US3034851A - Hydrogen peroxide-ammonium bicarbonate acidic bleaching composition and process - Google Patents
Hydrogen peroxide-ammonium bicarbonate acidic bleaching composition and process Download PDFInfo
- Publication number
- US3034851A US3034851A US612965A US61296556A US3034851A US 3034851 A US3034851 A US 3034851A US 612965 A US612965 A US 612965A US 61296556 A US61296556 A US 61296556A US 3034851 A US3034851 A US 3034851A
- Authority
- US
- United States
- Prior art keywords
- bleaching
- solution
- hydrogen peroxide
- ammonium
- bleached
- 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
Links
- 238000004061 bleaching Methods 0.000 title claims description 54
- 238000000034 method Methods 0.000 title claims description 10
- 230000002378 acidificating effect Effects 0.000 title claims description 6
- 239000000203 mixture Substances 0.000 title description 33
- OJIAPQAMKSISIO-UHFFFAOYSA-N azane;carbonic acid;hydrogen peroxide Chemical compound N.OO.OC(O)=O OJIAPQAMKSISIO-UHFFFAOYSA-N 0.000 title 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 47
- 239000001099 ammonium carbonate Substances 0.000 claims description 31
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 23
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 11
- 238000009736 wetting Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-PWCQTSIFSA-N Tritiated water Chemical compound [3H]O[3H] XLYOFNOQVPJJNP-PWCQTSIFSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 60
- 235000012501 ammonium carbonate Nutrition 0.000 description 20
- 229940059913 ammonium carbonate Drugs 0.000 description 18
- 150000002978 peroxides Chemical class 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- -1 ammonium carbonate compound Chemical class 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000007844 bleaching agent Substances 0.000 description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical class [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011087 paperboard Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- 239000002655 kraft paper Substances 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004254 Ammonium phosphate Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 3
- 235000019289 ammonium phosphates Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 235000019838 diammonium phosphate Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- 241000609240 Ambelania acida Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical class N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010905 bagasse Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- 241001674048 Phthiraptera Species 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 235000011162 ammonium carbonates Nutrition 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- RZKNJSIGVZOHKZ-UHFFFAOYSA-N diazanium carbonic acid carbonate Chemical compound [NH4+].[NH4+].OC(O)=O.OC(O)=O.[O-]C([O-])=O RZKNJSIGVZOHKZ-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- KNXVOGGZOFOROK-UHFFFAOYSA-N trimagnesium;dioxido(oxo)silane;hydroxy-oxido-oxosilane Chemical compound [Mg+2].[Mg+2].[Mg+2].O[Si]([O-])=O.O[Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O KNXVOGGZOFOROK-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
Definitions
- Hydrogen peroxide solutions have heretofore been'employed or proposed for bleaching various solid surfaces such as those of wood, paperboard, paper and floor covering products such as linoleum and rubber tiles.
- the use of strongly alkaline peroxide solutions have almost invariably been regarded as necessary for bleaching such surfaces.
- Solutions rendered alkaline by means of caustic soda, sodium silicate or other common nonvolatile alkalies have been most widely used.
- bleaching is effected by drying, e.g. by heatin such'a solution on the surface to be bleached. This leaves a bleached surface coated with an objectionable gritty-residue of non-volatile alkali. Such residue can be removed by further processing at extra cost, e.g.
- a further object is to provide an improved peroxide method for bleaching such surfaces which avoids both the use of strongly alkaline peroxide solutions and the formation of solid residue when the bleach solution is dried on the solid surfaces being bleached.
- a particular object is to provide bleaching compositions which are especially well suited for use in practicing the improved method of the invention. Still further objects will be apparent from the following description.
- bleaching compositions which are aqueous solutions consisting essentially of hydrogen peroxide (H 0 at a concentration in the range 10 to 50% and an ammonium carbonate at a concentration of at least 5% (both percentages being based upon the total'weight of the composition), and by the use of such compositions in the bleaching of solid surfaces.
- H 0 hydrogen peroxide
- ammonium carbonate at a concentration of at least 5%
- ammonium carbonates can be used in practicing the invention. These include ammonium bicarbonate, NH HCO ammonium sesquicarbonate, 2NH HCO -(NHQ CO -H O; ammonium carbonate, (NI-l 00 1-1 0; and the common ammonium carbonate of commerce, known also as Sal volatile or Hartshorn salt, generally regarded as a double salt or mixture of the bicarbonate and carbamate, 7 W
- ammonium carbonate compounds can also be used.
- the preferred ammonium carbonate compound is the bicarbonate since its use gives-bleaching compositions whichare non-alkaline (pH about 6.6-6.9) and somewhat more stable than those obtained using ammonium carbonate.
- the concentration of the ammonium carbonate or bicarbonate in the "bleaching composition should be, at least 5% by weight based upon the weight of the composition in order to obtain the rapid and-effective bleaching generally desired. Higher concentrations up to the saturation concentration can be used, concentrations rangingfrom about 10 to 23% being generally preferred.
