AU2001272936B2 - A tunnel waterproofing construction method - Google Patents

A tunnel waterproofing construction method Download PDF

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AU2001272936B2
AU2001272936B2 AU2001272936A AU2001272936A AU2001272936B2 AU 2001272936 B2 AU2001272936 B2 AU 2001272936B2 AU 2001272936 A AU2001272936 A AU 2001272936A AU 2001272936 A AU2001272936 A AU 2001272936A AU 2001272936 B2 AU2001272936 B2 AU 2001272936B2
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tunnel
cement concrete
rubber
spraying
film
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AU2001272936A1 (en
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Keiichi Kosuge
Yoshio Shimizu
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WR Grace and Co Conn
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WR Grace and Co Conn
WR Grace and Co
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    • EFIXED CONSTRUCTIONS
    • E21EARTH OR ROCK DRILLING; MINING
    • E21DSHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
    • E21D11/00Lining tunnels, galleries or other underground cavities, e.g. large underground chambers; Linings therefor; Making such linings in situ, e.g. by assembling
    • E21D11/38Waterproofing; Heat insulating; Soundproofing; Electric insulating
    • E21D11/383Waterproofing; Heat insulating; Soundproofing; Electric insulating by applying waterproof flexible sheets; Means for fixing the sheets to the tunnel or cavity wall
    • EFIXED CONSTRUCTIONS
    • E21EARTH OR ROCK DRILLING; MINING
    • E21DSHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
    • E21D11/00Lining tunnels, galleries or other underground cavities, e.g. large underground chambers; Linings therefor; Making such linings in situ, e.g. by assembling
    • E21D11/38Waterproofing; Heat insulating; Soundproofing; Electric insulating
    • EFIXED CONSTRUCTIONS
    • E21EARTH OR ROCK DRILLING; MINING
    • E21DSHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
    • E21D11/00Lining tunnels, galleries or other underground cavities, e.g. large underground chambers; Linings therefor; Making such linings in situ, e.g. by assembling
    • E21D11/04Lining with building materials
    • E21D11/10Lining with building materials with concrete cast in situ; Shuttering also lost shutterings, e.g. made of blocks, of metal plates or other equipment adapted therefor
    • E21D11/105Transport or application of concrete specially adapted for the lining of tunnels or galleries ; Backfilling the space between main building element and the surrounding rock, e.g. with concrete

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  • Engineering & Computer Science (AREA)
  • Structural Engineering (AREA)
  • Mining & Mineral Resources (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Lining And Supports For Tunnels (AREA)

