AU2013203025A1

AU2013203025A1 - Composition

Info

Publication number: AU2013203025A1
Application number: AU2013203025A
Authority: AU
Inventors: Stephen Maxwell PAPA; Gregory George REYNOLDS
Original assignee: Individual
Current assignee: Individual
Priority date: 2012-08-08
Filing date: 2013-04-08
Publication date: 2014-02-27
Also published as: WO2014022891A1

Abstract

Abstract A cementitious copolymer composition comprising: 70 to 95 volume percent of a copolymer mixture; 5 to 20 volume percent of a cementitious additive; and 0 to 10 volume percent of an aqueous solution, - .0 n- 30 .0 6.0___ -- 260.00 '~4.00 __ 200.00U S2.0 100.00 ~Ten sile Strength s.- Elongation El ong~ati on 150.00 -119 -120.00 S90.00 _ S60.00 - __ Lu 30.00 ' ~' F1 F2 R4 F6

Description

Composition TECHNICAL FIELD [0001] The present invention is directed towards a cementitious copolymer composition and a method for it use in the construction or repair of roads. BACKGROUND ART [0002] The following discussion of the background art is intended to facilitate an understanding of the present invention only. The discussion is not an acknowledgement or admission that any of the material referred to is or was part of the common general knowledge as at the priority date of the application. [0003] Typically, road compositions are prepared from aggregate compositions of asphalt (bitumen) and rock, wherein the asphalt is utilised as a binder in order to create a hardened product which is laid over a rock or cement foundation. Asphalt pavement material is commonly composed of 5% asphalt cement and 95% aggregates (stone, sand, and gravel). Due to its highly viscous nature, asphalt cement must be heated so it can be mixed with the aggregates and spread across the intended surface. [0004] For driver safety, the asphalt compositions must meet certain performance criteria or specifications in order to be considered useful for road paving. To ensure acceptable performance there are minimum standards set up by government organisations which a composition must adhere to in order to be allowed to be used as road pavement. These minimum specifications relate to properties such as viscosity, toughness, tenacity and ductility. [0005] If these specifications are not met, damage to the resulting road can occur, including permanent deformation, cracking and flexural fatigue. This damage greatly reduces the effective life of paved roads and ultimately driver safety. [0006] Of the above issue, the cracking of the road surface is over the greatest concern. If proper drainage protocols are not in place, the cracks allow for moisture intrusion through the surface of the road and spread throughout the underlying aggregate material. The moisture will then sodden the material and over time, will break the asphalt / aggregate bond, damaging the integrity of the pavement material, causing the pavement to disintegrate. This then requires entire sections of the road to be dug up and new road be placed down. [0007] Previously, it has been demonstrated that the properties of conventional asphalt compositions can be improved by the addition of other substances, such as polymers. A wide variety of polymers have been employed in asphalt compositions. For example, polymers derived from styrene and conjugated dienes are particularly useful, as these polymers have good solubility in asphalt compositions and the resulting modified compositions have improved physical properties. [0008] U.S. Pat. No. 4,145,322, discloses a process for preparing a bitumen-polymer composition consisting of mixing a bitumen, with a block copolymer, having an average molecular weight between 30,000 and 300,000. The colpolymer has the theoretical formula SxBy, in which S corresponds to styrene structure groups and B corresponds to conjugated diene structure groups, and x and y are integers. The resulting bitumen polymer composition is used for road-coating, industrial coating, or other industrial applications. Whilst it remains that the majority of the physical properties of the resulting road composition are increased, they remain un-useful for the purposes of road compositions, mainly due to increased viscosity of the resulting product, where separation of the asphalt and polymer may occur. [0009] Another concern of the use of asphalt compositions concerns the use of volatile solvents in such compositions. Specifically, environmental concerns restrict the use of volatile solvents in such compositions. Moreover, the use of large amounts of volatile solvents in bitumen compositions may lower the viscosity of the resulting composition so that it no longer meets viscosity specifications designated for road paving applications. Additionally, the reduction of other emissions during asphalt applications becomes a target. For example, the reduction of the amount of sulfur compounds that are emitted during asphalt applications is of primary concern. These emissions are compounded by the fact that the asphalt is required to be heated substantially during the application process. [0010] The present invention seeks to overcome, or at least ameliorate, one or more of the deficiencies of the prior art mentioned above, or to provide the consumer with a useful or commercial choice.