- the concentration of hydrogen peroxide (H 0 in the bleaching composition generally should be at least 10% of the weight of the composition. Higher concentrations, e.g., up to about 50% are suitab'leand those'iri the range-'20 to 40% are generally preferred because of their rapid effective bleaching action, particularly when they also contain an ammonium-carbonate' at a concentration in the preferred range.
- the present compositions are readily prepared simply by dissolving the required amount of the ammonium carbonate compound in a commercial aqueous hydrogen peroxide, e.g., of about 27 to 50% strength.
- Aqueous bleaching compositions of the above type .free of reagentsother than hydrogen peroxide and the ammonium carbonate compound are highly effective for the present purpose and are generally preferred. They are substantially neutral in reaction, e.g. the pH. of the peroxide-carbonate compositions will range from about 7.6 to 7.9 and the pH of the peroxide-bicarbonate com positions will range from about 6.6 to 6.9.
- the pH. of the peroxide-carbonate compositions will range from about 7.6 to 7.9 and the pH of the peroxide-bicarbonate com positions will range from about 6.6 to 6.9.
- peroxide stabilizer Any of the known peroxide stabilizers can be used, particularly when they are employed. in small amounts as will generally be the case.
- the preferred stabilizers are compounds which when used'insmall amounts will not increase significantly the alkalinity of the' composition.
- Illustrative of these are ammonium acetate, ammonium dihydrogen phosphate and citric acid, which are effective stabilizers at concentrations of about 0.5-to 1.0% in the composition.
- any of the solid surfaces heretofore known to respond to bleaching with hydrogen peroxide can in general be bleached by means of the present compositions.
- Illustrative are the surfaces of wood and wooden articles, paperboard, paper, fiber basedf acoustical tile such as wood pulp and bagasse tiles, and floor coverings such as linoleum and rubber tile.
- These floor covering products are generally prepared-fromcompositions which contain unsaturated materials'such as drying oils or rubber which give surfaces with a yellowish discoloration during the usual heat curing operation in the manufacture of such products.
- Such surfaces can be rapidly and effectively" bleached simply by wetting or coating them uniformly with the present bleaching composition and permitting the wet surface to 'dry at ordinaryv or elevated temperatures.
- Example 2 A bleaching solution prepared by dissolving 1 part of ammonium bicarbonate (NH I-ICO in 4 parts of 35% aqueous hydrogen peroxide was applied uniformly at a rate of 8 lbs. per 1000 sq. ft. to a paperboard having a surface layer of semi-bleached kraft pulp. The surface with the applied solution was heated and dried by contact for 10 seconds with a smooth metal surface preheated to a temperature of 325 F. The treatment increased the brightness of the board from 54 to 67.
- NH I-ICO ammonium bicarbonate
- Example 3 A bleaching solution prepared by dissolving 1 part of ammonium bicarbonate in 4 parts of 50% aqueous hydrogen peroxide was applied with a roller applicator to the surface of a rubber floor tile at a rate of about 6 lbs. per 1000 sq. ft.
- the tile composition was about 17% GRS rubber (butadiene-styrene copolymer), 10% silica, 30% clay, 20% whiting and asbestine, and 23% pigment.
- the tile surface Prior to application of the bleaching solution, the tile surface was wet with a 50% solution of C-cetyl betaine, a wetting agent.
- the tile surface with the applied bleaching solution was dried and bleached by contacting it for a few seconds with a smooth chromium plated metal surface preheated to 300 F.
- the tile originally had a mottled white and black surface, the white portions having a definite yellowish shade. After the above treatment, the black portions were unchanged but the yellowness had been removed from the white portions.
- This bleaching solution left no solid residue on either the tile or the metal surface used for heating, and caused no significant roughening of the tile surface.
- Similar bleaching solutions containing alkalies such as caustic soda and sodium silicate are used in place of the above solution, they tend to give a roughened tile surface and leave an objectionable residue both on the tile and the metal surface used for heating.
- Example 4 A rubber floor tile of the composition given in Example 3 was treated substantially as described in that example except that the bleaching solution was prepared by dissolving 1 part of ammonium bicarbonate in 9 parts of 50% aqueous hydrogen peroxide and the tile with the applied solution was heated by being placed for 5 minutes in an oven maintained at 220 F. The original yellowish white portions of the tile were converted to a clear white and no roughening of the tile surface resulted.
- Linoleum which generally has a yellowish discoloration resulting from heat curing during manufacture, can be bleached by the method of Examples 3 and 4.
- a solution was prepared by adding 20 parts of caustic soda, 1 part of 42 B. aqueous sodium silicate and 1 part of calcium oxide, to 130 parts of water. One part of the resulting solution was then added to 3 parts of 35 aqueous hydrogen peroxide to give the bleaching solution.