Description

WO 01/96710 PCT/US01/18174 A TUNNEL WATERPROOFING CONSTRUCTION METHOD Field of the Invention This invention relates to a waterproofing construction and method for tunnels, and more particularly to the constructions and use of a vulcanization-type rubber film on a tunnel waterproofing surface.
Background of the Invention In this invention, paste, mortar, and concrete are used as general terms to refer to cement concrete.
The principle tunnel construction method in Japan currently is the NATM method. In the NATM construction method, a primary coating is applied by means of spraying mortar or concrete immediately after excavation of the tunnel to prevent falling rock and water leakage in the excavation region. After this, a secondary coating of concrete is applied to stabilizing the tunnel by maintaining tunnel strength.
At this time, a waterproofing sheet is installed for the waterproofing purposes, and insulation between the primary coating concrete and the secondary coating concrete, so that leakage of water into the tunnel can be prevented, and so that cracks due to binding of the secondary concrete coating to earth mounds, which might move, can be prevented. Most recently, tunnel excavation has been performed by tunnel boring machines (TBM construction method), and waterproofing sheets are installed for the same objectives.
SUBSTITUTE SHEET (RULE 26) WO 01/96710 PCT/US01/18174 Installation of this waterproofing sheet involves installation on the primary coating concrete surface by hunman hands. In particular, there is the problem that it is an operation that is performed on a stand at the ceiling of the tunnel, such that it is dangerous, and there are limitations on movement during the installation operations.
In addition, there is the problem that the application surface is the excavation surface, which is uneven, making application after the primary coating difficult to accomplish.
Further, because the width of the sheet is narrow one to two meters), it is necessary to superimpose numerous waterproofing sheets. The overlapping of the waterproofing sheets requires great effort and is sometimes uneconomical.
There is the further problem that water infiltrates between the waterproofing sheet and the secondary concrete coating due to damage of the sheet by poorly welded components. Also, the irregularities in the excavated surface of the tunnel often defeats the waterproofing capacity of the sheet.
In order to solve these problems, methods for performing waterproofing by spraying an aqueous solution of a polymerizable monomer and forming a waterproofing film was disclosed in Japanese Patent Application (Early Disclosure) No. 61-19683 (1986) and Japanese Patent Application (Early Disclosure) No. 3- 137182 (1991).
However, there are still problems in that moist surfaces cause poor adhesion, and the film becomes non-uniform due to dripping after spraying. Also, the spraying is foggy, which deteriorates the working environment, and the price is high, making the application uneconomical.
2 SUBSTITUTE SHEET (RULE 26) The present inventors conducted various studies of the aforementioned problems. As a result, they discovered a novel tunnel waterproofing construction method in which a rubber emulsion vulcanizable at ambient temperatures is applied by blowing it and forming a film without seams. The film has excellent physical properties and waterproofing capacity, and the method is extremely economical because it avoids dripping and fogging during spray application. It has fewer organic volatile components in comparison with urethane-based compositions; it has no unpleasant odors; and it has excellent workability and waterproofing properties inside the tunnel. Cracks do not develop in the secondary cement concrete coating.
The above discussion of background art is included to explain the context of the present invention. It is not to be taken as an admission that any of the material referred to was published, known or part of the common general knowledge in Australia as at the priority date of any of the claims of this specification.
Summary of the Invention According to a first aspect, the present invention provides a tunnel waterproofing construction method, including: spray-applying a primary spray cement concrete onto a tunnel excavation surface; spraying onto said primary spray cement concrete on said surface a rubber emulsion operative to vulcanize at ambient temperature to form a rubber film; and coating a secondary cement concrete onto said rubber film.
In one preferred embodiment, the present invention provides a tunnel waterproofing construction method, wherein a primary spray cement concrete coating is spray applied onto a tunnel excavation surface, a rubber emulsion operative to vulcanize at ambient temperature is spray-applied onto the primary spray cement concrete coating, thereby forming a rubber film thereon, and a secondary cement concrete coating is applied onto the rubber film surface.
More particularly, the tunnel excavation surface is made "nonlanded" by the primary spray cement concrete coating (in other words, the irregularities of the excavated earth surface are evened out) so that the ambient-temperature vulcanizable emulsion can be spray-applied onto the primary spray cement concrete and thereafter a secondary cement coating can be established thereon.
In further exemplary embodiments, a buffer-water conductive layer is installed on the primary spray cement concrete coating, and the ambient-temperature vulcanizable emulsion is thereafter applied thereon to form a rubber film, whereupon XAMeganXIo delete\72936-01 .doc the secondary cement concrete coating may subsequently be established on the rubber film.
According to a second aspect, the present invention provides a tunnel waterproofing construction made using a method of the above-mentioned type.
Detailed Description of Embodiments of the Invention Exemplary embodiments of the present invention may now be described in further detail.
This invention is a construction method in which a film without seams and having good physical properties is formed, preferably by spray-applying a primary spray cement concrete on an excavated tunnel surface, after which an ambienttemperature vulcanization-type rubber emulsion is sprayed and a vulcanization reaction is obtained at ambient temperature. From the standpoints of facilitating attachment of the primary spray cement concrete and achieving good workability, the ambienttemperature vulcanization-type rubber emulsion should comprise a substance that contains the rubber emulsion (hereafter referred to as agent A) and an oil-extended oil in which the vulcanization agent is dispersed (hereafter referred to as agent Agent A and agent B are sprayed while being mixed at the nozzle tip (used for spraying A and
B).
The rubber emulsion that is used in agent A can be a synthetic rubber, such as styrene butadiene rubber, chloroprene rubber, or isoprene rubber, as well as natural rubber. In addition, blends of these rubbers may be used. Of these substances, styrene butadiene rubber is desirable from the standpoints of vulcanization physical properties and economic factors, and chloroprene is desirable from the standpoint of increased flame-retarding properties.
