WO1997011039A1 - Use of protein-polysaccharide complex composition for enhancing internal adhesion of cementitious compositions for stabilizing soil, beaches and roads and compositions therefor - Google Patents

Use of protein-polysaccharide complex composition for enhancing internal adhesion of cementitious compositions for stabilizing soil, beaches and roads and compositions therefor Download PDF

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Publication number
WO1997011039A1
WO1997011039A1 PCT/US1996/013725 US9613725W WO9711039A1 WO 1997011039 A1 WO1997011039 A1 WO 1997011039A1 US 9613725 W US9613725 W US 9613725W WO 9711039 A1 WO9711039 A1 WO 9711039A1
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WO
WIPO (PCT)
Prior art keywords
protein
composition
polysaccharide
weight
water
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Application number
PCT/US1996/013725
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French (fr)
Inventor
Blaise Mcardle
Original Assignee
Blaise Mcardle
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
Priority claimed from US08/523,162 external-priority patent/US5591473A/en
Priority claimed from US08/523,163 external-priority patent/US5514412A/en
Priority claimed from US08/610,658 external-priority patent/US5626658A/en
Application filed by Blaise Mcardle filed Critical Blaise Mcardle
Priority to AU69019/96A priority Critical patent/AU6901996A/en
Publication of WO1997011039A1 publication Critical patent/WO1997011039A1/en

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C7/00—Coherent pavings made in situ
    • E01C7/08—Coherent pavings made in situ made of road-metal and binders
    • E01C7/18—Coherent pavings made in situ made of road-metal and binders of road-metal and bituminous binders
    • E01C7/26—Coherent pavings made in situ made of road-metal and binders of road-metal and bituminous binders mixed with other materials, e.g. cement, rubber, leather, fibre
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
    • C09K17/18—Prepolymers; Macromolecular compounds
    • C09K17/34—Bituminous materials
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C7/00—Coherent pavings made in situ
    • E01C7/08—Coherent pavings made in situ made of road-metal and binders
    • E01C7/10—Coherent pavings made in situ made of road-metal and binders of road-metal and cement or like binders
    • E01C7/14—Concrete paving
    • E01C7/142—Mixtures or their components, e.g. aggregate
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C7/00—Coherent pavings made in situ
    • E01C7/36—Coherent pavings made in situ by subjecting soil to stabilisation
    • E—FIXED CONSTRUCTIONS
    • E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
    • E02B—HYDRAULIC ENGINEERING
    • E02B3/00—Engineering works in connection with control or use of streams, rivers, coasts, or other marine sites; Sealings or joints for engineering works in general
    • E02B3/04—Structures or apparatus for, or methods of, protecting banks, coasts, or harbours
    • E02B3/12—Revetment of banks, dams, watercourses, or the like, e.g. the sea-floor
    • E02B3/122—Flexible prefabricated covering elements, e.g. mats, strips
    • E02B3/126—Flexible prefabricated covering elements, e.g. mats, strips mainly consisting of bituminous material or synthetic resins