[0011] Those skilled in the art will appreciate that the invention described herein is susceptible to variations and modifications other than those specifically described. The invention includes all such variation and modifications. The invention also includes all of the steps, features, formulations and compounds referred to or indicated in the specification, individually or collectively and any and all combinations or any two or more of the steps or features. [0012] Each document, reference, patent application or patent cited in this text is expressly incorporated herein in their entirety by reference, which means that it should be read and considered by the reader as part of this text. That the document, reference, patent application or patent cited in this text is not repeated in this text is merely for reasons of conciseness. [0013] Throughout the specification, unless the context requires otherwise, the term "copolymer mixture" will be understood to be a polymerised composition of two or more monomeric species. [0014] Throughout this specification, unless the context requires otherwise, the word "comprise" or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers. SUMMARY OF INVENTION [0015] In accordance with the present invention, there is provided a cementitious copolymer composition comprising: 70 to 95 volume percent of a copolymer mixture; 5 to 20 volume percent of a cementitious additive; and 0 to 10 volume percent of an aqueous solution, [0016] In one form of the invention the cementitious additive comprises a Portland or blended cement.

[0017] Preferably, the cementitious additive comprises: 10 to 90 percent by weight of Portland Cement clinker; 0 to 80 percent by weight of blast furnace slag; 0 to 60 percent by weight of fly ash; 0 to 10 percent by weight of silica flume; 3 to 8 percent by weight of gypsum; and 0 to 10 percent by weight limestone. [0018] The copolymer mixture may be either provided as a resin or as a powdered solid. [0019] In one form of the present invention the copolymer consists one or more ethylenically unsaturated monomers. Prefferably, the ethylenically unsaturated monomers are selected from the group consisting of vinyl esters, methacrylates, vinylaromatics, olefins, 1,3-dienes and vinyl halides and optionally further monomers copolymerizable therewith. [0020] Suitable monomers from the group of vinyl esters are, for example, those of carboxylic acids having 1 to 15 carbon atoms. Preferably vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of branched monocarboxylic acids having 9 to 11 carbon atoms. [0021] Suitable monomers from the group of acrylic acid esters or methacrylic acid esters are, for example acetate. Preferably, methacrylic acid esters or acrylic acid esters are methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl methacrylate, t- butyl methacrylate, 2-ethylhexyl acrylate. Particularly preferred are methyl Methacrylate, methyl acrylate, n-butyl methacrylate, t-butyl acrylate or 2 ethylhexyl acrylate.