- Each of Solutions A, B, and C was sprayed onto separate marked portions of the vertical surface .of a solid block of walnut wood. As much of each solution was sprayed on as would remain on the vertical surface. After spraying, the block was allowed to dry 30 minutes at room temperature and then was heated at 130 F. for 15 minutes. The surfaces treatedwith Solutions B and C were bleached to about the same degree while that treated with Solution A was bleached slightly less. The surface treated with Solution C was covered with a gritty alkaline residue and contained a large amount of residual peroxide. The surfaces bleached with Solutions A and B were slightly acidic and contained only small amounts of residual peroxide.
- Solutions A and B are distinctly advantageous over Solution C for use in bleaching wood in preparation for finishing with the usual stains, varnishes and lacquers.
- Example 6 The following bleach solutions were prepared by mixing the components indicated in the proportions shown:
- ammonium phosphate to the bleach formula imparts flame resistant properties to the bleached tile, so that it will be advantageous in instances Where it is desired to bleach and impart flameproofing properties simultaneously to include some ammonium phosphate compound along with the ammonium carbonate compound in the bleaching composition.
- Example 7 Bagasse acoustical tile samples were successfully bleached by the general method of Example 6 using bleaching Solution A of that example. In several trials the brightness was increased from about 47 to 62 employing Solution A at full strength and at dilutions of 1:1 and 1:2. Similar results were also obtained when the tile samples with the applied solution were dried at room temperature.
- Example 8 A bleaching solution was prepared by dissolving 1 part of ammonium bicarbonate in 9 parts of 35% aqueous hydrogen peroxide. The solution was applied uniformly to the surface of a kraft paper at the rate of 3 lbs. per 1000 sq. ft. The paper surface with its applied solution was then immediately dried and bleached by contacting it for 10 seconds with a smooth metal surface preheated to 300 F. This treatment increased the surface brightness of the paper from 29.5 to 53.5. The surface brightness of a kraft paperboard was increased from 26.5 to 47.3 by a similar treatment.
- the present bleaching compositions can be applied to the surface to be bleached by spraying, dipping, brushing or sponging methods, or by other conventional ways of applying solutions such as by the use of a roller applicator.
- the bleaching solution effectively bleaches at ordi nary temperature, but it is generally preferred to employ higher temperatures such as may be obtained by the use of hot air or infrared radiation. Heating by directly contacting the surface coated with the bleaching solution with a smooth metal surface preheated to the desired tem: perature gives excellent results. Metal surfaces at temperatures of 300 to 400 F. have been successfully used, as have also hot-air ovens at temperatures up to about 700 F. Oven or metal surface temperatures should, of course, not be so high as to damage the surface being treated. Heating for a time sufficient to dry the bleaching solution on the surface is generally satisfactory and heating times of a few seconds at the higher temperatures up to 10 to minutes at lower temperatures are generally suitable. Air drying over longer times at ordinary temperature can also be used.
- the hydrogen peroxide concentration may range up to about 50%, the preferred range being 20 to 40%. Concentrations of hydrogen peroxide below 10% and of the ammonium carbonate below 5% are usually too low to give the rapid bleaching desired.
- the preferred concentrations for the ammonium carbonate compound range from about 10 to 23% but higher concentrations up to saturation can be used.
- the bleaching composition may be desirable in some instances to add to the bleaching composition small amounts of a peroxide stabilizer, or of a wetting agent or of a flameproofing agent such as an ammonium phosphate.
- a peroxide stabilizer or of a wetting agent or of a flameproofing agent such as an ammonium phosphate.
- a flameproofing agent such as an ammonium phosphate.
- the presence of such other agents is not essen tial to the obtainment of good and rapid bleaching and aqueous solutions containing no other reagent than hydrogen peroxide and the chosen ammonium carbonate compound will generally be satisfactory for most purposes.
- the present invention provides bleaching compositions which are especially Well suited for bleaching solid surfaces of the type heretofore known to respond to bleaching with hydrogen peroxide. Bleaching of such surfaces can be effected rapidly and effectively by the present method to obtain directly bleached surfaces which are not roughened and are free of undesired residual materials.
- An aqueous acidic bleaching solution having a pH in the range of from 6.6 to 6.9 consisting essentially of water, 1050% by weight hydrogen peroxide and 10-23% by weight ammonium bicarbonate.
Description
United States Patent lice This invention relates to the bleachingof various surfaces and to bleaching compositions which are especially well suited for such use.
Hydrogen peroxide solutions have heretofore been'employed or proposed for bleaching various solid surfaces such as those of wood, paperboard, paper and floor covering products such as linoleum and rubber tiles. The use of strongly alkaline peroxide solutions have almost invariably been regarded as necessary for bleaching such surfaces. Solutions rendered alkaline by means of caustic soda, sodium silicate or other common nonvolatile alkalies have been most widely used. Usually, bleaching is effected by drying, e.g. by heatin such'a solution on the surface to be bleached. This leaves a bleached surface coated with an objectionable gritty-residue of non-volatile alkali. Such residue can be removed by further processing at extra cost, e.g. by neutralization with an acid followed by washing. The use of ammonia as the alkaline agent has been proposed to avoid forma' tion of such alkaline residue,'but hydrogen peroxide solutions alkalized with ammonia do not give as effective bleaching as is generally desired. a
It is an object of the invention to providean improved peroxide method for bleaching such solid surfaces. A further object is to provide an improved peroxide method for bleaching such surfaces which avoids both the use of strongly alkaline peroxide solutions and the formation of solid residue when the bleach solution is dried on the solid surfaces being bleached. A particular object is to provide bleaching compositions which are especially well suited for use in practicing the improved method of the invention. Still further objects will be apparent from the following description.