Definitions

  • Protein-Polysaccharide Complex Composition for Enhancing Internal Adhesion of Cementitious Compositions for Stabilizing Soil, Beaches and Roads and Compositions Therefor
  • This invention relates generally to protein complex compositions, methods of preparation of protein-polysaccharide complex compositions and uses of protein complex composition and, specifically, to a protein-polysaccharide complex composition including a water-soluble polysaccharide, a substantially water- insoluble protein and an acidulant.
  • This invention relates to the treatment of ground surfaces such as soil, beaches, loose gravel, road surfaces and road beds and the treatment of road construction materials to improve their resistance against erosion caused by environmental forces and physical wear.
  • This invention further relates to a process for treating cementitious containing materials including asphalt with a binding composition containing a protein-polysaccharide complex to improve resistance to erosion caused by environmental forces and physical wear and to enhance internal adhesion of the compositions.
  • the use of the binding compositions in asphalt paving compositions reduces the amount of bitumen or asphalt emulsion necessary to produce asphalt paving compositions while increasing the wear resistance of the asphalt paving composition.
  • Proteins or prolamines, such as zein have many utilities due to their amphoteric nature. Proteins have been used in a wide variety of applications including in the production of paper coatings, grease-resistant coatings, laminated boards, solid color prints, printing inks, food coatings, and microencapsulants Prolamines are substantially insoluble in water and in alcohol but are soluble in alcohol-water mixtures
  • Erosion of soils, beaches and paved and unpaved road surfaces is caused by environmental conditions such as wind, rain, water flow, temperature change such as freeze-thaw cycle and physical traffic
  • Erosion has been combatted on soil surfaces by planting vegetation that binds the upper layer of the soil Such plantings are not suitable on land subject to erosion if the land is to be subsequently used for agricultural purposes Also, a wide variety of chemical combinations have been used to treat soils in order to prevent erosion from wind and water to control fugitive dust Many of the previously applied stabilization chemicals may produce deleterious long term effects upon the soil surface or on the surrounding watershed
  • cementitious materials such as compositions containing hydraulic, rubber, Portland and organic cement or concrete are utilized in road paving formations, building structures, building and structural component formation, roofing compositions, waterproofing coatings, bonding compositions and in many other diverse applications.
  • Erosion of cementitious structures such as paved road surfaces or other structures is caused by environmental conditions such as wind, rain, water flow, freeze-thaw cycle temperature change and physical wear from traffic. Typically the effects of such erosion is manifested by cracks and potholes in asphalt and cement pavement; or by cracks in asphalt shingles, cement and concrete structures.
  • Asphalt paving compositions are produced by a combination of aggregate formed from crushed rock or stones and other filler materials and asphalt wrap applied in the form of a bituminous coating or an asphalt emulsion. Asphalt and other bituminous materials are obtained as the bottoms products during petroleum refining. Due to the fluctuation in the price and availability of oil for refining, it would be extremely desirable to develop an additive to asphalt containing materials such as asphalt pavement that reduces the amount of bitumen necessary to produce high quality asphalt products including paving compositions.
  • Another object of the present invention is to provide a composition and method to control dust from gravel and stone during comminution and subsequent deposition on ground surfaces and roadways
  • a further object is to provide a stabilizing composition and method to impregnate asphalt and cementitious compositions to improve the resistance of the subsequently formed surface coatings against erosion
  • a protein- polysaccharide complex composition including at least one water-soluble polysaccharide, at least one substantially water-insoluble protein and an acidulant is provided.
  • the invention is directed to the protein-polysaccharide complex composition of matter possessing the characteristics, properties and the relationship of constituents, and the several steps in preparation of the composition exemplified in the methods hereinafter disclosed
  • the present invention is directed to a process for treating ground surfaces such as soil, beaches, loose gravel and road surfaces with a binding composition containing a protein-polysaccharide complex to reduce or substantially prevent erosion
  • the protein-polysaccharide complex can be applied to ground surfaces as a dry granular mixture or in solution and can be mixed with a variety of adjuvants
  • the protein-polysaccharide complex can be mixed into asphalt and cement compositions during manufacture DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • the protein-polysaccharide complex compositions of the present invention include at least one water-soluble polysaccharide, at least one substantially water- insoluble protein and an acidulant.
  • the protein-polysaccharide complex composition can be used as a food preservative, a carrier for pharmaceuticals, an absorbent for waste water treatment, a surfactant to emulsify oil preparations or to control foaming characteristics of anionic and cationic surfactant blends, an absorbent for removing oil from water, soil or sand, an odor suppressant, a carrier for inorganic compounds including metal oxides, a soil stabilizing agent, a herbicide, a dye carrier, a clarifying agent, a plasticizer for polymers, a stabilizer and adhesion promoter for cement and asphalt and an adhesion promoter for binding particulates including silica in polymers including natural and synthetic rubbers.
  • the protein-polysaccharide complex (PPC) composition of the present invention includes a water-soluble polysaccharide, a substantially water-insoluble protein, and an acidulant.
  • the polysaccharides are water-soluble, and if used to produce a product for human or animal consumption, are generally recognized as safe (G.R.A.S.) by the U.S. Food and Drug Administration.
  • the water- soluble polysaccharides are plant-derived polysaccharides and related materials such as pectin.
  • the polysaccharides are guar gum, pectin, gum arabic and mixtures thereof.
  • the polysaccharide preferably is present in an amount ranging between about 90% to 99.5% by weight of the total PPC composition, preferably in an amount ranging between about 95% to 99% by weight of the total PPC composition.
  • the total PPC composition is defined as the total weight of the protein and polysaccharide components.
  • the protein can be any protein that is predominately or substantially water-insoluble, however, vegetable proteins are advantageously utilized due to their availability
  • the vegetable protein is a prolamine
  • a prolamine is a cereal-derived protein that is insoluble in water, absolute alcohol or neutral solvents and soluble in dilute (80%) alcohol
  • Suitable examples of prolamines include, but are not limited to, corn-derived prolamine or zem, barley-derived prolamine or hordein and wheat-derived prolamine or gliadin
  • the substantially water-insoluble protein is present in an amount ranging between about 0 5% to 10% by weight of the total PPC composition, preferably in an amount ranging between about 1 % to 5% by weight of the total PPC
  • the vegetable protein or prolamine used in the composition is zein or corn gluten Zein is extracted from corn or maize PPC compositions containing zein are used to form odorless, tasteless, clear, hard and almost invisible films
  • ammo acids have been isolated from zem including glutamic acid or glutamine, leucine, proline, alanine, phenylalanine, isoleucme, serine, tyrosine and asparagine The remaining seven am o acids are present in amounts of less than 3% by weight Of the eight ammo acids that are necessary for protein synthesis in the human body, zein has virtually no lysine or tryptophan
  • Zem is extracted from corn gluten by physical separation means as opposed to chemical separation means
  • Whole corn zem contains a heterogeneous mixture of disulfide linked aggregates
  • Commercial extraction results in a product with a molecular weight of 25,000 to 35,000 Zein contains a high proportion of hydrocarbon group side chains and has a high percentage of amide groups present with a relatively low amount of free carboxylic acid groups
  • Relatively small amounts of organic acids or acidulants are used to lower the pH of the aqueous polysaccharide solutions during preparation of the PPC compositions
  • the acidulants enhance the water dispersibility of the PPC compositions, i e to facilitate reconstitution of the protein-polysaccharide complex compositions in water