[0022] Suitable monomers from the group of vinylaromatics are styrene, methyl styrene or vinyl toluenenyl. [0023] A suitable monomer from the group of vinyl halide is vinyl chloride. [0024] Suitable monomers from the group of olefins are ethylene, propylene, and the preferred dienes are 1,3-butadiene and isoprene. [0025] In preferred form of the present the copolymer mixture is copolymer of one or more ninyl ester and ethylene. Still preferably the copolymer mixture is a vinyl acetate ethylene (VAE) resin. [0026] Preferably, the volume percentage of the vinyl acetate in the copolymer mixture is selected from the group comprising any one of 99 to 75%, wherein the remainder of the content comprises ethylene. [0027] Still preferably, the volume percentage of the vinyl acetate in the copolymer mixture is selected from the group comprising any one of 80 to 92%, wherein the. remainder of the content comprises ethylene. In a highly preferred form of the present invention, the copolymer mixture comprises 86% vinyl acetate and 14% ethylene. [0028] In one form of the present invention, two or more vinyl acetate ethylene dispersions of varying monomer ratios may also be combined to provide the copolymer mixture. [0029] In one form of the present invention the aqueous solution is water. [0030] Preferably, the composition is able to be applied by a spray applicator, brush or roller. [0031] In accordance with the present invention there is provided a method for coating a surface, the method comprising the steps of preparing the surface; and applying one or more coats of the cementitious copolymer composition of the invention to the surface. [0032] The surface may be bitumen, asphalt, concrete, compacted ground, graded ground, embankments, tailings dams, bunds for mines, or steel. Preferably, the surface is trafficable. [0033] Preferably, the preparation of the surface comprises cleaning the surface. Preferably the cleaning of the surface removes dirt, debris and/or any oils on the surface. [0034] In one form of the present invention, the application of the cementitious copolymer composition is applied to the surface is either through a spray applicator, a roller or a brush. [0035] Preferably, two coats of the cementitious copolymer composition are applied to the surface. Preferably still, three coats of the cementitious copolymer composition are applied to the surface. [0036] In one form of the present invention, the surface is a bitumen or concrete road. [0037] Preferably, the cementitious copolymer composition is applied in one or more coats such that the depth of the cementitious copolymer composition is between 1 and 15 mm. Preferably still the cementitious copolymer composition is applied in one or more coats such that the depth of the cementitious copolymer composition is between 5 and 13 mm. Preferably still the cementitious copolymer composition is applied in one or more coats such that the depth of the cementitious copolymer composition is between 8 and 12 mm. [0038] In one form of the present invention, the method for coating of a surface may be used to encapsulate steel structures in order to provide additional strength and water resistance. [0039] In accordance with the present invention, there is provided a method for the repair of damaged road surfaces, the method comprising the steps of; Preparing the damaged road surface; and applying one or more coats of a cementitious copolymer composition of the invention to the damaged road surface. [0040] Preferably, the preparation of the damaged road surface comprises cleaning the surface. Preferably the cleaning of the damaged surface removes dirt, debris and/or any oils on the surface. [0041] In one form of the present invention, the application of the cementitious copolymer composition is applied to the damaged road surface through a spray applicator, a roller or a brush. [0042] Preferably, two coats of the cementitious copolymer composition are applied to the damaged road surface. Preferably still, three coats of the cementitious copolymer composition are applied to the damaged road surface. DESCRIPTION OF EMBODIMENTS Physical Characteristics of Components [0043] In order for a composition to be utilised for the construction of roads its physical properties must adhere to a set of standard prerequisites. [0044] The applicants have discovered a new cementitious copolymer composition which, when applied to an appropriate substrate surface will be highly flexible, water resistant and non-rigid, whilst have a high tensile strength, load bearing and impact resistance. [0045] Advantageously, due to its composition, the composition of the present invention also remains highly water resistant. This prevents moisture water permeating through to the road substrate. This prevents the previously described breakdown of asphalt roads, a common cause of road failures.

Co-polymers [0046] Vinyl acetate + ethylene (VAE) dispersions are copolymers produced through dispersion polymerization of hard polar monomer vinyl acetate and soft hydrophobic monomer ethylene. An optimal plasticizing monomer for vinyl acetate/ethylene functions as an internal plasticizer, which gives internal plasticity to VAE polymers, prevents plasticizer migration, and ensures lasting flexibility for VAE polymers. VAE copolymers are characterized by high rotation freedom, low spatial hindrance, high backbone flexibility, stable structure, a certain degree of water resistance and a desirable degree of resistance to acids and alkalis. The molecular chains of these copolymers are capable of maintaining stable properties in dilute acid and alkali conditions, by adjusting the polymer structure's copolymer component ratio, i.e. the ratio of vinyl acetate, ethylene or special functional monomers, to develop high-performance dispersions. Examples [0047] Aspects of the present invention will now be illustrated with reference to a series of experimental examples. The description of the examples should not be understood to be limiting the generality of the preceding description of the invention. For the purposes of comparison, the experimental examples include reference to compositions outside the scope of the present invention. The inclusion of such compositions does not derogate from the preceding discussion [0048] The following formations of the dispersion in various polymers where evaluated to determine rheology and elongation. Table I F1 F2 F3 OPC 25.00 25.00 25.00 Silica sand 50R Polymer V 320 75.00 EP701 75.00 EP705K 75.00 Total 1100.00 100.00 1100.00 [0049] Wherein, V 320 is a poly(vinyl alcohol) stabilized vinyl acetate-ethylene copolymer dispersion with a glass transition temperature (Tg) of +14 C.

