WO2019126847A1 - Fibre de renforcement de fibrociment, procédé de production de cette fibre et article de fibrociment - Google Patents

Fibre de renforcement de fibrociment, procédé de production de cette fibre et article de fibrociment Download PDF

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Publication number
WO2019126847A1
WO2019126847A1 PCT/BR2018/050093 BR2018050093W WO2019126847A1 WO 2019126847 A1 WO2019126847 A1 WO 2019126847A1 BR 2018050093 W BR2018050093 W BR 2018050093W WO 2019126847 A1 WO2019126847 A1 WO 2019126847A1
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WO
WIPO (PCT)
Prior art keywords
fiber
pet
fibers
fibre
cement
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/BR2018/050093
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English (en)
Portuguese (pt)
Inventor
Guilherme Silva BOLLINI
Valdir ZAMPIERI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain do Brasil Produtos Industriais e para Construcao Ltda
Original Assignee
Saint Gobain do Brasil Produtos Industriais e para Construcao Ltda
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
Application filed by Saint Gobain do Brasil Produtos Industriais e para Construcao Ltda filed Critical Saint Gobain do Brasil Produtos Industriais e para Construcao Ltda
Priority to MX2020006766A priority Critical patent/MX2020006766A/es
Priority to BR112020012722-1A priority patent/BR112020012722B1/pt
Publication of WO2019126847A1 publication Critical patent/WO2019126847A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B16/04—Macromolecular compounds
    • C04B16/06—Macromolecular compounds fibrous
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
    • E04C5/07—Reinforcing elements of material other than metal, e.g. of glass, of plastics, or not exclusively made of metal

Definitions

  • the present invention discloses a high tenacity fiber reinforcement fiber, wherein the fiber is a blended monofilament comprising polypropylene homopolymer, polyethylene terephthalate homopolymer and a polyolefin polymer compatibilizing material.
  • Composite materials result from a physical and / or chemical combination of two or more materials, the main purpose of which is to obtain, in the same material, individual characteristic properties or a synergy of performances previously not obtained in each, separately .
  • the material having the greatest mass or volume content is referred to as a matrix in which other materials in the form of fibers or particles are dispersed, responsible for modifying and imparting new properties to the final material composed of the mixture of the phases .
  • Portland cement can be considered as a ceramic product, resulting from the calcination and sintering of a suitable mixture of carbonates and clays at temperatures in the order of 1500 ° C.
  • Ordinary Portland cement is the product resulting from the grinding of the sintered pellets (Portland clinker), together with additives to control their initial solidification, from which they no longer work.
  • Concretes and mortars made from Portland cement mixtures, aggregates and sands are the most widely used composite materials in the construction industry. They are versatile materials of high durability and low cost. Despite the high mechanical resistance to compression, they are fragile and brittle products with low tensile strength and where the propagation of cracks happens very fast. THE incorporation of fibers or reinforcements has as main objective to modify the brittle behavior of these materials to obtain a more ductile mechanical and plastic behavior.
  • metal reinforcements in the form of continuous bars or reinforcing screens is a common practice as a way of improving the mechanical behavior in traction of concrete parts and structures, and are more commonly known by the industry as "reinforced concrete”.
  • Metallic or polymeric cut fibers may also be incorporated into the blend. These fibers exhibit lengths of the order of centimeters, and are then called macrofibres.
  • Asbestos cement in turn, is also a composite material composed of a mixture of Portland cement, natural and / or synthetic fibers and mineral aggregates, as well as process additives.
  • Asbestos-specific reinforcing fibers have unique dimensions, geometries and characteristics as they meet requirements that together confer durability, performance and processability. They are typically cut fibers in smaller lengths (4 mm to 12 mm), micrometer diameters (10-20 mih) and have high tensile strengths (> 500 MPa).
  • Asbestos cement was originally developed and patented by Ludwig Hatschek in 1901 from mixtures of Portland cement and asbestos fibers. Hatschek technology is to this day one of the most widespread and used in the manufacture of these products. This technology is based on the filtration of an aqueous lotion consisting of cement, reinforcing fibers and mineral aggregates on a rotating metal screen. The thin film deposited on the rotating screen ( ⁇ 0.3 mm) is continuously collected by a felt, vacuum-drained and accumulated in a large cylindrical metal press called a forming roller. Once the desired thickness is reached (usually between 4 and 20 mm), the fresh product green ") is cut having sufficient plasticity to be shaped into different geometries.
  • the products After forming, the products are usually held between metal molds until the initial cement hardening. After the initial curing, the products are removed from the molds and stacked for final curing in the open air. Both corrugated asbestos cement tiles and cementitious tiles produced by Hatschek follow this well-known production route.
  • Hatschek technology can be used for the production of autoclaved products, where the healing and hydration steps are accelerated in autoclaves with higher pressures and temperatures (common conditions: 9-10 bar; 180 ° C; 12 hours).
  • Other manufacturing processes known as Magnani, Flow-on and Mazza are also considered variants of the Hatschek process.