The objects of the invention are accomplished by the formation of bleaching compositions which are aqueous solutions consisting essentially of hydrogen peroxide (H 0 at a concentration in the range 10 to 50% and an ammonium carbonate at a concentration of at least 5% (both percentages being based upon the total'weight of the composition), and by the use of such compositions in the bleaching of solid surfaces. Such surfaces can be readily and effectively bleached by subjecting the same to the action of such a composition. The solidsurface can simply be wet or coated uniformly with the composition which is then dried on the surface either at ordinary or elevated temperatures. e
Any of the ammonium carbonates can be used in practicing the invention. These include ammonium bicarbonate, NH HCO ammonium sesquicarbonate, 2NH HCO -(NHQ CO -H O; ammonium carbonate, (NI-l 00 1-1 0; and the common ammonium carbonate of commerce, known also as Sal volatile or Hartshorn salt, generally regarded as a double salt or mixture of the bicarbonate and carbamate, 7 W
NH HcO 'NH cOoNl-L Mixtures of any two or more of these ammonium carbonate compounds can also be used. The preferred ammonium carbonate compound is the bicarbonate since its use gives-bleaching compositions whichare non-alkaline (pH about 6.6-6.9) and somewhat more stable than those obtained using ammonium carbonate.
.weight.
, 3,034,851 Patented May 1 5,
The concentration of the ammonium carbonate or bicarbonate in the "bleaching composition should be, at least 5% by weight based upon the weight of the composition in order to obtain the rapid and-effective bleaching generally desired. Higher concentrations up to the saturation concentration can be used, concentrations rangingfrom about 10 to 23% being generally preferred.
The concentration of hydrogen peroxide (H 0 in the bleaching composition generally should be at least 10% of the weight of the composition. Higher concentrations, e.g., up to about 50% are suitab'leand those'iri the range-'20 to 40% are generally preferred because of their rapid effective bleaching action, particularly when they also contain an ammonium-carbonate' at a concentration in the preferred range. The present compositions are readily prepared simply by dissolving the required amount of the ammonium carbonate compound in a commercial aqueous hydrogen peroxide, e.g., of about 27 to 50% strength. No cooling is required during their preparation to prevent peroxide decomposition- This is particularly so when making the preferred peroxidebicarbonate compositions, since ammonium bicarbonate dissolves in aqueous hyrogen peroxide with a negative heat of solution.
Aqueous bleaching compositions of the above type .free of reagentsother than hydrogen peroxide and the ammonium carbonate compound are highly effective for the present purpose and are generally preferred. They are substantially neutral in reaction, e.g. the pH. of the peroxide-carbonate compositions will range from about 7.6 to 7.9 and the pH of the peroxide-bicarbonate com positions will range from about 6.6 to 6.9. However, since such compositions tend to decompose uponlon'g standing, it may be desirable in instances where they are to be prepared considerably in advance of their use to add to the composition a small amount of peroxide stabilizer. Any of the known peroxide stabilizers can be used, particularly when they are employed. in small amounts as will generally be the case. The preferred stabilizers are compounds which when used'insmall amounts will not increase significantly the alkalinity of the' composition. Illustrative of these are ammonium acetate, ammonium dihydrogen phosphate and citric acid, which are effective stabilizers at concentrations of about 0.5-to 1.0% in the composition. In someinstances, it may alsobe advantageous to add to the composition a small amount of a wetting agent to improve the wetting property of the composition.
Any of the solid surfaces heretofore known to respond to bleaching with hydrogen peroxide can in general be bleached by means of the present compositions. Illustrative are the surfaces of wood and wooden articles, paperboard, paper, fiber basedf acoustical tile such as wood pulp and bagasse tiles, and floor coverings such as linoleum and rubber tile. These floor covering products are generally prepared-fromcompositions which contain unsaturated materials'such as drying oils or rubber which give surfaces with a yellowish discoloration during the usual heat curing operation in the manufacture of such products. Such surfaces can be rapidly and effectively" bleached simply by wetting or coating them uniformly with the present bleaching composition and permitting the wet surface to 'dry at ordinaryv or elevated temperatures. I j
v The invention is illustrated by the following examples in which all percentages and parts of reagents are by Example 1 Two solutions were prepared as follows: A. One part of solid ammonium carbonate,
( flz a'fiz 3 (30% NH equivalent), was dissolved in 9 parts of 35% aqueous hydrogen peroxide. The resulting solution had a pH of 7.75. B. One part of 28% aqueous ammonia was added to 9 parts of 35% aqueous hydrogen peroxide. The resulting solution had a pH of 8.75.