EP 701 is a polymer dispersion based on vinyl acetate and ethylene. This grade is designed as a plaster/plastic bonding agent and can use without plasticizer or solvent an additives to difficult bonding substrates. EP 705K is a PVOH-protected vinyl acetate-ethylene copolymer of which viscosity is moderate and formaldehyde free. The backbone of the polymer itself gives the dried adhesive film both toughness and flexibility which persist even with water immersion and fluctuations in temperature. Rheology [0050] The rheologies of each of the prepared formulations are described in Table 2. Table 2 F1 F2 F3 Medium viscosity Low viscosity High viscosity Full of foam Slow thickening after Slow thickening after Severe thickening 2Hrs 2Hrs occurs after 5 minutes ad product has no flow after 2 hours In Figure 1 there is shown the results of the tensile strength and elongation testing for Formulas 1 to 3. Elogation Testing [0051] The formations of the dispersion in various polymers were evaluated to compare elongation, the results are shown in Table 3: Table 3 F1 F2 F3 F4 F5 OPC 1 1 1 2 Low heat cement 1 VINNAPAS@ 5044 1.5 1.5 1.5 1.5 1.5 Fly ash(Morwell) 1 Extendosphere BLF 1 H20/1OOg dry 41.6 41.6 87.5 35.2 34.3 [0052] Wherein, VINNAPAS@ 5044 is a copolymer powder of vinyl acetate and ethylene. It is dispersible in water and has very good saponification resistance. Because of its relatively high ethylene content, this resin is soft and flexible. Extendospheres are SG hollow spheres. [0053] In Figures 2 and 3 there is shown the results of the elongation testing and tensile strength testing respectively for F1 to F5. Product Compression Testing [0054] Samples of the composition of the present invention underwent cyclonic missile impact testing in accordance with AS/NZS Standards (TMC39). Three 100 mm x 100mm sample panels of an average thickness of 8.2 mm were prepared for the purposes of the test. Specimens were placed in an Avery Denison Compression Machine and compressed at a speed of 1 m/min, a 5 kg steel planner 100mm x 51 mm section was placed over mounted specimen. The samples comprised of 85 volume percent of copolymer mixture; 10 volume weight of cementitious additive; and 5 volume weight percent of water. The copolymer mixture used was LN 5408 (sourced from Wacker Polymers) which comprises approximately 85% vinyl acetate and approximately 15% ethylene and the cementitious additive was Ordinary Portland Cement (sourced from Boral Chemicals). [0055] The results of the compression testing indicate that the specimen was not compromised after being compressed at 400, 600 and 1500 KN for a 2 min load time. There was no evidence that the integral strength of the specimen itself being compromised and the specimen returned to its normal thickness after 2 days. The results of each of the compression tests are shown in Tables 4 to 6. Table 4: Compression Test Results at 400 KN Specimen Hold Time Starting Finishing Retracting Average Number Thickness Thickness Thickness Retraction (30 mins) 1 2 mins 8.2 mm 6.6 mm 7.4 mm 0.8 mm 2 2 mins 8.1 mm 6.3 mm 6.9 mm 0.6 mm 3 2 mins 8.2 mm 6.7 mm 7.5 mm 0.8 mm Table 5: Compression Test Results at 600 KN Specimen Hold Time Starting Finishing Retracting Average Number Thickness Thickness Thickness Retraction (30 mins) 1 2 mins 8.0 mm 6.0 mm 7.4 mm 0.6 mm 2 2 mins 8.0 mm 6.0 mm 6.9 mm 0.6 mm 3 2 mins 8.0 mm 6.0 mm 7.5 mm 0.5 mm Table 6: Compression Test Results at 1500 KN Specimen Hold Time Starting Finishing Retracting Number Thickness Thickness Thickness 1 1 mins 8.0 mm 6.0 mm 7.4 mm 2 1 mins 8.0 mm 6.0 mm 6.9 mm 3 1 mins 8.0 mm 6.0 mm 7.5 mm Deformation Resistance [0056] Samples of the composition of the present invention underwent deformation resistance by wheel tracking testing in accordance with Austroads Test Method AG PT/T231. The samples comprised of 85 volume percent of copolymer mixure; 10 volume weight of cementitious additive; and 5 volume weight percent of water. The copolymer mixture used was LN 5408 (sourced from Wacker Polymers) which comprises approximately 85% vinyl acetate and approximately 15% ethylene and the cementitious additive was Ordinary Portland Cement (sourced from Boral Chemcials). Two 300 mm x 300mm sample panels of an average thickness of 50 mm were prepared for the purposes of the test. Specimens were mounted to the testing apparatus and wheel tracking on the sample was undertaken for a minimum of 10,000 load passes. The results are shown in Table 7. Table 7: Results of Deformation Resistance Testing Specimen Temperature Thickness Passes Tracking Rate Rut Depth Number (0C) (mm) (mm/1000 passes) (mm) 1 60 50 20000 0.0106 0.8 2 60 50 20000 0.0119 1.4 1 60 50 20000 0.0108 0.8 2 60 50 20000 0.011 1.1 [0055] In Figure 4, there is shown a graphical representation of the results of the deformation resistance testing. [0057] The results of the deformation resistance by wheel tracking testing demonstrated a compliance with AS/NZS standards and a relatively low rut depth.