  • Relatively small amounts of a pH adjusting compound in the form of an acid or an acidulant are preferably used to lower the pH of the aqueous polysaccharide solutions during preparation of the PPC compositions to between 1 to 11.5, preferably about 3.8 to 8.5.
  • the acidulants enhance the water dispersibility of the PPC compositions, thereby facilitating reconstitution of the protein-polysaccharide complex compositions in water.
  • any pH adjusting acidic compound is useful in the present invention, including inorganic acids such as carbonic acid, sulfuric acid, hydrochloride acid and the like, it is preferable to utilize organic acids, preferably C, to C 2o organic acids.
  • Suitable organic acidulants include, but are not limited to, citric acid, malic acid, adipic acid, tannic acid, lactic acid, ascorbic acid, acetic acid, fumaric acid and the like and mixtures thereof. In a preferred embodiment, citric acid is used.
  • the acidulants are used in an amount between about 0.25% to 5% by weight of the total PPC compositions, preferably in an amount between about 0.5% to 1% by weight.
  • the acidulant is preferably added to the water of an aqueous organic solvent system prior to addition of the organic component.
  • a PPC composition is prepared by dissolving the substantially water-insoluble protein or prolamine in an aqueous organic solvent system containing the acidulant to form a protein solution.
  • the soluble polysaccharide is then added to the protein solution to form a protein-polysaccharide complex in solution.
  • the solvent is separated or evaporated from the solution to yield the final protein-polysaccharide complex (PPC) composition.
  • the aqueous organic solvent system is a mixture containing at least one organic solvent in water.
  • Suitable organic solvents include, but are not limited to, alcohols such as ethyl alcohol and isopropyl alcohol; edible glycols such as propylene glycol and certain polyethylene glycols; and, ketones such as acetone.
  • the aqueous organic solvent system is either aqueous ethyl alcohol or aqueous isopropyl alcohol. Alcohols generally can hold up to six grams of zein in solution for each 100 milliliters of alcohol.
  • the desired ratio of water to organic solvent in the aqueous organic solvent system is dependent on factors such as the miscibility of the solvent in the water and the amount of protein to be dissolved.
  • the organic solvent system is aqueous ethyl alcohol or aqueous isopropyl alcohol
  • the amount of water generally ranges between about 10% to 40% by weight and the amount of alcohol generally ranges between about 60% to 90% by weight. More preferably, the amount of water in such systems is between about 25% to 35% and the amount of alcohol is between about 65% to 75%.
  • the substantially water-insoluble protein or prolamine is added to the aqueous organic solvent system in an amount between about 100 and 300 grams of prolamine per liter of aqueous organic solvent system, more preferably in an amount between about 120 to 240 grams per liter.
  • the dissolution is carried out at a temperature between about 20°C (ambient room temperature) and about 60°C, preferably about 30°C using conventional agitation methods to form a protein solution. Soluble polysaccharide in minute fiber or particulate form is then admixed with the protein solution to form a PPC in solution.
  • a protein containing gluten such as corn gluten can be directly added into the aqueous organic solvent system instead of pure zein thus passing the zein protein portion of the gluten into solution while the deprotenated non-zein remainder of the gluten can be separated by vacuum filtering or other standard separation techniques.
  • An incidental amount of up to 100%, preferably up to 10% by weight of deprotenated gluten can be present in the recovered in admixture with the protein-polysaccharide complex without adversely affecting the properties of the complex.
  • the PPC in solution generally contains between about 90% to 99.5% of polysaccharide and between about 0.5% to 10% of a protein based on the combined total weight of the polysaccharide and the protein. More preferably, the PPC in solution contains between about 95% to 99% of polysaccharide and between about 1 % to 5% of vegetable protein based on the total weight of polysaccharide and protein.
  • the substantially water-insoluble protein or prolamine thoroughly impregnate the soluble polysaccharide particles during the process of admixing the soluble polysaccharide with the protein solution.
  • the aqueous organic solvent system used to prepare the protein solution should wet the soluble- polysaccharide particles so that the hydrophilic soluble polysaccharide particles are impregnated or coated with the hydrophobic protein to form the PPC solution.
  • the admixing process is carried out until a complete uniform mixture is attained.
  • the process is carried out at a temperature between about 20°C and 60°C, preferably between about 20°C and 25°C for a time period of between about 10 and about 30 minutes, preferably between about 10 and 15 minutes.
  • the PPC solution is agitated during the admixing process by conventional agitation methods including, but not limited to, manual shaking, mechanical shaking, magnetic stirring, mechanical stirring or a combination thereof.
  • Additives that promote impregnation may be added at any point during the admixing process.
  • Suitable additives include, but are not limited to, detergents and emulsifiers.
  • Exemplary additives are polysorbates, edible vegetable oils and egg albumin.
  • Dispersibility and film forming characteristics of the PPC composition can be modified by adding up to 5%, preferably 0.125% to 5%, by weight of particulate metal oxides or sulfides containing metals from Periodic Table Groups 4 to 13, preferably Groups 8 to 10, most preferably any valent form of iron oxide and iron sulfide.
  • metal oxides or sulfides can be added to the initial solvent system to admix with the PPC composition during formation or be subsequently added to and mixed with the dry powdered PPC composition.
  • the solution or powder applied to the ground surfaces may additionally contain one or more additives at a total level of up to 20 % by weight of the combined polysaccharide and protein components of the PPC composition including fillers, pigments, stabilizers, thickening agents, buffers, fertilizers, mineral salts and plant protection agents.
  • Particularly useful fillers include waxes, paraffins, resin, lignin stabilizers, SiO 2 , drilling muds and borax (sodium borate). Borax is preferably added only to a dry mixture of a PPC composition.
  • the solvent is separated or evaporated to yield a protein-polysaccharide complex composition, that is, particulate polysaccharide impregnated or complexed with a protein
  • solvent removal techniques including, but not limited to, vacuum drying, centrifugation, evaporation, freeze drying, air drying, convection oven drying or a combination thereof
  • the protein-polysaccharide complex composition provided in accordance with the invention can be further processed by grinding or milling to a desired mesh particle size for use in tablets, granules, powders, pellets, extrusions, flours and the like
  • the composition can be formed into a powder
  • the surface treating PPC composition of the present invention can be used to coat comminuted rock, such as crushed stone or gravel, to suppress dust
  • the protein-polysaccharide complex coating composition can be applied to the surface of the crushed stone or gravel during the pulverization or the crushing procedure to reduce the emission of dust during comminution of the larger stone pieces
  • the protein-polysaccharide complex coating composition in solution can be sprayed onto the surface of the gravel or crushed stone or after the deposition of the gravel or crushed stone on a ground surface such as a road bed, driveway or parking lot
  • the PPC composition is applied at a rate of 5 to 200 grams of PPC composition per 100 fi 2 of stone surface to be coated
  • the ground surfaces can be stabilized against erosion by treating the ground surface with 1 to 6000 grams of PPC composition per 100 /t 2 of ground surface area, preferably 5 to 20 grams of PPC composition per 100 ft 2 of soil or road ground surface area and 2000 to 6000 grams, most preferably 2000 to 4000 grams of PPC composition per 100 ft 2 of beach or sandy ground surface area Beach areas to be stabilized against erosion require higher end application rates due to the porosity of the sand and to provide stabilization of the sand against destructive wave action
  • the PPC composition can be applied in solution by spraying or in granular form by spreading means such as a broadcast spreader or the like.
  • the PPC composition can be added in granular form or in solution directly to cementitious or asphalt compositions in amounts of protein-polysaccharide complex (PPC) ranging from 0.0002 to 1%, preferably 0.0001 to 0.1% by weight of the total cementitious or asphalt composition.
  • PPC protein-polysaccharide complex
  • the addition of this PPC additive to cement or asphalt improves tensile strength and internal adhesion properties of cement or asphalt.