The surfaces of samples of an unbleached kraft paperboard were sprayed uniformly with one or the other of the above solutions at an application rate of 3 lbs. of solution per 1000 sq. ft. of board surface. Immediately after spraying, the sprayed surface was contacted for about seconds with a smooth aluminum surface previously heated to a temperature of 325 to 350 R, whereby the surface was rapidly dried and bleached. Although uniform bleaching resulted in each instance, the degree of bleaching was much greater when Solution A was used. The brightness (percent reflectance of blue light) of the samples as measured by a Hunter Multipurpose Reflectometer was 15 for the unbleached board, 29 for the board bleached with Solution A and 24 for the board bleached with Solution B.
In similar trials it was found that other ammonium salts such as the acetate, the citrate and monoand diammonium phosphates, when used in place of ammonium carbonate in Solution A, gave distinctly poorer bleaching results in that bleaching was much less and uneven and the dried bleached surfaces were gritty due to residual salt.
Example 2 A bleaching solution prepared by dissolving 1 part of ammonium bicarbonate (NH I-ICO in 4 parts of 35% aqueous hydrogen peroxide was applied uniformly at a rate of 8 lbs. per 1000 sq. ft. to a paperboard having a surface layer of semi-bleached kraft pulp. The surface with the applied solution was heated and dried by contact for 10 seconds with a smooth metal surface preheated to a temperature of 325 F. The treatment increased the brightness of the board from 54 to 67.
Example 3 A bleaching solution prepared by dissolving 1 part of ammonium bicarbonate in 4 parts of 50% aqueous hydrogen peroxide was applied with a roller applicator to the surface of a rubber floor tile at a rate of about 6 lbs. per 1000 sq. ft. The tile composition was about 17% GRS rubber (butadiene-styrene copolymer), 10% silica, 30% clay, 20% whiting and asbestine, and 23% pigment. Prior to application of the bleaching solution, the tile surface was wet with a 50% solution of C-cetyl betaine, a wetting agent. The tile surface with the applied bleaching solution was dried and bleached by contacting it for a few seconds with a smooth chromium plated metal surface preheated to 300 F.
The tile originally had a mottled white and black surface, the white portions having a definite yellowish shade. After the above treatment, the black portions were unchanged but the yellowness had been removed from the white portions. This bleaching solution left no solid residue on either the tile or the metal surface used for heating, and caused no significant roughening of the tile surface. When similar bleaching solutions containing alkalies such as caustic soda and sodium silicate are used in place of the above solution, they tend to give a roughened tile surface and leave an objectionable residue both on the tile and the metal surface used for heating.
Example 4 A rubber floor tile of the composition given in Example 3 was treated substantially as described in that example except that the bleaching solution was prepared by dissolving 1 part of ammonium bicarbonate in 9 parts of 50% aqueous hydrogen peroxide and the tile with the applied solution was heated by being placed for 5 minutes in an oven maintained at 220 F. The original yellowish white portions of the tile were converted to a clear white and no roughening of the tile surface resulted.
Linoleum, which generally has a yellowish discoloration resulting from heat curing during manufacture, can be bleached by the method of Examples 3 and 4.
Example 5 Three bleaching solutions were prepared as follows:
A. One part of ammonium carbonate was dissolved in 9 parts of 35 aqueous hydrogen peroxide.
B. One part of ammonium carbonate was dissolved in 4 parts of 35% aqueous hydrogen peroxide.
C. A solution was prepared by adding 20 parts of caustic soda, 1 part of 42 B. aqueous sodium silicate and 1 part of calcium oxide, to 130 parts of water. One part of the resulting solution was then added to 3 parts of 35 aqueous hydrogen peroxide to give the bleaching solution.
Each of Solutions A, B, and C was sprayed onto separate marked portions of the vertical surface .of a solid block of walnut wood. As much of each solution was sprayed on as would remain on the vertical surface. After spraying, the block was allowed to dry 30 minutes at room temperature and then was heated at 130 F. for 15 minutes. The surfaces treatedwith Solutions B and C were bleached to about the same degree while that treated with Solution A was bleached slightly less. The surface treated with Solution C was covered with a gritty alkaline residue and contained a large amount of residual peroxide. The surfaces bleached with Solutions A and B were slightly acidic and contained only small amounts of residual peroxide. Since the successful application of a finish to a bleached wood surface requires that the surface be nonalkaline, e.g., neutral or slightly acidic, and substantially free of residual peroxide, Solutions A and B are distinctly advantageous over Solution C for use in bleaching wood in preparation for finishing with the usual stains, varnishes and lacquers.