  • Asbestos fibers are the most common and known fibrous reinforcement used in asbestos cement products, mainly because they have special properties which make them suitable for reinforcing products with hydraulic binder matrices. These fibers provide adequate mechanical reinforcement, aid the filtration and particle retention process, as well as having excellent dispersion and compatibility with the cementitious matrix.
  • glass fibers exhibit initially satisfactory resistances, but suffer chemical decomposition due to the alkaline character of the matrix and the properties of mechanical resistance fall catastrophically in a short time.
  • Carbon fibers are very fragile, have low adhesion and high cost; steel fibers exhibit high density and suffer corrosion; cellulose fibers have insufficient durability; polyacrylonitrile and polyvinyl alcohol fibers are costly and, finally, conventional polyolefin fibers have insufficient mechanical properties, despite having attractive costs and excellent resistance to alkalinity of the matrix.
  • Synthetic polyolefinic fibers such as polypropylene (PP) are potentially used for the same purpose with lower costs and higher availability, but to date they have presented some drawbacks such as low interfacial adhesion to the cementitious matrix, example.
  • PP polypropylene
  • several studies focused on the surface modification of these fibers were performed.
  • Mcalpin et al. Published in patent US 4,861,812 the use of a polyolefin fiber containing a modifying agent product from the reaction of an alkylaminoalkoxysilane blend with a maleic anhydride modified polyolefin to increase its wettability in a solution with cement and thus its adhesion with the matrix.
  • Vidts et al. There is shown a post-fabrication surface treatment method of PP fibers for reinforcement of fiber cement containing firstly a corona treatment step and thereafter a surface treatment through a deposit from an aqueous solution of an organic polymer containing polar groups, which may comprise maleic anhydride, acrylic acid and methacrylic acid.
  • EP 1 362 936 A1 a co-extruded PP fiber whose edge consisted of a blend of polypropylene and a thermoplastic elastomer (ethylene-propylene, hydrogenated styrene-butadiene, styrene- butadiene-styrene, styrene-ethylene-butylene-styrene) which may or may not be modified with polar groups (maleic anhydride, acrylic acid, methacrylic acid).
  • polar groups maleic anhydride, acrylic acid, methacrylic acid
  • the present invention describes a fiber reinforcement fiber, wherein the fiber is a blended monofilament comprising polypropylene homopolymer, polyethylene terephthalate homopolymer and a polyolefin polymer compatibilizing material.
  • the fiber is a blended monofilament comprising polypropylene homopolymer, polyethylene terephthalate homopolymer and a polyolefin polymer compatibilizing material.
  • a process for producing such fibers, as well as fiber cement articles employing the monofilaments employing the monofilaments.
  • Figure 1 shows an electron microscopic image of the filament produced with pure PP.
  • Figure 2a shows an electron microscopic image of the filament of the present invention made with PP and PET.
  • Figure 2b shows another electron microscopic image of the filament of the present invention made with PP and PET.
  • Figure 3 shows a sequence of electron microscopy images showing the increased compatibility of the PET with the PP matrix according to the increase in the addition content of the compatibilizing material.
  • Figure 4 shows a graph of the results of mechanical strength using different concentrations of fibers.
  • Figure 5 shows a graph of the results of mechanical strength using different concentrations of fibers, in addition to different lengths.
  • Figure 6 shows a graph of the hot water durability results of fiber cement articles using prior art and the present invention.
  • Figure 7 shows a graph of the flexural strength results of fiber cement articles using fibers of the foregoing and of the present invention in different concentrations and lengths.
  • Figure 8a shows an electron microscopic image of the monofilament of the present invention immersed in the cementitious matrix after accelerated aging with evidence at the anchor sites with the cementitious matrix.
  • Figure 8b shows an electron microscopic image of filaments produced with pure PP immersed in the cementitious matrix after accelerated aging with evidence of poor surface adhesion with the cementitious matrix.
  • the present invention relates to a polypropylene (PP) monofilament fiber blended with polyethylene terephthalate (PET) used for reinforcement of fiber cement materials.
  • PP polypropylene
  • PET polyethylene terephthalate
  • the monofilament disclosed and claimed herein forms strong interfaces with cementitious matrices, thus enabling the use of shorter fibers, generating a greater number of individual fibers with the same mass addition, resulting, consequently, in superior mechanical performance of asbestos cement products.
  • PET provides a hydrophilic character to the fiber and, consequently, improved chemical adhesion to the cementitious matrix. Moreover, the imperfect mixing of PP with PET produces the surface micro-roughness in the fiber and, consequently, improvement of its physical adhesion.
  • Figure 1 shows an electron microscopy image of a pure PP filament with a diameter of 14 micrometers, where it is possible to verify that the fiber is smooth.
  • Figure 2a and Figure 2b images of electron microscopy of PP blended with PET are presented, where it is noticed that the monofilament presents microrugosities, facilitating the physical adhesion with the cementitious matrix.
  • the compatibilizing material of the present invention is a polyolefinic polymer grafted with a polar group and whose long chains bind with the pure PP homopolymer of the fiber matrix through physical entanglement.