  • the incorporation of a PPC composition into cement and asphalt increases the elasticity and longevity of the subsequently formed cement or asphalt product or cementitious or asphalt paving coating, thereby reducing the likelihood of the product or coating to crack.
  • Granular PPC composition is preferably added to the dry cement or asphalt during formation.
  • PPC additives to asphalt compositions during asphalt fabrication processes promotes increased internal adhesion between the asphalt wrap and the virgin aggregate such as comminuted stone, resulting in an asphalt product having improved road surface characteristics.
  • Reduced amounts of asphalt wrap can be used to produce asphalt compositions containing PPC as an additive since the PPC additive promotes adhesion and coating of the asphalt wrap onto the virgin aggregate.
  • composition used according to the present invention forms a protective binding layer on the ground surface by hydrogen bonding with silica and silicates present in the soil or road surface.
  • the present process for treating cementitious containing materials including asphalt with a binding composition containing a protein-polysaccharide complex improves resistance of the subsequently formed cementitious composition to erosion caused by environmental forces and physical wear and enhances the internal adhesion of the cementitious composition.
  • the use of the binding compositions in asphalt paving compositions reduces the amount of bitumen or asphalt emulsion necessary to produce asphalt paving compositions while increasing the wear resistance of the asphalt paving composition.
  • the incorporation of a PPC composition into cementitious composition including cement and asphalt increases the elasticity and longevity of the subsequently formed cement or asphalt product or cementitious or asphalt paving coating, thereby reducing the likelihood of the product or coating to crack Granular PPC composition is preferably added to the dry cement or asphalt during formation
  • Asphalt paving compositions containing PPC as an additive can reduce the amount of asphalt or bitumen necessary to produce the paving composition since the PPC additive promotes adhesion and coating of the asphalt onto the virgin aggregate It is believed that the use of an effective amount of the PPC additive to enhance the internal adhesion of asphalt or bitumen in a paving composition can result in up to a 25% by weight reduction of the amount of required asphalt or bitumen content
  • asphalt road paving composition incorporating the PPC additive of the present invention may contain 4 3 to 4 7% by weight of asphalt emulsion or lower in the asphalt paving composition in normal asphalt paving compositions containing at least 5 5% by weight of asphalt emulsion
  • composition used according to the present invention forms a protective binding layer on the aggregate in the paving composition by hydrogen bonding with silica and silicates present in the aggregate
  • the binding compositions of the present invention are particular useful in asphalt materials utilized in many applications including road coating and paving formations, roofing compositions, roofing materials (shingles, felt, etc ), waterproofing coatings and compositions and in many other diverse applications
  • the binding compositions of the present invention are also useful in other cementitious materials such as cementitious compositions containing hydraulic, rubber, Portland and organic cement or concrete utilized in road paving formations, building structures, building and structural component formation, roofing compositions, waterproofing coatings, bonding compositions and in many other diverse applications
  • the following examples of preparation and use of the PPC composition are presented for purposes of illustration only and are not to be construed to limit the scope of the invention described herein.
  • a 10% zein solution was prepared by dissolving 10 grams of unstripped zein in 90 grams of an aqueous isopropyl alcohol solution.
  • the aqueous isopropyl alcohol solution contained 15% water by weight and 85% isopropyl alcohol by weight. Dissolution was carried out in a 500 ml beaker and the solution was initially stirred using a mechanical stirrer at a speed of over 100 rpm in order to fully wet the zein. Once all of the zein was dispersed, the stirring speed was reduced by about ! for an additional five minutes to insure complete dissolution of the zein in the aqueous isopropyl alcohol solution and to produce a protein solution. The ambient temperature was maintained at 22 °C throughout this procedure.
  • the resulting PPC solution was dried under reduced pressure of 0.05 atmospheres, at a temperature of 60°C using a lab-line Duo-Vac vacuum oven manufactured by LabLine Corp., Melrose Park, IL.
  • the resulting recovered dried PPC composition was a yellowish-beige color and was milled to a granular form (80 mesh).
  • the iron oxide/PPC mixture was not recovered from the solution but 4405.3 ml containing approximately 2516.5 grams of PPC was directly mixed into a 250 gallon gravity spray applicator filled with water.
  • Example 1 Three asphalt paving compositions were prepared as displayed in Table 1.
  • the composition of Example 1 contained 10 grams of PPC composition prepared jn accordance with the procedure of Example A.
  • the asphalt paving composition of Example 2 contained 10 grams of iron oxide/PPC composition prepared in accordance with the procedure of Example B.
  • the asphalt paving composition of Example 3 was a control and contained no PPC composition. All percentages in the table are by weight of the total asphalt paving composition except air voids are represented in volume percentage. The stability was measured by the Marshall Test.
  • EXAMPLE C Dry granular PPC as prepared in accordance with the procedure of Example A additionally containing 10% by weight of expended corn gluten was mixed with 0.5% by weight of iron oxide for dispersal in a hand held fertilizer applicator. The dry granular PPC was also premixed with 2% by weight of borax. EXAMPLE P The granular PPC prepared in accordance with the procedure of Example A was dispersed in water at a rate of 10 grams of PPC to 4000 ml of water for application through a gravity sprayer.
  • Road surfaces treated with the PPC composition using the compositions of Examples B and D were after-treated with 4000 ml of a 2% by weight aqueous borax solution per 100 /t 2 of ground surface.
  • the dirt roads were evaluated for erosion over a sixteen month period. During the evaluation period the dirt road surface was graded six separate occasions, plowed of snow regularly during the winter months and salted with salt coated with SiO 2 as a flowing agent after snowfalls.
  • Example D 125825 grams per//t 2 Road surfaces treated with the PPC composition using the compositions of Examples B and D were after-treated with 2% by weight of an aqueous borax solution per 4000 ml of PPC in solution.
  • Example D The PPC composition of Example D was spayed on a road surface abutting a cornfield at an application rate 1400 grams of PPC at a concentration of 10 grams of PPC per 4000 ml.
  • Example 9 The PPC composition of Example B was applied onto a 50 /t 2 area of beach at a concentration of 30 grams of PPC per 4000 ml of water at an application rate of 1 gallon per fi 2 .
  • the beach and adjacent beach located at Long Boat Key in Florida was subsequently subjected to hurricane conditions and substantial beach erosion washed away the adjacent beach surface, however, the PPC treated sand surface remained substantially intact after the storm.
  • Example 9
  • a soupy PPC solution containing was prepared as described in Example A After addition of the guar gum was complete, 20 grams of dried egg albumin (Henigson, Inc , White Plains, NY) was added and dispersed completely The solution was dried under reduced pressure at 60°C using a Lab-Line Duo-Vac vacuum oven The resulting PPC composition was a yellowish-beige color and was milled to a granular form
  • the PPC compositions provided in accordance with the present invention are useful in a variety of utilities including as a food preservative, a carrier for pharmaceuticals, an absorbent for waste water treatment, a surfactant to emulsify oil preparations or to control foaming characteristics of anionic and cationic surfactant blends, a carrier for inorganic compounds including metal oxides, an absorbent for removing oil from water, sand or soil, an odor suppressant, a soil stabilizing agent, a dye carrier, a herbicide, a clarifying agent or a plasticizer for polymers, a stabilizer and adhesion promoter for cement and asphalt compositions and an adhesive promoter for binding particulates including silica in polymers including natural and synthetic rubbers.
  • the dried PPC composition is preferably added to the water in an amount ranging between about 2 to 50 grams per gallon of water, preferably in an amount between about 2 to 10 grams per gallon.
  • the PPC composition is thoroughly dispersed in the water by mixing, for example, with a mechanical stirrer to form a homogeneous dispersion.
  • ingredients or compounds recited in the singular are intended to include compatible mixtures of such ingredients wherever the sense permits.