Example 6 The following bleach solutions were prepared by mixing the components indicated in the proportions shown:
Solutions Component A B o D E F G 35% aq.F[zO2,parts 80 80 80 NH4HCO3, parts (NH4)2HPO4, parts Sodium tripolyphosphate, parts. Borax, parts sequestering agent, parts Water, parts TABLE OF RESULTS Appliea- Sample Brightness Solution tion Rate, Brightness Increase,
Grams/Sq. Points The sample using Solution F did not. attain maximum brightness until several hours after removal from the All.
oven. In all other instances, maximum brightness Was reached during drying in the oven.
A comparison of the resuits for Solutions A, B, .C and G with those for Solution F shows that the presence of ammonium bicarbonate in the bleach solutionvery mark-' edly increases bleaching. The results for Solution E show that sodium tripolyphosphate and borax are not a satisfactory substitute for ammonium bicarbonate. The results for Solutions A, B, C and D show clearly that the brightness obtained decreases markedly and progressively as ammonium bicrabonate is progressively replaced by diammonium phosphate. However, the addition of an ammonium phosphate to the bleach formula imparts flame resistant properties to the bleached tile, so that it will be advantageous in instances Where it is desired to bleach and impart flameproofing properties simultaneously to include some ammonium phosphate compound along with the ammonium carbonate compound in the bleaching composition.
Example 7 Bagasse acoustical tile samples were successfully bleached by the general method of Example 6 using bleaching Solution A of that example. In several trials the brightness was increased from about 47 to 62 employing Solution A at full strength and at dilutions of 1:1 and 1:2. Similar results were also obtained when the tile samples with the applied solution were dried at room temperature.
Example 8 A bleaching solution was prepared by dissolving 1 part of ammonium bicarbonate in 9 parts of 35% aqueous hydrogen peroxide. The solution was applied uniformly to the surface of a kraft paper at the rate of 3 lbs. per 1000 sq. ft. The paper surface with its applied solution was then immediately dried and bleached by contacting it for 10 seconds with a smooth metal surface preheated to 300 F. This treatment increased the surface brightness of the paper from 29.5 to 53.5. The surface brightness of a kraft paperboard was increased from 26.5 to 47.3 by a similar treatment.
The present bleaching compositions can be applied to the surface to be bleached by spraying, dipping, brushing or sponging methods, or by other conventional ways of applying solutions such as by the use of a roller applicator. The bleaching solution effectively bleaches at ordi nary temperature, but it is generally preferred to employ higher temperatures such as may be obtained by the use of hot air or infrared radiation. Heating by directly contacting the surface coated with the bleaching solution with a smooth metal surface preheated to the desired tem: perature gives excellent results. Metal surfaces at temperatures of 300 to 400 F. have been successfully used, as have also hot-air ovens at temperatures up to about 700 F. Oven or metal surface temperatures should, of course, not be so high as to damage the surface being treated. Heating for a time sufficient to dry the bleaching solution on the surface is generally satisfactory and heating times of a few seconds at the higher temperatures up to 10 to minutes at lower temperatures are generally suitable. Air drying over longer times at ordinary temperature can also be used.
least 5% ammonium carbonate compound. The hydrogen peroxide concentration may range up to about 50%, the preferred range being 20 to 40%. Concentrations of hydrogen peroxide below 10% and of the ammonium carbonate below 5% are usually too low to give the rapid bleaching desired. The preferred concentrations for the ammonium carbonate compound range from about 10 to 23% but higher concentrations up to saturation can be used.
As indicated previously, it may be desirable in some instances to add to the bleaching composition small amounts of a peroxide stabilizer, or of a wetting agent or of a flameproofing agent such as an ammonium phosphate. However, the presence of such other agents is not essen tial to the obtainment of good and rapid bleaching and aqueous solutions containing no other reagent than hydrogen peroxide and the chosen ammonium carbonate compound will generally be satisfactory for most purposes.
The present invention provides bleaching compositions which are especially Well suited for bleaching solid surfaces of the type heretofore known to respond to bleaching with hydrogen peroxide. Bleaching of such surfaces can be effected rapidly and effectively by the present method to obtain directly bleached surfaces which are not roughened and are free of undesired residual materials.
I claim:
1. An aqueous acidic bleaching solution having a pH in the range of from 6.6 to 6.9 consisting essentially of water, 1050% by weight hydrogen peroxide and 10-23% by weight ammonium bicarbonate.
2. The method of bleaching a solid surface comprising wetting said surface with an aqueous acidic bleaching solution having a pH in the range of from about 6.6 to
6.9 consisting essentially of water, 10-50% hydrogen peroxide and 10-23 by weight ammonium bicarbonate.