Application of the composition [0058] Application of the composition of the present invention will now be illustrated with reference to a series of possible application methods. The description of the examples should not be understood to be limiting the generality of the preceding description of the invention. Road Coatings [0059] The composition of the present invention can be applied directly to surface areas by a ground spray application method. For high traffic areas, the coating is built up over multiple layers to obtain a final coating of approximately 12mm. [0060] Road base coatings are constructed in such a way that usage can be obtained for weight distribution of between 40 to 150 tonne depending on specifications. It is suitable also for storage & lay down areas in isolated areas where access is limited and ground undulations are un-removable. It is further envisaged that when the composition of the present invention is applied to large surface areas, the composition may be applied by way of a spray tanker. Car Parks [0061] The composition of the present invention may be applied to a pre-existing car park surface. The composition may be sprayed over the car park bitumen or concrete surfaces to fully waterproof the substrate, and is rated to with stand high traffic weight volumes from 40 to 150 tonne. has also shown to have an exceptional wear factor on heavy traffic passes that exceeds existing road coatings. [0062] When applied to the surface, the composition of the present invention repairs cracks, bonds the existing surface, and has a high wear factor. Once applied, the coating is UV stable, chemical resistant and waterproof, preventing moisture penetration entering the existing substrate.

Commercial/Construction [0063] The composition of the present invention may also be utilised in commercial and construction applications where water damage is of concern. It is envisaged that the composition of the present invention may be used under slabs on commercial sites thus giving a seamless liner that can withstand moisture and insect invasion, or as a barrier on walls that require backfill. [0064] Modifications and variations such as would be apparent to the skilled addressee are considered to fall within the scope of the present invention.

Claims

1. A cementitious copolymer composition comprising: 70 to 95 volume percent of a copolymer mixture; 5 to 20 volume percent of a cementitious additive; and 0 to 10 volume percent of an aqueous solution,

2. A cementitious copolymer composition according to claim 1, wherein the cementitious additive comprises a Portland or blended cement.

3. A cementitious copolymer composition according to claim 1 or 2, wherein the cementitious additive comprises: 10 to 90 percent by weight of Portland Cement clinker; 0 to 80 percent by weight of blast furnace slag; 0 to 60 percent by weight of fly ash; 0 to 10 percent by weight of silica flume; 3 to 8 percent by weight of gypsum; and 0 to 10 percent by weight limestone.

4. A cementitious copolymer composition according to any one of the preceding claims, wherein the copolymer mixture may be either provided as a resin or as a powdered solid.

5. A cementitious copolymer composition according to any one of the preceding claims, wherein the copolymer consists one or more ethylenically unsaturated monomers.

6. A cementitious copolymer composition according to claim 5, wherein the ethylenically unsaturated monomers are selected from the group consisting of vinyl esters, methacrylates, vinylaromatics, olefins, 1,3-dienes and vinyl halides and optionally further monomers copolymerizable therewith.