Abstract

This invention relates to a process for treating cementitious containing materials including asphalt with a binding composition containing a protein-polysaccharide complex to improve resistance to erosion caused by environmental forces and physical wear and to enhance internal adhesion of the compositions. The use of the binding compositions in asphalt paving compositions reduces the amount of bitumen or asphalt emulsion necessary to produce asphalt paving compositions while increasing the wear resistance of the asphalt paving composition. This invention further relates to a process and compositions for conditioning soils, beaches and roadways by treating the surface or the roadway construction materials of these areas with a granular composition or an aqueous solution containing a protein-polysaccharide complex. The treated surfaces and roadway materials have improved erosion resistance. A protein-polysaccharide complex composition is prepared by admixing a water-soluble polysaccharide with a substantially water-insoluble protein in an alcohol/water solution. In the recovered complex the water-insoluble protein impregnates or coats the water-soluble polysaccharide without affecting the beneficial properties of the polysaccharide and protein.

Description

Use of Protein-Polysaccharide Complex Composition for Enhancing Internal Adhesion of Cementitious Compositions for Stabilizing Soil, Beaches and Roads and Compositions Therefor
FIELD OF THE INVENTION
This invention relates generally to protein complex compositions, methods of preparation of protein-polysaccharide complex compositions and uses of protein complex composition and, specifically, to a protein-polysaccharide complex composition including a water-soluble polysaccharide, a substantially water- insoluble protein and an acidulant. This invention relates to the treatment of ground surfaces such as soil, beaches, loose gravel, road surfaces and road beds and the treatment of road construction materials to improve their resistance against erosion caused by environmental forces and physical wear. This invention further relates to a process for treating cementitious containing materials including asphalt with a binding composition containing a protein-polysaccharide complex to improve resistance to erosion caused by environmental forces and physical wear and to enhance internal adhesion of the compositions. The use of the binding compositions in asphalt paving compositions reduces the amount of bitumen or asphalt emulsion necessary to produce asphalt paving compositions while increasing the wear resistance of the asphalt paving composition.
BACKGROUND OF THE INVENTION Proteins or prolamines, such as zein, have many utilities due to their amphoteric nature. Proteins have been used in a wide variety of applications including in the production of paper coatings, grease-resistant coatings, laminated boards, solid color prints, printing inks, food coatings, and microencapsulants Prolamines are substantially insoluble in water and in alcohol but are soluble in alcohol-water mixtures
It is desirable to obtain a protein complex for applications in aqueous environments to utilize the amphoteric characteristics of the protein component
Erosion of soils, beaches and paved and unpaved road surfaces is caused by environmental conditions such as wind, rain, water flow, temperature change such as freeze-thaw cycle and physical traffic
Erosion has been combatted on soil surfaces by planting vegetation that binds the upper layer of the soil Such plantings are not suitable on land subject to erosion if the land is to be subsequently used for agricultural purposes Also, a wide variety of chemical combinations have been used to treat soils in order to prevent erosion from wind and water to control fugitive dust Many of the previously applied stabilization chemicals may produce deleterious long term effects upon the soil surface or on the surrounding watershed
Beach erosion due to storm damage, tidal effects, rain and wind remains a constant plague to seaside communities and beach front property owners There is currently no known effective beach surface treatment to substantially reduce the occurrence of beach erosion, rather beaches simply erode and are then rebuilt by expensive sand refurbishing
Rural road surfaces are typically formed by scraping and depositing of a layer of gravel or a bituminous or cementitious coating Such road surfaces being constantly subjected to severe environmental conditions and traffic suffer erosion in the form of potholes, ruts, washboarding, and cracking
Particles of dust and dirt arise from gravel during its formation from larger stone pieces as well as during subsequent deposition and usage on road surfaces Typically dusty soils have been stabilized with aqueous solutions of polymers sometimes containing wetting agents such as in U S Patent Nos 4,592,931 , 3,900,611 , 3,876,576, 3,763,072, and 3,696,621 Asphalt materials are utilized in many applications including road coating and paving formations, roofing compositions, roofing materials (shingles, felt, etc.), waterproofing coatings and compositions and in many other diverse applications. Other cementitious materials such as compositions containing hydraulic, rubber, Portland and organic cement or concrete are utilized in road paving formations, building structures, building and structural component formation, roofing compositions, waterproofing coatings, bonding compositions and in many other diverse applications. Erosion of cementitious structures such as paved road surfaces or other structures is caused by environmental conditions such as wind, rain, water flow, freeze-thaw cycle temperature change and physical wear from traffic. Typically the effects of such erosion is manifested by cracks and potholes in asphalt and cement pavement; or by cracks in asphalt shingles, cement and concrete structures.
Several methods have been suggested in the prior art to stabilize cementitious compositions including asphalt compositions, however, none of these methods significantly enhance the cementitious structures against the powerful forces of erosion.
Asphalt paving compositions are produced by a combination of aggregate formed from crushed rock or stones and other filler materials and asphalt wrap applied in the form of a bituminous coating or an asphalt emulsion. Asphalt and other bituminous materials are obtained as the bottoms products during petroleum refining. Due to the fluctuation in the price and availability of oil for refining, it would be extremely desirable to develop an additive to asphalt containing materials such as asphalt pavement that reduces the amount of bitumen necessary to produce high quality asphalt products including paving compositions.
It is an object of the present invention to produce a water soluble complex containing both a substantially water insoluble protein and a polysaccharide displaying beneficial characteristics of both proteins and polysaccharides.
It is an object of the present invention to provide a process for the production of a protein complex formed by impregnating or coating a polysaccharide with a substantially water-insoluble protein. It is an object of the present invention to provide an inexpensive composition and simple and reliable method to stabilize dusty ground surfaces against erosion
Another object of the present invention is to provide a composition and method to control dust from gravel and stone during comminution and subsequent deposition on ground surfaces and roadways
A further object is to provide a stabilizing composition and method to impregnate asphalt and cementitious compositions to improve the resistance of the subsequently formed surface coatings against erosion
Still other objects and advantages of the invention will in part be obvious and will in part be apparent from the specification
SUMMARY OF THE INVENTION
Generally speaking, in accordance with the invention a protein- polysaccharide complex composition including at least one water-soluble polysaccharide, at least one substantially water-insoluble protein and an acidulant is provided Methods of preparation of the composition and numerous methods of use are also provided
The invention is directed to the protein-polysaccharide complex composition of matter possessing the characteristics, properties and the relationship of constituents, and the several steps in preparation of the composition exemplified in the methods hereinafter disclosed
The present invention is directed to a process for treating ground surfaces such as soil, beaches, loose gravel and road surfaces with a binding composition containing a protein-polysaccharide complex to reduce or substantially prevent erosion The protein-polysaccharide complex can be applied to ground surfaces as a dry granular mixture or in solution and can be mixed with a variety of adjuvants The protein-polysaccharide complex can be mixed into asphalt and cement compositions during manufacture DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The protein-polysaccharide complex compositions of the present invention include at least one water-soluble polysaccharide, at least one substantially water- insoluble protein and an acidulant. The protein-polysaccharide complex composition can be used as a food preservative, a carrier for pharmaceuticals, an absorbent for waste water treatment, a surfactant to emulsify oil preparations or to control foaming characteristics of anionic and cationic surfactant blends, an absorbent for removing oil from water, soil or sand, an odor suppressant, a carrier for inorganic compounds including metal oxides, a soil stabilizing agent, a herbicide, a dye carrier, a clarifying agent, a plasticizer for polymers, a stabilizer and adhesion promoter for cement and asphalt and an adhesion promoter for binding particulates including silica in polymers including natural and synthetic rubbers.
The protein-polysaccharide complex (PPC) composition of the present invention includes a water-soluble polysaccharide, a substantially water-insoluble protein, and an acidulant. The polysaccharides are water-soluble, and if used to produce a product for human or animal consumption, are generally recognized as safe (G.R.A.S.) by the U.S. Food and Drug Administration. In general, the water- soluble polysaccharides are plant-derived polysaccharides and related materials such as pectin.
Examples of polysaccharides that can be used to prepare the PPC composition include, but are not limited to water-soluble cellulose derivatives, seaweed polysaccharides such as alginate and carrageenin, seed mucilaginous polysaccharides, complex plant exudate polysaccharides such as gum arabic, tragacanth, guar gum, pectin, ghatti and the like, and microbially synthesized polysaccharides such as xanthan gum. In a preferred embodiment, the polysaccharides are guar gum, pectin, gum arabic and mixtures thereof.
The polysaccharide preferably is present in an amount ranging between about 90% to 99.5% by weight of the total PPC composition, preferably in an amount ranging between about 95% to 99% by weight of the total PPC composition. The total PPC composition is defined as the total weight of the protein and polysaccharide components. Similarly, the protein can be any protein that is predominately or substantially water-insoluble, however, vegetable proteins are advantageously utilized due to their availability In general, the vegetable protein is a prolamine A prolamine is a cereal-derived protein that is insoluble in water, absolute alcohol or neutral solvents and soluble in dilute (80%) alcohol Suitable examples of prolamines include, but are not limited to, corn-derived prolamine or zem, barley-derived prolamine or hordein and wheat-derived prolamine or gliadin
The substantially water-insoluble protein is present in an amount ranging between about 0 5% to 10% by weight of the total PPC composition, preferably in an amount ranging between about 1 % to 5% by weight of the total PPC
In a preferred embodiment of the invention, the vegetable protein or prolamine used in the composition is zein or corn gluten Zein is extracted from corn or maize PPC compositions containing zein are used to form odorless, tasteless, clear, hard and almost invisible films
Sixteen ammo acids have been isolated from zem including glutamic acid or glutamine, leucine, proline, alanine, phenylalanine, isoleucme, serine, tyrosine and asparagine The remaining seven am o acids are present in amounts of less than 3% by weight Of the eight ammo acids that are necessary for protein synthesis in the human body, zein has virtually no lysine or tryptophan
Zem is extracted from corn gluten by physical separation means as opposed to chemical separation means Whole corn zem contains a heterogeneous mixture of disulfide linked aggregates Commercial extraction results in a product with a molecular weight of 25,000 to 35,000 Zein contains a high proportion of hydrocarbon group side chains and has a high percentage of amide groups present with a relatively low amount of free carboxylic acid groups