References Cited in the file of this patent UNITED STATES PATENTS 1,063,678 Gruter June 3, 1913 1,321,644 King Nov. 11, 1919 1,668,875 Stein May 8, 1928 1,960,500 Longo May 29, 1934 1,986,672 Bergman Jan. 1, 1935 2,037,119 Comey Apr. 14, 1936 2,166,954 Kaufimann July 25, 1939 2,173,474 Evoy Sept. 19, 1939 2,194,358 Hundt Mar. 19, 1940 2,312,218 Mac Bean Feb. 23', 1943 2,747,734 Rase et al. May 29, 1956 2,801,978 Perlman Aug. 6, 1957 2,882,237 Mahoney Apr. 14, 1959 FOREIGN PATENTS 501,292 Great Britain Feb. 24, "1939 637,928 Great Britain May 31, 1950 Australia Aug. 9, 1955 OTHER REFERENCES Matthews: Bleaching and Related Processes, Chemical Catalog Co., N.Y., 1921, pages 583-584. V
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent. No. 3,034,851 May 15, 1962 Robert B. Dustman Jr.
It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 6, line 30, after "from" insert about Signed and sealed this 11th day of September 1962.
(SEAL) Attest:
DAVID L. LADD ERNEST W. SWIDER Commissioner of Patents Attesting Officer
Claims (1)
- 2. THE METHOD OF BLEACHING A SOLID SURFACE COMPRISING WETTING SAID SURFACE WITH AN AQUEOUS ACIDIC BLEACHING SOLUTION HAVING A PH IN THE RANGE OF FROM ABOUT 6.6 TO 6.9 CONSISTING ESSENTIALLY OF WATER, 10-50% HYDROGEN PEROXIDE AND 10-23% BY WEIGHT AMMONIUM BICARBONATE.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US612965A US3034851A (en) | 1956-10-01 | 1956-10-01 | Hydrogen peroxide-ammonium bicarbonate acidic bleaching composition and process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US612965A US3034851A (en) | 1956-10-01 | 1956-10-01 | Hydrogen peroxide-ammonium bicarbonate acidic bleaching composition and process |
Publications (1)
Publication Number | Publication Date |
---|---|
US3034851A true US3034851A (en) | 1962-05-15 |
Family
ID=24455324
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US612965A Expired - Lifetime US3034851A (en) | 1956-10-01 | 1956-10-01 | Hydrogen peroxide-ammonium bicarbonate acidic bleaching composition and process |
Country Status (1)
Country | Link |
---|---|
US (1) | US3034851A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4377489A (en) * | 1981-03-16 | 1983-03-22 | Ceil Clean Corporation, Inc. | Inorganic persulfate cleaning solution for acoustic materials |
US4481129A (en) * | 1981-12-23 | 1984-11-06 | Lever Brothers Company | Bleach compositions |
US4586961A (en) * | 1985-02-15 | 1986-05-06 | Halliburton Company | Methods and compositions for removing copper and copper oxides from surfaces |
US10254248B2 (en) | 2015-04-21 | 2019-04-09 | Battelle Memorial Institute | Collection, release, and detection of analytes with polymer composite sampling materials |
US10453664B2 (en) | 2015-04-21 | 2019-10-22 | Battelle Memorial Institute | Collection, release, and detection of analytes with polymer composite sampling materials |
Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1063678A (en) * | 1911-06-03 | 1913-06-03 | R H Comey Company | Process of bleaching vegetable fiber and fabrics. |
US1321644A (en) * | 1919-11-11 | philadelphia | ||
US1668875A (en) * | 1925-10-14 | 1928-05-08 | Stein Fur Dyeing Co Inc | Method of treating fur skins and the like |
US1960500A (en) * | 1929-07-02 | 1934-05-29 | Longo Luigi | Washing-fluid |
US1986672A (en) * | 1935-01-01 | Bleaching powder | ||
US2037119A (en) * | 1933-07-31 | 1936-04-14 | R H Comey Brooklyn Company Inc | Continuous bleaching process |
GB501292A (en) * | 1937-08-27 | 1939-02-24 | Thomas Hankinson Jones | Improvements in or relating to the treatment of wool |
US2166954A (en) * | 1937-05-11 | 1939-07-25 | Buffalo Electro Chem Co | Bleaching of wood |
US2173474A (en) * | 1939-04-14 | 1939-09-19 | Evoy Martin | Bleaching |
US2194358A (en) * | 1937-05-24 | 1940-03-19 | Degussa | Bleaching artificial textile fibers |
US2312218A (en) * | 1940-04-16 | 1943-02-23 | Angus A Macbean | Process for bleaching wood |
GB637928A (en) * | 1946-11-12 | 1950-05-31 | Solo Zd Y Na Zapalky | Bleaching process using hydrogen peroxide as bleaching agent |
US2747734A (en) * | 1953-06-12 | 1956-05-29 | Milton F Rose | Composition of matter for removing abradant substances from exfoliated vermiculite and process of using same |
US2801978A (en) * | 1956-11-02 | 1957-08-06 | B T Babbitt Inc | Ammonia-containing detergents |
US2882237A (en) * | 1956-05-29 | 1959-04-14 | Shell Dev | Method for oxidizing carbonaceous deposits |
-
1956
- 1956-10-01 US US612965A patent/US3034851A/en not_active Expired - Lifetime