X:\Megan'No delete\72936-01.doc.
WO 01/96710 PCT/US01/18174 From the standpoint of obtaining a good film, the solid component of the rubber emulsion should be 15 to 40 parts by mass, and preferably 20-30 parts by mass, in 100 parts of total solid components after blending agent A and agent B.
From the standpoint of the stability of the rubber emulsion, a strong alkali such as KOH or NaOH may be used as a pH regulator in an amount ordinarily of parts by mass, and, at a maximum of 2.5 parts by mass, per 100 parts by mass of rubber solid components.
From the standpoint of facilitating regulation of the physical properties of the rubber after vulcanization, an oil in which an aromatic oil and paraffin oil are mixed is desirable as the oil-extended oil used for agent B. Paraffin oil is used at a ratio of less than 50 parts by mass per 100 parts by mass of rubber solid components for the purpose of adjusting viscosity when it is blended with agent A. Chlorinated paraffin can also be used for the purpose of increasing flame-retarding properties. Asphalt can also be used in agent B. The ratio should be less than 30 parts by mass per 100 parts by mass of rubber solid components.
The vulcanization agent that is dispersed in the oil-extended oil used in agent B may be a sulfur vulcanization agent, with sulfur being preferred. The quantity of vulcanization agent should be 0.5 to 20 parts by mass per 100 parts by mass of rubber solid components.
A vulcanization accelerator may be used in combination with agent B.
Examples of vulcanization accelerators can include zinc isopropyl xanthate, zinc dibutyldithiocarbamate dibutylamine complex and zinc oxide. The quantity of vulcanization accelerator used should be 0.1 to 5.0 parts by mass per 100 parts by SUBSTITUTE SHEET (RULE 26) WO 01/96710 PCT/US01/18174 mass of rubber solid components when zinc isopropyl xanthate is used, 0.1 to parts by mass per 100 parts by mass of rubber solid components when zinc dibutyldithiocarbamate dibutylamine complex is used, and 0.5 to 20.0 parts by mass per 100 parts by mass of rubber solid components when zinc oxide is used.
In addition, additives such as fumed silica, polymer fibers, and powdered rubber may be used in agent B in amounts of 0.5 to 25 parts by mass per 100 parts by mass of the total solid components.
In addition, various types of inorganic substances (metal oxides such as calcium oxide, Portland cement, high alumina cement and calcium sulfate) and various types of coloring agent can also be used in agent B.
The tunnel waterproofing construction method may be a construction method based on the NATM construction method of the TBM construction method, in which a rubber emulsion operative to vulcanize at ambient temperature is spray applied onto an excavated tunnel surface after a primary spray cement concrete is sprayed thereon, or after a buffer-water conductive layer drainage) is established on the primary spray-applied cement concrete, with vulcanization and hardening being effected at ambient temperature.
Moreover, smoothing out the irregularities of the excavation surface by "nonlanded" regulation) by spray-applying the primary spray cement concrete on the tunnel excavation surface (from an economic standpoint, it is desirable to effect "nonlanded" regulation by further spraying of a general primary spray cement concrete after ordinary spraying of a fast-drying spray cement concrete), or by applying a buffer-water conducting layer to the primary spray cement concrete surface 6 SUBSTITUTE SHEET (RULE 26) WO 01/96710 PCT/US01/18174 after spraying a primary spray cement concrete on the tunnel excavation surface and then further spraying a rubber emulsion operative to vulcanize at ambient temperature is desirable from the standpoints of further increasing the insulation effect and making it difficult for cracking to occur in the secondary coating cement structure. Further, better results are obtained when these measured are used in combination.
The establishment of a buffer-water conductive layer (drainage) has the particular advantage that makes it possible to form a film when the ambient temperature vulcanizable emulsion is formed, even when there is some water leakage from the primary spray cement concrete.
Examples of buffer-water conductive layers include layers formed by spraying fibrous substances such as moistened pulp and layers in which nonwoven fabrics such as long polyester fibers and polypropylene, or in which irregularly shaped plates are affixed.
Although there are no particular limitations on the method for affixing nonwoven fabrics or irregularly shaped plates to the primary spray cement concrete surface, adhesive agents and rivets may be used.
The spraying machine that is used in the waterproofing construction method of this invention is a type whereby agent A and agent B are introduced under pressure by separate pumps, with their ratios being regulated, and they are mixed at the nozzle component or before the nozzle, after which the mixture is sprayed at ordinary air pressure. However, an airless spraying machine may be used, or an air application machine may be used.
7 SUBSTITUTE SHEET (RULE 26) WO 01/96710 PCT/US01/18174 By spraying and applying the ambient-temperature-hardening rubber emulsion to a thickness on the order of 1 to 3 mm. (which emulsion may also be more thickly sprayed), a film without seams and of good physical properties is formed at normal temperature.
After the film has been formed in this way, a secondary coating cement concrete is applied and construction is completed.
The invention may be illustrated by the following examples.
Example 1 A U-shaped simulation tunnel having openings of 4 m, a height of 3.5 m, and a length of 3 m was made. Irregularities of the tunnel earth mound surface were presumed in the simulation tunnel, and fifteen concrete blocks of 15 cm in width, cm in height, and 20 cm in length were installed at suitable intervals to form an irregular surface.
Fast-drying mortar was sprayed as the primary spray mortar and "nonlanded" adjustment of the irregular surface was effected the sprayed surface irregularities were evened out).
Immediately after spraying, a two-agent rubber emulsion operative to vulcanize at ambient temperature (available from Grace Construction Products, United States, under the brand name PROCOR 75), comprised of agent A of which styrene butadiene rubber was the principle component, and agent B which contained calcium oxide, sulfur, aromatic oil, paraffin oil, zinc oxide, clay and calcium carbonate, was applied by spraying on the mortar surface to a thickness of 2 mm by an 8 SUBSTITUTE SHEET (RULE 26) WO 01/96710 PCT/US01/18174 air spraying machine after mixing agent A and agent B at the nozzle component. One day after spraying, secondary coating concrete was applied to a thickness of 30 cm.
As a result, the following points were found.
1. There was a good film application capacity using the spray operations, and it was possible for two operators to apply film in an amount of more than 100 m 2 /hour.
2. There was no generation of fog during spraying, no dripping from roof surfaces, no unpleasant odor, and a spraying of uniform thickness could be performed.