Relatively small amounts of organic acids or acidulants are used to lower the pH of the aqueous polysaccharide solutions during preparation of the PPC compositions The acidulants enhance the water dispersibility of the PPC compositions, i e to facilitate reconstitution of the protein-polysaccharide complex compositions in water Relatively small amounts of a pH adjusting compound in the form of an acid or an acidulant are preferably used to lower the pH of the aqueous polysaccharide solutions during preparation of the PPC compositions to between 1 to 11.5, preferably about 3.8 to 8.5. The acidulants enhance the water dispersibility of the PPC compositions, thereby facilitating reconstitution of the protein-polysaccharide complex compositions in water. Although any pH adjusting acidic compound is useful in the present invention, including inorganic acids such as carbonic acid, sulfuric acid, hydrochloride acid and the like, it is preferable to utilize organic acids, preferably C, to C2o organic acids. Suitable organic acidulants include, but are not limited to, citric acid, malic acid, adipic acid, tannic acid, lactic acid, ascorbic acid, acetic acid, fumaric acid and the like and mixtures thereof. In a preferred embodiment, citric acid is used.
The acidulants are used in an amount between about 0.25% to 5% by weight of the total PPC compositions, preferably in an amount between about 0.5% to 1% by weight. The acidulant is preferably added to the water of an aqueous organic solvent system prior to addition of the organic component.
A PPC composition is prepared by dissolving the substantially water-insoluble protein or prolamine in an aqueous organic solvent system containing the acidulant to form a protein solution. The soluble polysaccharide is then added to the protein solution to form a protein-polysaccharide complex in solution. The solvent is separated or evaporated from the solution to yield the final protein-polysaccharide complex (PPC) composition.
The aqueous organic solvent system is a mixture containing at least one organic solvent in water. Suitable organic solvents include, but are not limited to, alcohols such as ethyl alcohol and isopropyl alcohol; edible glycols such as propylene glycol and certain polyethylene glycols; and, ketones such as acetone. In a preferred embodiment of the invention, the aqueous organic solvent system is either aqueous ethyl alcohol or aqueous isopropyl alcohol. Alcohols generally can hold up to six grams of zein in solution for each 100 milliliters of alcohol.
The desired ratio of water to organic solvent in the aqueous organic solvent system is dependent on factors such as the miscibility of the solvent in the water and the amount of protein to be dissolved. When the organic solvent system is aqueous ethyl alcohol or aqueous isopropyl alcohol, the amount of water generally ranges between about 10% to 40% by weight and the amount of alcohol generally ranges between about 60% to 90% by weight. More preferably, the amount of water in such systems is between about 25% to 35% and the amount of alcohol is between about 65% to 75%.
The substantially water-insoluble protein or prolamine is added to the aqueous organic solvent system in an amount between about 100 and 300 grams of prolamine per liter of aqueous organic solvent system, more preferably in an amount between about 120 to 240 grams per liter. The dissolution is carried out at a temperature between about 20°C (ambient room temperature) and about 60°C, preferably about 30°C using conventional agitation methods to form a protein solution. Soluble polysaccharide in minute fiber or particulate form is then admixed with the protein solution to form a PPC in solution.
In an alternative embodiment, a protein containing gluten such as corn gluten can be directly added into the aqueous organic solvent system instead of pure zein thus passing the zein protein portion of the gluten into solution while the deprotenated non-zein remainder of the gluten can be separated by vacuum filtering or other standard separation techniques. An incidental amount of up to 100%, preferably up to 10% by weight of deprotenated gluten can be present in the recovered in admixture with the protein-polysaccharide complex without adversely affecting the properties of the complex.
The PPC in solution generally contains between about 90% to 99.5% of polysaccharide and between about 0.5% to 10% of a protein based on the combined total weight of the polysaccharide and the protein. More preferably, the PPC in solution contains between about 95% to 99% of polysaccharide and between about 1 % to 5% of vegetable protein based on the total weight of polysaccharide and protein.
It is important that the substantially water-insoluble protein or prolamine thoroughly impregnate the soluble polysaccharide particles during the process of admixing the soluble polysaccharide with the protein solution. The aqueous organic solvent system used to prepare the protein solution should wet the soluble- polysaccharide particles so that the hydrophilic soluble polysaccharide particles are impregnated or coated with the hydrophobic protein to form the PPC solution.
The admixing process is carried out until a complete uniform mixture is attained. In general, the process is carried out at a temperature between about 20°C and 60°C, preferably between about 20°C and 25°C for a time period of between about 10 and about 30 minutes, preferably between about 10 and 15 minutes. The PPC solution is agitated during the admixing process by conventional agitation methods including, but not limited to, manual shaking, mechanical shaking, magnetic stirring, mechanical stirring or a combination thereof.
Additives that promote impregnation may be added at any point during the admixing process. Suitable additives include, but are not limited to, detergents and emulsifiers. Exemplary additives are polysorbates, edible vegetable oils and egg albumin.
Dispersibility and film forming characteristics of the PPC composition can be modified by adding up to 5%, preferably 0.125% to 5%, by weight of particulate metal oxides or sulfides containing metals from Periodic Table Groups 4 to 13, preferably Groups 8 to 10, most preferably any valent form of iron oxide and iron sulfide. These metal oxides or sulfides can be added to the initial solvent system to admix with the PPC composition during formation or be subsequently added to and mixed with the dry powdered PPC composition. The solution or powder applied to the ground surfaces may additionally contain one or more additives at a total level of up to 20 % by weight of the combined polysaccharide and protein components of the PPC composition including fillers, pigments, stabilizers, thickening agents, buffers, fertilizers, mineral salts and plant protection agents. Particularly useful fillers include waxes, paraffins, resin, lignin stabilizers, SiO2, drilling muds and borax (sodium borate). Borax is preferably added only to a dry mixture of a PPC composition.
Once the PPC solution has been prepared, the solvent is separated or evaporated to yield a protein-polysaccharide complex composition, that is, particulate polysaccharide impregnated or complexed with a protein Any number of solvent removal techniques may be used including, but not limited to, vacuum drying, centrifugation, evaporation, freeze drying, air drying, convection oven drying or a combination thereof
It is preferred that the solvent removal technique be one that does not require the use of excessive or prolonged heat that will oxidatively darken the product Although oxidative darkening has little effect on the utility of the product it may affect its appeal and desirability One preferred method of extracting the solvent is vacuum drying which safety removes and recovers the solvent while drying the product to provide the PPC composition
The protein-polysaccharide complex composition provided in accordance with the invention can be further processed by grinding or milling to a desired mesh particle size for use in tablets, granules, powders, pellets, extrusions, flours and the like In a preferred embodiment, the composition can be formed into a powder
The surface treating PPC composition of the present invention can be used to coat comminuted rock, such as crushed stone or gravel, to suppress dust The protein-polysaccharide complex coating composition can be applied to the surface of the crushed stone or gravel during the pulverization or the crushing procedure to reduce the emission of dust during comminution of the larger stone pieces The protein-polysaccharide complex coating composition in solution can be sprayed onto the surface of the gravel or crushed stone or after the deposition of the gravel or crushed stone on a ground surface such as a road bed, driveway or parking lot The PPC composition is applied at a rate of 5 to 200 grams of PPC composition per 100 fi2 of stone surface to be coated
The ground surfaces can be stabilized against erosion by treating the ground surface with 1 to 6000 grams of PPC composition per 100 /t2 of ground surface area, preferably 5 to 20 grams of PPC composition per 100 ft2 of soil or road ground surface area and 2000 to 6000 grams, most preferably 2000 to 4000 grams of PPC composition per 100 ft2 of beach or sandy ground surface area Beach areas to be stabilized against erosion require higher end application rates due to the porosity of the sand and to provide stabilization of the sand against destructive wave action As previously discussed, the PPC composition can be applied in solution by spraying or in granular form by spreading means such as a broadcast spreader or the like.
In an alternative embodiment, the PPC composition can be added in granular form or in solution directly to cementitious or asphalt compositions in amounts of protein-polysaccharide complex (PPC) ranging from 0.0002 to 1%, preferably 0.0001 to 0.1% by weight of the total cementitious or asphalt composition. The addition of this PPC additive to cement or asphalt improves tensile strength and internal adhesion properties of cement or asphalt. The incorporation of a PPC composition into cement and asphalt increases the elasticity and longevity of the subsequently formed cement or asphalt product or cementitious or asphalt paving coating, thereby reducing the likelihood of the product or coating to crack. Granular PPC composition is preferably added to the dry cement or asphalt during formation.
The use of PPC additives to asphalt compositions during asphalt fabrication processes promotes increased internal adhesion between the asphalt wrap and the virgin aggregate such as comminuted stone, resulting in an asphalt product having improved road surface characteristics. Reduced amounts of asphalt wrap can be used to produce asphalt compositions containing PPC as an additive since the PPC additive promotes adhesion and coating of the asphalt wrap onto the virgin aggregate.
It is believed that the composition used according to the present invention forms a protective binding layer on the ground surface by hydrogen bonding with silica and silicates present in the soil or road surface.
The present process for treating cementitious containing materials including asphalt with a binding composition containing a protein-polysaccharide complex improves resistance of the subsequently formed cementitious composition to erosion caused by environmental forces and physical wear and enhances the internal adhesion of the cementitious composition. The use of the binding compositions in asphalt paving compositions reduces the amount of bitumen or asphalt emulsion necessary to produce asphalt paving compositions while increasing the wear resistance of the asphalt paving composition. The incorporation of a PPC composition into cementitious composition including cement and asphalt increases the elasticity and longevity of the subsequently formed cement or asphalt product or cementitious or asphalt paving coating, thereby reducing the likelihood of the product or coating to crack Granular PPC composition is preferably added to the dry cement or asphalt during formation
The use of PPC additives to asphalt compositions during asphalt fabrication processes promotes increased internal adhesion between the asphalt wrap and the virgin aggregate such as comminuted stone, resulting in an asphalt product having improved road surface characteristics Asphalt paving compositions containing PPC as an additive can reduce the amount of asphalt or bitumen necessary to produce the paving composition since the PPC additive promotes adhesion and coating of the asphalt onto the virgin aggregate It is believed that the use of an effective amount of the PPC additive to enhance the internal adhesion of asphalt or bitumen in a paving composition can result in up to a 25% by weight reduction of the amount of required asphalt or bitumen content Preferably asphalt road paving composition incorporating the PPC additive of the present invention may contain 4 3 to 4 7% by weight of asphalt emulsion or lower in the asphalt paving composition in normal asphalt paving compositions containing at least 5 5% by weight of asphalt emulsion