7. A cementitious copolymer composition according to any one of the preceding claims, wherein the copolymer mixture is a vinyl acetate ethylene (VAE) resin.

8. A cementitious copolymer composition according to any one of the preceding claims, wherein the volume percentage of the vinyl acetate in the copolymer mixture is selected from the group comprising any one of 99 to 75%, and the remainder of the content comprises ethylene.

9. A cementitious copolymer composition according to any one of the preceding claims, wherein the volume percentage of the vinyl acetate in the copolymer mixture is selected from the group comprising any one of 80% to 92% vinyl acetate and the remainder of the content comprises ethylene.

10.A cementitious copolymer composition according to any one of the preceding claims, wherein the copolymer mixture comprises 90% vinyl acetate and 10% ethylene.

11.A cementitious copolymer composition according to any one of claim 1 to 5, wherein two or more vinyl acetate ethylene dispersions of varying monomer ratios may also be combined to provide the copolymer mixture.

12.A cementitious copolymer composition according to any one of the preceding claims, wherein the aqueous solution is water.

13.A cementitious copolymer composition according to any one of the preceding claims, wherein the composition is able to be applied by a spray applicator, brush or roller.

14.A method for coating a surface, the method comprising the steps of: . preparing the surface; and ii. applying one or more coats of the cementitious copolymer composition of the invention to the surface.

15.A method for coating a surface according to claim 12, wherein the surface may be bitumen, asphalt, concrete, compacted ground, graded ground, embankments, tailings dams, bunds for mines, or steel.

16.A method according to claim 12 or claim 13 wherein, the surface is trafficable.

17.A method for coating a surface according to any one of claims 12 to 14, wherein the preparation of the surface comprises cleaning the surface.

18.A method for coating a surface according to claim 15, wherein the cleaning of the surface removes dirt, debris and/or any oils on the surface.

19.A method for coating a surface according to any one of claims 12 to 16, wherein the application of the cementitious copolymer composition is applied to the surface is either through a spray applicator, a roller or a brush.

20.A method for coating a surface according to any one of claims 12 to 17, wherein two coats of the cementitious copolymer composition are applied to the surface.

21. A method for coating a surface according to any one of claims 12 to 18, wherein three coats of the cementitious copolymer composition are applied to the surface.

22.A method for coating a surface according to any one of claims 12 to 19, wherein the surface is a bitumen or concrete road.

23.A method for coating a surface according to any one of claims 12 to 20, wherein the cementitious copolymer composition is applied in one or more coats such that the depth of the cementitious copolymer composition is between 1 and 15 mm.

24.A method for coating a surface according to any one of claims 12 to 21, wherein the cementitious copolymer composition is applied in one or more coats such that the depth of the cementitious copolymer composition is between 5 and 13 mm.

25.A method for coating a surface according to any one of claims 12 to 22, wherein the cementitious copolymer composition is applied in one or more coats such that the depth of the cementitious copolymer composition is between 8 and 12 mm.

26.A method for coating a surface according to any one of claims 12 to 23, wherein the method for coating of a surface may be used to encapsulate steel structures in order to provide additional strength and water resistance.

27.A method for the repair of damaged road surfaces, the method comprising the steps of; i. Preparing the damaged road surface; and ii. applying one or more coats of a cementitious copolymer composition of the invention to the damaged road surface.

28.A method for the repair of damaged road surfaces according to claim 25, wherein the preparation of the damaged road surface comprises cleaning the surface.

29.A method for the repair of damaged road surfaces, according to claim 25 or 26, wherein the cleaning of the damaged surface removes dirt, debris and/or any oils on the surface.

30.A method for the repair of damaged road surfaces, according to any one of claims 25 to 27, wherein the application of the cementitious copolymer composition is applied to the damaged road surface through a spray applicator, a roller or a brush.

31.A method for the repair of damaged road surfaces, according to any one of claims 25 to 28, wherein two coats of the cementitious copolymer composition are applied to the damaged road surface.

32.A method for the repair of damaged road surfaces, according to any one of claims 25 to 28, wherein three coats of the cementitious copolymer composition are applied to the damaged road surface.

33.A cementitious copolymer composition, substantially as hereinbefore described with reference to any one of formulations F1 to F5.