3. A uniform, good film with no cracks or pinholes could be obtained. In addition, no differences were observed in the thickness of the film immediately after application and after hardening.
4. Checks were made by visual observation for the occurrence of cracks after removal of secondary coating cement concrete from the mold frame and three months thereafter. As a result, cracks were not found.
The properties of the film formed by spray application are indicated below. A good ambient-temperature vulcanization type rubber film was obtained. Film strength: 0.82 (N/mm 2 (ambient temperature); 1.1 N/mm2 (-300 Elongation: 700% (ambient temperature); greater than 800% 30 0 Recovery after 100% elongation: 95%. Tearing strength: 4.55 N/mm 2 Resistance to static water pressure: The test methods for the various physical properties were as follows.
9 SUBSTITUTE SHEET (RULE 26) WO 01/96710 PCT/US01/18174 Film strength, elongation and recovery were tested in accordance with ASTM D 412-92.
Tearing strength was tested in accordance with ASTM D 642-86.
Resistance to static water pressure was tested in accordance with ASTM D 5385-93 (Determination in cases in which ambient-temperature vulcanization type rubber emulsions are sprayed onto concrete surfaces).
Example 2 A U-shaped simulation tunnel having openings of 4 m, a height of 3.5 m, and a length of 3 m was made. Irregularities of the tunnel earth-mound surface were presumed in the simulation tunnel, and fifteen concrete blocks of 15 cm in width, cm in height, and 20 cm in length were installed at suitable intervals to form an irregular surface.
Fast-drying mortar was sprayed as the primary spray mortar, and "nonlanded" adjustment of the irregular surface was effected uneven spraying on tunnel wall was evened out).
Immediately after spraying, a nonwoven fabric made of polyester fibers was affixed by rivets to the primary spray mortar surface.
A two-agent, ambient-temperature vulcanization-type rubber emulsion (PROCOR 75 brand from Grace Construction Products, United States) was applied to the surface of the nonwoven fabric and was applied by spraying to the mortar surface by an air spraying machine so that the thickness was 2 mm after mixing agent A and agent B at the nozzle component, with a film being formed. One day after spraying, secondary coating concrete was applied to a thickness of 30 cm.
SUBSTITUTE SHEET (RULE 26) WO 01/96710 PCT/US01/18174 As a result, the following points were found.
1. There was a good film application capacity using the spraying operations, and it was possible for two operators to apply film in an amount of more than 100 m 2 /hour.
2. There was no dripping from roof surfaces, no unpleasant odor, and spraying of a uniform thickness could be performed.
3. A uniform, good film with no cracks or pinholes could be obtained. In addition, no differences were observed in the thickness of the film immediately after application and after hardening.
4. Checks were made by visual observation for the occurrence of cracks after removal of secondary coating cement concrete from the mold frame and three months thereafter. As a result, no cracks were found.
Example 3 A U-shaped simulation tunnel having openings of 4m, a height of 3.5 m, and a length of 3 m was made. Irregularities of the tunnel earth mound surface were presumed in the simulation tunnel, and fifteen concrete blocks of 15 cm in width, cm in height, and 20 cm in length were installed at suitable intervals to form an irregular surface.
Fast-drying mortar was sprayed as the primary spray mortar without making "nonlanded" adjustment of the irregular surface. Immediately after spraying, a twoagent, ambient-temperature-type rubber emulsion (manufactured by Grace Construction Products, United States, under the brand name PROCOR 75) was 11SUBSTITUTE SHEET (RULE 26) SUBSTITUTE SHEET (RULE 26) WO 01/96710 PCT/US01/18174 applied by spraying to the mortar surface by an air spraying machine so that the thickness was 2 mm after mixing agent A and agent B at the nozzle component, with a film being formed. One day after spraying, secondary coating concrete was applied to a thickness of 30 cm.
As a result, the following points were found.
1. There was a good film application capacity using the spraying operations, and it was possible for two operators to apply film in an amount of more than 100 m2/hour.
2. Checks were made by visual observation for the occurrence of cracks after removal of secondary coating cement concrete from the mold frame and three months thereafter. As a result, it was found that one crack had developed in the secondary coating concrete surface. However, when the core in that region was removed and checked, there were no abnormalities in the film and water leakage was not seen.
Comparative Example 1 The same procedure was carried out as in Example 3 except that mixtures comprised of aqueous acrylate and methacrylate solutions and of redox catalyst systems were used instead of two-agent, ambient temperature type rubber emulsion (brand name PROCOR 75, manufactured by Grace Construction Products, USA).
As a result, the following points were found.
12 SUBSTITUTE SHEET (RULE 26) WO 01/96710 PCT/US01/18174 1. There was marked fogging due to spraying, and the working environment was poor. In addition, icicle-like dripping occurred on the sprayed surface, and operating characteristics were poor.
2. Checks were made by visual observations for occurrence of cracks after removal of the secondary coating concrete from the mold frame and three months thereafter. As a result, it was found that two cracks had developed in the secondary coating concrete surface.
The following results (and capabilities) were achieved by the tunnel waterproofing construction method using the ambient-temperature vulcanization type emulsion of this invention.
1. The ambient-temperature vulcanization-type emulsion is not toxic.
Because the water component in this emulsion does not separate, water infiltration into the working environment does not occur. The ambienttemperature vulcanization-type emulsion does not cause fogging that can occur during spraying. For these reasons, workability can be greatly improved, safety during operations can be improved, and the environment can be protected.
2. By effecting vulcanization at ambient temperature, a film having good physical properties and not having seams can be formed.
3. A film having superior waterproofing properties can be applied in stable fashion.
13 SUBSTITUTE SHEET (RULE 26) WO 01/96710 PCT/US01/18174 4. Because organic solvents are not used, there is little possibility of the occurrence of fire or intoxication during operations and toxic gases are not generated during such fires.
The tunnel waterproofing construction method of this invention exhibits good application characteristics and wide application can be made to a large surface by a small number of workers. Therefore, overall costs can be reduced.
6. Cracking of the secondary coating cement concrete can be further decreased as a result of the facts that: the primary spray cement concrete surface is subjected to "nonlanded" regulation, a buffer material-water conductive layer is established, and that both treatments and are performed.
14 SUBSTITUTE SHEET (RULE 26)