It is believed that the composition used according to the present invention forms a protective binding layer on the aggregate in the paving composition by hydrogen bonding with silica and silicates present in the aggregate The binding compositions of the present invention are particular useful in asphalt materials utilized in many applications including road coating and paving formations, roofing compositions, roofing materials (shingles, felt, etc ), waterproofing coatings and compositions and in many other diverse applications The binding compositions of the present invention are also useful in other cementitious materials such as cementitious compositions containing hydraulic, rubber, Portland and organic cement or concrete utilized in road paving formations, building structures, building and structural component formation, roofing compositions, waterproofing coatings, bonding compositions and in many other diverse applications The following examples of preparation and use of the PPC composition are presented for purposes of illustration only and are not to be construed to limit the scope of the invention described herein.
EXAMPLE A
A 10% zein solution was prepared by dissolving 10 grams of unstripped zein in 90 grams of an aqueous isopropyl alcohol solution. The aqueous isopropyl alcohol solution contained 15% water by weight and 85% isopropyl alcohol by weight. Dissolution was carried out in a 500 ml beaker and the solution was initially stirred using a mechanical stirrer at a speed of over 100 rpm in order to fully wet the zein. Once all of the zein was dispersed, the stirring speed was reduced by about ! for an additional five minutes to insure complete dissolution of the zein in the aqueous isopropyl alcohol solution and to produce a protein solution. The ambient temperature was maintained at 22 °C throughout this procedure.
Two hundred grams of milled guar gum powder (fine-60 mesh, TIC GUMS, Belcamp, MD) was slowly added to the protein solution with vigorous stirring using a mechanical stirrer at a speed of over 100rpm. Manual stirring was started as the mixture thickened. Additional aqueous isopropyl alcohol was added to attain a soupy appearance indicative of successful impregnation of the soluble guar gum particles by the zein solution. Agitation of this soupy liquid mixture was maintained for fifteen minutes.
The resulting PPC solution was dried under reduced pressure of 0.05 atmospheres, at a temperature of 60°C using a lab-line Duo-Vac vacuum oven manufactured by LabLine Corp., Melrose Park, IL. The resulting recovered dried PPC composition was a yellowish-beige color and was milled to a granular form (80 mesh).
EXAMPLE B
The procedure of Example A was followed, however 1.5 grams of iron oxide
(FeO) (Harcros high moment iron oxide TB5600 - lot F4122, Easton, PA) was mixed per each 10 grams of zein contemporaneously with the addition of the guar gum.
The iron oxide/PPC mixture was not recovered from the solution but 4405.3 ml containing approximately 2516.5 grams of PPC was directly mixed into a 250 gallon gravity spray applicator filled with water.
Examples 1 to 3 Three asphalt paving compositions were prepared as displayed in Table 1. The composition of Example 1 contained 10 grams of PPC composition prepared jn accordance with the procedure of Example A. The asphalt paving composition of Example 2 contained 10 grams of iron oxide/PPC composition prepared in accordance with the procedure of Example B. The asphalt paving composition of Example 3 was a control and contained no PPC composition. All percentages in the table are by weight of the total asphalt paving composition except air voids are represented in volume percentage. The stability was measured by the Marshall Test.
Table 1
Example No. 1 2 3
Dry weight of Sample 717 768 1193
% Asphalt content 4.15 4.7 4.29
% Aggregate passing by weight No. 8 sieve 33.5 37.5 34.3 No. 200 sieve 2.8 2.7 3.4
Air voids, % 7.7 8.1 9.4
Stability @ 77°F, (lbs.) 2458.3 2275.7 2759.0
EXAMPLE C Dry granular PPC as prepared in accordance with the procedure of Example A additionally containing 10% by weight of expended corn gluten was mixed with 0.5% by weight of iron oxide for dispersal in a hand held fertilizer applicator. The dry granular PPC was also premixed with 2% by weight of borax. EXAMPLE P The granular PPC prepared in accordance with the procedure of Example A was dispersed in water at a rate of 10 grams of PPC to 4000 ml of water for application through a gravity sprayer.
EXAMPLE 4 Each of the three PPC compositions as prepared in Examples B, C and D were applied to a 20,000 /t* surface of a dirt road in Rome, Maine at the following application rates:
PPC Composition Application Rate (αrams PPC/ft2ι
Example B .125825 grams per/ft2
Example C .125825 grams per/ft2
Example D .125825 grams per//t2
Road surfaces treated with the PPC composition using the compositions of Examples B and D were after-treated with 4000 ml of a 2% by weight aqueous borax solution per 100 /t2 of ground surface.
The dirt roads were evaluated for erosion over a sixteen month period. During the evaluation period the dirt road surface was graded six separate occasions, plowed of snow regularly during the winter months and salted with salt coated with SiO2 as a flowing agent after snowfalls.
During rainfalls the water on the surface of the treated dirt road was quickly absorbed until saturated and the remaining water flowed onto both sides of the road. Contiguous areas of untreated dirt road displayed massive erosion and washboarding even after the surface of the road had been graded and compacted with a roller.
During the winter months each section of the PPC treated road surfaces took longer to freeze than the untreated dirt road sections and maintained a constant temperature after the road had frozen. During periods of dryness dust arising from the road surface from the PPC treated surfaces was substantially reduced compared to contiguous untreated dirt road surfaces.
EXAMPLE 5 Each of the three PPC compositions as prepared in Examples B, C and D were applied to a 2,000 fi2 surface of a dirt road under swampy conditions at the following application rates:
PPC Composition Application Rate (αrams PPC/ft2)
Example B .125825 grams per/ft2
Example C .125825 grams per//t2
Example D .125825 grams per//t2
Road surfaces treated with the PPC composition using the compositions of Examples B and D were after-treated with 2% by weight of an aqueous borax solution per 4000 ml of PPC in solution.
After three days the road surface reached its water equilibrium and the road surface stabilized and became passable.
One 2,000 /t2 area of swampy road surface was treated with the PPC composition of Example C additionally containing 50 grams of borax per 252 grams of PPC. This treated road surface became firm within 24 hours, resisted water overflowing the road and did not erode.
EXAMPLE 6 Each of the three PPC compositions as prepared in Examples B, C and D were applied to 10,000 /t2 of a dirt service road stretching along a mixed paved road of asphalt that passed over base concrete culverts. The PPC compositions were applied at the following application rates:
PPC Composition Application Rate (grams PPC/ft2)
Example B .125825 grams per/ft2
Example C .125825 grams per//t2
Example D .125825 grams per//t2 Road surfaces treated with the PPC composition using the compositions of Examples B and D were after-treated with 2% by weight of an aqueous borax solution per 4000 ml of PPC in solution.
After periodic rainfall and over a 120 day period not noticeable erosion occurred on the service road surface. Furthermore, the PPC compositions had spread over the concrete and the asphalt coated surfaces. Substantially no cracking or pot-holing of these coated surfaces were noted over a 12 month period. Contiguous non-PPC treated surfaces displayed substantially higher degrees of cracking and pot-holing.
EXAMPLE 7
The PPC composition of Example D was spayed on a road surface abutting a cornfield at an application rate 1400 grams of PPC at a concentration of 10 grams of PPC per 4000 ml.
Road surfaces treated with the PPC composition using the compositions of Examples B and D were after-treated with 2% by weight of an aqueous borax solution per 4000 ml of PPC in solution. Six hours after application it began to rain and it rained daily for seven consecutive days. The PPC composition had in port washed from the roadway and onto the soil surface abutting the treated roadway. The road surface was firm and showed no signs of erosion two days after the rain ceased. The soil surfaces abutting the road surface were extremely swampy and unplowable along non-PPC treated road surfaces, however, the soil areas abutting the PPC treated road surface were firm to the extent that the soil could be plowed.
EXAMPLE 8
The PPC composition of Example B was applied onto a 50 /t2 area of beach at a concentration of 30 grams of PPC per 4000 ml of water at an application rate of 1 gallon per fi2. The beach and adjacent beach located at Long Boat Key in Florida was subsequently subjected to hurricane conditions and substantial beach erosion washed away the adjacent beach surface, however, the PPC treated sand surface remained substantially intact after the storm. Example 9
A soupy PPC solution containing was prepared as described in Example A After addition of the guar gum was complete, 20 grams of dried egg albumin (Henigson, Inc , White Plains, NY) was added and dispersed completely The solution was dried under reduced pressure at 60°C using a Lab-Line Duo-Vac vacuum oven The resulting PPC composition was a yellowish-beige color and was milled to a granular form
Example 10
Fifty grams (50g) of citric acid was added to 0675kg of water used to prepare 4 5kg of an 85 15 alcohol water aqueous organic solvent system Five hundred grams of zem was added to the aqueous organic solvent system in a suitable vessel The aqueous organic solvent was kept in motion during the addition with the aid of a mechanical stirrer Accordingly, a solution of 10% by weight of zein in aqueous alcohol was prepared
Nine and one-half kg of guar gum was added to the 10% zem solution with mixing in a Stokes Heavy Duty sigma-type blender After about 30 minutes of continuous mixing, the mass was homogeneous, slightly tan and had a wet, sand¬ like consistency The mass was dried in an explosion-proof drier to yield a protein- polysaccharide complex
Example 11
Dry granular PPC as prepared in accordance with the procedure of Example A additionally containing 10% by weight of expended corn gluten was mixed with 05% by weight of iron oxide for dispersal in a hand held fertilizer applicator The dry granular PPC was also premixed with 2% by weight of borax
The PPC compositions provided in accordance with the present invention are useful in a variety of utilities including as a food preservative, a carrier for pharmaceuticals, an absorbent for waste water treatment, a surfactant to emulsify oil preparations or to control foaming characteristics of anionic and cationic surfactant blends, a carrier for inorganic compounds including metal oxides, an absorbent for removing oil from water, sand or soil, an odor suppressant, a soil stabilizing agent, a dye carrier, a herbicide, a clarifying agent or a plasticizer for polymers, a stabilizer and adhesion promoter for cement and asphalt compositions and an adhesive promoter for binding particulates including silica in polymers including natural and synthetic rubbers.
The dried PPC composition is preferably added to the water in an amount ranging between about 2 to 50 grams per gallon of water, preferably in an amount between about 2 to 10 grams per gallon. The PPC composition is thoroughly dispersed in the water by mixing, for example, with a mechanical stirrer to form a homogeneous dispersion.
It will thus be seen that the objects set forth above, among those made apparent from the preceding description, are efficiently attained and, since certain changes may be made in the described product, and in carrying out the above process, and in the construction set forth without departing from the spirit and scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limited sense.
It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween.
Particularly, it is to be understood that in said claims, ingredients or compounds recited in the singular are intended to include compatible mixtures of such ingredients wherever the sense permits.