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1321644A (en) * | 1919-11-11 | philadelphia | ||
US1986672A (en) * | 1935-01-01 | Bleaching powder | ||
US1063678A (en) * | 1911-06-03 | 1913-06-03 | R H Comey Company | Process of bleaching vegetable fiber and fabrics. |
US1668875A (en) * | 1925-10-14 | 1928-05-08 | Stein Fur Dyeing Co Inc | Method of treating fur skins and the like |
US1960500A (en) * | 1929-07-02 | 1934-05-29 | Longo Luigi | Washing-fluid |
US2037119A (en) * | 1933-07-31 | 1936-04-14 | R H Comey Brooklyn Company Inc | Continuous bleaching process |
US2166954A (en) * | 1937-05-11 | 1939-07-25 | Buffalo Electro Chem Co | Bleaching of wood |
US2194358A (en) * | 1937-05-24 | 1940-03-19 | Degussa | Bleaching artificial textile fibers |
GB501292A (en) * | 1937-08-27 | 1939-02-24 | Thomas Hankinson Jones | Improvements in or relating to the treatment of wool |
US2173474A (en) * | 1939-04-14 | 1939-09-19 | Evoy Martin | Bleaching |
US2312218A (en) * | 1940-04-16 | 1943-02-23 | Angus A Macbean | Process for bleaching wood |
GB637928A (en) * | 1946-11-12 | 1950-05-31 | Solo Zd Y Na Zapalky | Bleaching process using hydrogen peroxide as bleaching agent |
US2747734A (en) * | 1953-06-12 | 1956-05-29 | Milton F Rose | Composition of matter for removing abradant substances from exfoliated vermiculite and process of using same |
US2882237A (en) * | 1956-05-29 | 1959-04-14 | Shell Dev | Method for oxidizing carbonaceous deposits |
US2801978A (en) * | 1956-11-02 | 1957-08-06 | B T Babbitt Inc | Ammonia-containing detergents |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4377489A (en) * | 1981-03-16 | 1983-03-22 | Ceil Clean Corporation, Inc. | Inorganic persulfate cleaning solution for acoustic materials |
US4485028A (en) * | 1981-03-16 | 1984-11-27 | Ceil Clean Corporation, Inc. | Inorganic persulfate cleaning solution for acoustic materials |
US4481129A (en) * | 1981-12-23 | 1984-11-06 | Lever Brothers Company | Bleach compositions |
US4586961A (en) * | 1985-02-15 | 1986-05-06 | Halliburton Company | Methods and compositions for removing copper and copper oxides from surfaces |
US10254248B2 (en) | 2015-04-21 | 2019-04-09 | Battelle Memorial Institute | Collection, release, and detection of analytes with polymer composite sampling materials |
US10453664B2 (en) | 2015-04-21 | 2019-10-22 | Battelle Memorial Institute | Collection, release, and detection of analytes with polymer composite sampling materials |
US10533968B2 (en) | 2015-04-21 | 2020-01-14 | Battelle Memorial Institute | Collection, release, and detection of analytes with polymer composite sampling materials |
US11581176B2 (en) | 2015-04-21 | 2023-02-14 | Battelle Memorial Institute | Collection, release, and detection of analytes with polymer composite sampling materials |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3935343A (en) | Molten salt method of producing fire resistant wood articles | |
US2526462A (en) | Moisture-resistant flameproofed product and method of making same | |
US3034851A (en) | Hydrogen peroxide-ammonium bicarbonate acidic bleaching composition and process | |
US2262634A (en) | Method of flameproofing combustible material | |
US4539045A (en) | Non-blooming fire retardants for wood substrates | |
US4107373A (en) | Flame retardant cellulosic materials | |
US1738976A (en) | Process for fireproofing cellulose | |
US2977241A (en) | One coat enamel process | |
US2778749A (en) | Paper products and manufacture thereof | |
US3017236A (en) | Hydrogen peroxide-alkali metal bicarbonate acidic bleaching process | |
US1837430A (en) | Method of preparing metal for painting | |
US2096400A (en) | Bleaching of wood | |
DE2516237A1 (en) | PROCESS FOR PERMANENTLY FLAME RESISTANT FINISHING OF TEXTILES | |
US2960382A (en) | Method of bleaching linoleum using hydrogen peroxide bleach | |
US2414327A (en) | Method of water- and sunproofing paper and textiles and the composition to be used in the method | |
US3682697A (en) | Water repelling compositions | |
US2234646A (en) | Water resistant alkali silicate composition | |
US1804633A (en) | Process of making fire proofed wood and like cellular products | |
US1503443A (en) | Process and material for preparing metal for coating | |
US2281599A (en) | Method for weighting textiles | |
US2132527A (en) | Water-resistant fabric | |
US2819754A (en) | Surface coverings | |
US2211569A (en) | Process of producing decorative fiberboard | |
US1116349A (en) | Composition for fireproofing materials. | |
US3677798A (en) | Polymeric chromium sulfatozirconate compositions,their preparation and use |