Claims (6)

1. A tunnel waterproofing construction method, including: spray-applying a primary spray cement concrete onto a tunnel excavation surface; spraying onto said primary spray cement concrete on said surface a rubber emulsion operative to vulcanize at ambient temperature to form a rubber film; and coating a secondary cement concrete onto said rubber film.
2. A method as claimed in claim 1 wherein said tunnel excavation surface is lined with said primary spray cement concrete.
3. A method as claimed in claim 1 or 2 wherein, after spray-applying said primary spray cement concrete on the tunnel excavation surface, a buffer-water conductive layer is installed on said primary cement concrete surface, and thereafter the rubber emulsion is applied on the buffer-water conductive layer to provide a rubber film, and thereafter a secondary cement concrete is coated onto the rubber film surface.
4. A tunnel waterproofing construction made by the method of any one of the preceding claims.
A tunnel waterproofing construction method substantially as herein described with reference to the accompanying examples.
6. A tunnel waterproofing construction substantially as herein described with reference to the accompanying examples. Dated: 11 December 2002 PHILLIPS ORMONDE FITZPATRICK Attorneys for: W.R. GRACE CO.-CONN. X:Wlegan\No delete\72936-Oi.doc
AU2001272936A 2000-06-12 2001-06-05 A tunnel waterproofing construction method Ceased AU2001272936B2 (en)