Claims

WHAT IS CLAIMED IS:
1. A method of enhancing intemal adhesion of an asphalt containing composition by admixing with said cementitious composition a protein- polysaccharide complex composition comprising: between about 90% to 99.5% by weight of a water-soluble polysaccharide impregnated with between about 10% to 0.5% by weight of a substantially water- insoluble protein in an amount effective to enhance the internal adhesion of said an effective amount to enhance the intemal adhesion of said asphalt containing composition.
2. The method of claim 1 wherein the water-soluble polysaccharide is selected from the group consisting of alginate, carrageenin, gum arabic, tragacanth, guar gum, pectin, ghatti, xanthan gum and mixtures thereof.
3. The method of claim 1 wherein the substantially water-insoluble protein is a prolamine.
4. The method of claim 1 wherein the substantially water-insoluble protein is zein.
5. The method of claim 1 wherein the protein-polysaccharide complex composition further includes at least one additive for promoting impregnation of the water-soluble polysaccharide by the protein.
6. The method of claim 1 wherein the substantially water-insoluble protein is hordein or gliadin.
7. The method of claim 1 wherein the effective amount of the protein- polysaccharide complex composition to enhance the intemal adhesion of said asphalt containing composition is from 0.0001 to 3.0 weight percent of the total asphalt containing composition.
8. The method of claim 1 wherein the water-soluble polysaccharide comprises guar gum and the substantially water-insoluble protein comprises zein.
9. The method of claim 1 wherein the protein-polysaccharide complex composition further comprises between about 0.25% to 5% by weight of an acidulant.
10. The method of claim 9 wherein the acidulant is selected from the group consisting of tannic acid, lactic acid, ascorbic acid, acetic acid, citric acid, malic acid, adipic acid, fumaric acid and mixtures thereof.
11. The method of claim 9 wherein the acidulant is citric acid.
12. The method of claim 1 wherein the protein-polysaccharide composition further comprises 0.125 to 5% by weight of a metal oxide filler calculated on the weight of protein-polysaccharide complex.
13. The method of claim 12 wherein the metal oxide filler is iron oxide.
14. The method of claim 1 wherein the protein-polysaccharide composition further comprises up to 20% by weight of borax.
15. The method of claim 1 wherein the protein-polysaccharide composition further comprises up to 10% by weight an adjuvant selected from the group consisting of expanded corn gluten, urea and tall oil.
16. An asphalt or bitumen containing composition having improved resistance to erosion and enhanced intemal adhesion comprising a protein- polysaccharide complex composition comprising: between about 90% to 99.5% by weight of a water-soluble polysaccharide impregnated with between about 10% to 0.5% by weight of a substantially water- insoluble protein.
17. The asphalt or bitumen composition of claim 16 wherein the water¬ soluble polysaccharide is selected from the group consisting of alginate, carrageenin, gum arabic, tragacanth, guar gum, pectin, ghatti, xanthan gum and mixtures thereof.
18. The asphalt or bitumen composition of claim 16 wherein the substantially water-insoluble protein is a prolamine.
19. The asphalt or bitumen composition of claim 16 wherein the substantially water-insoluble protein is zein.
20. The asphalt or bitumen composition of claim 16 wherein the protein- polysaccharide complex composition further includes at least one additive for promoting impregnation of the water-soluble polysaccharide by the protein.
21. The asphalt or bitumen composition of claim 16 wherein the substantially water-insoluble protein is hordein or gliadin.
22. The asphalt or bitumen composition of claim 16 wherein the effective amount of the protein-polysaccharide complex composition to enhance the internal adhesion of asphalt or bitumen containing compositions is from 0.0001 to 3.0 weight percent of the total asphalt or bitumen containing composition.
23. The asphalt or bitumen composition of claim 16 wherein the water¬ soluble polysaccharide comprises guar gum and the substantially water-insoluble protein comprises zein.
24. The asphalt or bitumen composition of claim 16 wherein the protein- polysaccharide complex composition further comprises between about 0.25% to 5% by weight of an acidulant.
25. The asphalt or bitumen composition of claim 24 wherein the acidulant is selected from the group consisting of tannic acid, lactic acid, ascorbic acid, acetic acid, citric acid, malic acid, adipic acid, fumaric acid and mixtures thereof.
26. The asphalt or bitumen composition of claim 24 wherein the acidulant is citric acid.
27. The asphalt or bitumen composition of claim 16 wherein the protein- polysaccharide composition further comprises 0.125 to 5% by weight of a metal oxide filler calculated on the weight of the protein-polysaccharide complex.
28. The asphalt or bitumen composition of claim 27 wherein the metal oxide filler is iron oxide.
29. The asphalt or bitumen composition of claim 16 wherein the protein- polysaccharide composition further comprises up to 20% by weight of borax.
30. The asphalt or bitumen composition of claim 16 wherein the protein- polysaccharide composition further comprises up to 10% by weight an adjuvant selected from the group consisting of expanded corn gluten, urea and tall oil.
31. The asphalt or bitumen composition of claim 16 wherein the protein- polysaccharide composition further comprises 1 to 5% by weight of rock fines or dust.
32 The asphalt or bitumen composition of claim 16 further comprising between 4 3 to 4 7 by weight of asphalt emulsion or bitumen
33 A method of enhancing internal adhesion of a cementitious composition by admixing with said cementitious composition an effective amount to enhance the internal adhesion of cementitious compositions of a protein- polysaccharide complex composition comprising between about 90% to 99 5% by weight of a water-soluble polysaccharide impregnated with between about 10% to 0 5% by weight of a substantially water- msoluble protein
34 The method of claim 33 wherein the water-soluble polysaccharide is selected from the group consisting of alginate, carrageenin, gum Arabic, tragacanth, guar gum, pectin, ghatti, xanthan gum and mixtures thereof
35 The method of claim 33 wherein the substantially water-insoluble protein is a prolamine
36 The method of claim 33 wherein the substantially water-insoluble protein is zem
37 The method of claim 33 wherein the protein-polysaccharide complex composition further includes at least one additive for promoting impregnation of the water-soluble polysaccharide by the protein
38 The method of claim 33 wherein the substantially water-insoluble protein is hordein or gliadin
39 The method of claim 33 wherein the effective amount of the protein- polysaccharide complex composition to enhance the internal adhesion of said cementitious composition is from 0.0001 to 3.0 weight percent of the total cementitious composition.
40. The method of claim 33 wherein the water-soluble polysaccharide comprises guar gum and the substantially water-insoluble protein comprises zein.
41. The method of claim 33 wherein the protein-polysaccharide complex composition further comprises between about 0.25% to 5% by weight of an acidulant.
42. The method of claim 41 wherein the acidulant is selected from the group consisting of tannic acid, lactic acid, ascorbic acid, acetic acid, citric acid, malic acid, adipic acid, fumaric acid and mixtures thereof.
43. The method of claim 42 wherein the acidulant is citric acid.
44. The method of claim 33 wherein the protein-polysaccharide composition further comprises 0.125 to 5% by weight of a metal oxide filler calculated on the weight of protein-polysaccharide complex.
45. The method of claim 44 wherein the metal oxide filler is iron oxide.
46. The method of claim 33 wherein the protein-polysaccharide composition further comprises up to 20% by weight of borax.
47. The method of claim 33 wherein the protein-polysaccharide composition further comprises up to 10% by weight an adjuvant selected from the group consisting of expanded corn gluten, urea and tall oil.
48 A cementitious composition having improved resistance to erosion and enhanced intemal adhesion comprising a protein-polysaccharide complex composition comprising between about 90% to 99 5% by weight of a water-soluble polysacchande impregnated with between about 10% to 0 5% by weight of a substantially water- msoluble protein
49 A method of stabilizing soil, beaches and road surfaces and preventing erosion by treating the surfaces with a protein-polysaccharide complex composition comprising between about 90% to 995% by weight of a water-soluble polysacchande impregnated with between about 10% to 05% by weight of a substantially water- msoluble protein
50 The method of claim 49 wherein the water-soluble polysaccharide is selected from the group consisting of alginate, carrageenin, gum arabic, tragacanth, guar gum, pectin, ghatti, xanthan gum and mixtures thereof
51 The method of claim 49 wherein the substantially water-insoluble protein is a prolamine
52 The method of claim 49 wherein the substantially water-insoluble protein is zein
53 The method of claim 49 wherein the composition further includes at least one additive for promoting impregnation of the water-soluble polysacchande by the protein
54 The method of claim 49 wherein the substantially water-insoluble protein is hordein or gliadin
55. The method of claim 49 wherein the surfaces are stabilized by treating the surfaces with a protein-polysaccharide complex composition in a particulate form.
56. The method of claim 49 wherein the water-soluble polysaccharide comprises guar gum and the substantially water-insoluble protein comprises zein.
57. The method of claim 49 further comprising: between about 0.25% to 5% by weight of an acidulant.
58. The method of claim 57 wherein the acidulant is selected from the group consisting of tannic acid, lactic acid, ascorbic acid, acetic acid, citric acid, malic acid, adipic acid, fumaric acid and mixtures thereof.
59. The method of claim 57 wherein the acidulant is citric acid.
60. The method of claim 49 wherein the protein-polysaccharide composition further comprises 0.125 to 5% by weight of a metal oxide filler calculated on the weight of protein-polysaccharide complex.
61. The method of claim 60 wherein the metal oxide filler is iron oxide.
62. The method of claim 49 wherein the protein-polysaccharide composition further comprises up to 20% by weight of borax.
63. The method of claim 49 wherein the protein-polysaccharide composition further comprises up to 10% by weight of expanded corn gluten.
64. The method of claim 49 wherein the soil, beach and road surfaces are treated with 1 to 6000 grams of protein-polysaccharide complex per 100 /t2 of surface area.
65. The method of claim 49 wherein beach surfaces are treated with 2000 to 6000 grams of protein-polysaccharide complex per 100 ft2 of surface area.
66. The method of claim 49 wherein soil and road surfaces are treated with 5 to 20 grams of protein-polysaccharide complex per 100 /t2 of surface area.
67. A method of suppressing dust emanating from comminuted stone by treating the comminuted stone with a solution comprising a protein-polysaccharide complex composition comprising: between about 90% to 99.5% by weight of a water-soluble polysaccharide impregnated with between about 10% to 0.5% by weight of a substantially water- insoluble protein.
68. The method of claim 67 wherein the water-soluble polysaccharide is selected from the group consisting of alginate, carrageenin, gum arabic, tragacanth, guar gum, pectin, ghatti, xanthan gum and mixtures thereof.
69. The method of claim 67 wherein the substantially water-insoluble protein is a prolamine.
70. The method of claim 67 wherein the substantially water-insoluble protein is zein.
71. The method of claim 67 wherein the composition further includes at least one additive for promoting impregnation of the soluble polysaccharide by the protein.
72. The method of claim 67 wherein the water-soluble polysaccharide comprises guar gum and the substantially water-insoluble protein comprises zein. 73 The method of claim 67 further comprising between about 0 25% to 5% by weight of an acidulant
74 The method of claim 67 wherein the acidulant is selected from the group consisting of tannic acid, lactic acid, ascorbic acid, acetic acid, citric acid, malic acid, adipic acid, fumaric acid and mixtures thereof
75 The method of claim 67 wherein the protein-polysaccharide composition further comprises 0 125 to 5% by weight of a metal oxide filler calculated on the weight of protein-polysaccharide complex
76 The method of claim 75 wherein the metal oxide filler is iron oxide
77 The method of claim 67 wherein the comminuted stone is treated with 5 to 2000 grams of protein-polysaccharide complex per 100 ft2 of stone surface to be treated
PCT/US1996/013725 1995-09-05 1996-09-04 Use of protein-polysaccharide complex composition for enhancing internal adhesion of cementitious compositions for stabilizing soil, beaches and roads and compositions therefor WO1997011039A1 (en)

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Applications Claiming Priority (6)

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US08/523,162 US5591473A (en) 1993-07-08 1995-09-05 Protein-polysaccharide complex composition, method of preparation and use
US08/523,162 1995-09-05
US08/523,163 1995-09-05
US08/523,163 US5514412A (en) 1995-09-05 1995-09-05 Method of stabilizing soil, beaches and roads
US08/610,658 US5626658A (en) 1995-09-05 1996-03-04 Method of enhancing internal adhesion of cementitious compositions and compositions therefor
US08/610,658 1996-03-04

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WO2010056098A1 (en) * 2008-11-11 2010-05-20 Gregorio Cuevas Pacheco Saccharomyces cerevisiae mucin, mixture and method for increasing compaction of soil and materials for construction

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US5395646A (en) * 1992-03-11 1995-03-07 Societe Nationale Elf Aquitaine Process for the protection of solid surfaces, particularly coastal areas, against pollution by hydrocarbons

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010056098A1 (en) * 2008-11-11 2010-05-20 Gregorio Cuevas Pacheco Saccharomyces cerevisiae mucin, mixture and method for increasing compaction of soil and materials for construction

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