixtures thereof, in which the silicate, expressed as 'SiO co-additive and chlorate are in the weight ratio of 1:1:4-40.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Fireproofing Substances (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US697637A 1968-01-15 1968-01-15 Sodium chlorate compositions of reduced fire hazard containing an alkali metal silicate fire retardant Expired - Lifetime US3645895A (en)

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US (1) US3645895A (forum.php)
BE (1) BE726813A (forum.php)
DE (1) DE1900997A1 (forum.php)
FR (1) FR2000236A1 (forum.php)
GB (1) GB1251714A (forum.php)
NL (1) NL6900680A (forum.php)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3867125A (en) * 1973-02-08 1975-02-18 Ken Mcgee Chemical Corp Composition for and method of defoliation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49133296A (forum.php) * 1973-04-26 1974-12-20

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3867125A (en) * 1973-02-08 1975-02-18 Ken Mcgee Chemical Corp Composition for and method of defoliation

Also Published As

Publication number Publication date
FR2000236A1 (forum.php) 1969-09-05
BE726813A (forum.php) 1969-07-14
DE1900997A1 (de) 1969-09-04
NL6900680A (forum.php) 1969-07-17
GB1251714A (forum.php) 1971-10-27

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Owner name: OCCIDENTAL CHEMICAL CORPORATION

Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICALS & PLASTICS CORP.;REEL/FRAME:004109/0487

Effective date: 19820330