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JP2000-175768 2000-06-12
JP2000175768A JP4459391B2 (en) 2000-06-12 2000-06-12 Tunnel waterproofing method
PCT/US2001/018174 WO2001096710A1 (en) 2000-06-12 2001-06-05 A tunnel waterproofing construction method

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JP4459391B2 (en) 2000-06-12 2010-04-28 電気化学工業株式会社 Tunnel waterproofing method
JP2002275828A (en) * 2001-03-16 2002-09-25 Denki Kagaku Kogyo Kk Waterproof structure and waterproof construction method
KR100894885B1 (en) * 2007-04-27 2009-04-30 (주)리뉴시스템 Execution method of waterproof for shield tunnel and waterproof structure
CN101614129B (en) * 2009-08-10 2011-07-27 招商局重庆交通科研设计院有限公司 Construction method of tunnel waterproof and water drainage system
KR101068624B1 (en) * 2011-03-30 2011-09-28 대지종건(주) Arc-shaped divided segments for non-excavation type constructed tunnels and construccting conduits
CN104373138B (en) * 2014-10-13 2017-03-29 中南大学 The construction method that waterproof layer is reinvented when a kind of tunnel lining structure is repaired
JP6534562B2 (en) * 2015-06-04 2019-06-26 デンカ株式会社 Structure and construction method
KR101790217B1 (en) * 2016-12-30 2017-10-25 씨카코리아(주) Waterproofing system
CA3096861A1 (en) * 2018-05-02 2019-11-07 Relborgn Pty Ltd Method, apparatus and composition for sealing of surfaces

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US3545213A (en) * 1967-03-22 1970-12-08 Gustav Sebor Structure for lining underground spaces
US4247221A (en) * 1978-05-02 1981-01-27 Kali Und Salz Ag Process for lining tunnels
US4695188A (en) * 1984-03-13 1987-09-22 Neste Oy Lined rock cistern or tunnel
US4915542A (en) * 1984-11-16 1990-04-10 Fernando Gordun B Process for waterproofing surfaces
US5993114A (en) * 1995-06-12 1999-11-30 Wrc Plc Apparatus and method for pipeline renovation
US5763014A (en) * 1996-01-04 1998-06-09 W. R. Grace & Co.-Conn. Liquid applied waterproofing
US6193439B1 (en) * 1996-01-08 2001-02-27 Mbt Holding Ag Process for cladding substrates and constructions produced thereby
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US6403686B1 (en) * 2000-04-11 2002-06-11 W.R. Grace & Co. - Conn. Rheologically-dynamic, liquid-applicable elastomeric compositions

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WO2001096710A1 (en) 2001-12-20
JP2001355397A (en) 2001-12-26
JP4459391B2 (en) 2010-04-28
CN1457383A (en) 2003-11-19
AU7293601A (en) 2001-12-24
EP1290313A1 (en) 2003-03-12
KR20030034093A (en) 2003-05-01
CA2411271A1 (en) 2001-12-20
CN1280524C (en) 2006-10-18
EP1290313A4 (en) 2005-04-27

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