  • the compatibilizing material of the present invention may be selected from the group consisting of maleic anhydride grafted polypropylene (PP-g-MAH), glycidyl methacrylate grafted polypropylene (PPG-GA), acrylic acid grafted polypropylene (PP- g-AA), glycidyl methacrylate-grafted ethylene (Eg-GA) and a terpolymer of ethylene, acrylic ester and maleic anhydride.
  • PPG-GA glycidyl methacrylate grafted polypropylene
  • Eg-GA glycidyl methacrylate-grafted ethylene
  • the compatibilizing material is p PP-g-MAH with 1% maleic anhydride, by weight.
  • the polar group of the compatibilizing material (MAH, AA or
  • FIG. 3 shows a scanning electron microscopy image obtained with the cryogenic fracture surface of the PP / PET composites, in which the effect of the increasing additions of the compatibilizing material on the distribution and reduction of the diameters of the PET spheres can be verified (situation of greater compatibility).
  • the resulting monofilament fiber may have a diameter between 10 and 15 ⁇ m, preferably a diameter between 12 and 14 ⁇ m.
  • this blended monofilament has high toughness, with a value higher than 850 MPa.
  • the PP used in the process according to the present invention has a flow index between 18 and 25 g / 10min.
  • the process of producing the fibers occurs in two distinct steps.
  • the first, called wiring consists of a single extender where the polypropylene homopolymer, the polyethylene terephthalate homopolymer and the polymeric compatibilizing material are fused, blended and spun into coils. Extrusion of the materials occurs at temperatures ranging from 220 ° C to 280 ° C, preferably from 250 ° to 270 ° C. In this first step, coils of thicker yarns are produced.
  • the coils are positioned in trolleys and stretched (the drawing preferably occurs by the cold-drawing method, because it is a process with temperatures below the melting temperature of the materials) around 6 to 10 times the initial length of the wires, thus reducing its diameter.
  • the draw ratio (given by the speed difference of the rollers between the beginning and end of the process) of the monofilament of the present invention is greater than 7-fold, more preferably 7-8 fold.
  • the draw rate limit is close to 6 times.
  • the addition of PET provides to stretch the reels at higher rates.
  • the high tensile strength is a great advantage as it enables the manufacture of thinner yarns, which is very beneficial for their performance in fiber cement reinforcement.
  • Thinner wires generate a larger area of surface contact with the same mass addition, consequently increasing adhesion to the cementitious matrix.
  • the PET is added in proportions between 5 and 30% by weight, preferably between 5 and 15% by weight. Even in small dosages of PET (between 5 and 10% by weight), it is possible to verify important gains in the draw of the fiber itself and in its interfacial adhesion to the cementitious matrix.
  • the monofilament fiber of the present invention exhibits a participation of PP and secondary additions of PET and compatibilizer in proportions of 65% to 94% of PP, 5% to 30% of PET and 1% % to 5% compatibilizer.
  • the process may comprise an application of lubricating oil over the yarns in order to reduce intrinsic difficulties in the manufacture of synthetic yarns (presence of static charges, for example) and to improve their dispersion in aqueous media with the starting materials during the manufacturing process of the fiber cement products.
  • the lubricating oil comprises a mixture of fatty acid polyethylene glycol ester compounds and natural oil based phosphoric acid ester compounds in a ratio of at least 8: 2 to maximum of 9: 1.
  • the filaments can be extruded into a number of different geometries, such as with circular section, oval, trilobal, X-shaped, or Y-shaped or other alternate geometries.
  • various asbestos articles such as corrugated tiles, boards for external or internal closures, partitions or linings.
  • the PET monofilament blended with PET is present in these articles in the range of 1.0% to 2.0% by weight.
  • the article produced comprises from 1.3% to 1.8% by weight of the monofilament fiber.
  • the article claimed herein comprises fibers of length between 4 and 12 mm, more specifically between 6 and 10 mm.
  • PET monofilament blended with PET of length 8 to 10 mm, preferably 9 mm provides equal or superior performance in terms of mechanical strength, bending strength and durability compared to pure PP fiber with a length of 10 mm.
  • Table 1 shows the monofilaments used in the
  • Figure 4 shows the test results. Based on it is possible to verify that the monofilament of the present invention (tests 2, 3 and 4) achieves similar or superior performance against test 1 (pure PP). That is, it can be concluded that even with a smaller amount of fiber, the mechanical performance of the tiles tested was superior with PET monofilament blended with PET, indicating a surprising improvement of the present invention.
  • Table 3 shows the composition of the fibers used in the fiber cement article.
  • Table 4 shows the fiber compositions comprised in the flat plates used in the test.
  • Table 5 shows production data found in the fabrication of the yarns in question. In it, it is possible to observe the differences in geometry and properties caused by the addition of PET to the PP with proportional increase of the compatibilizing material of PP-g-MAH.
  • the addition of PET increases the final density of the yarns, which facilitates their mixing and dispersion in the preparation mixture for manufacturing the fiber cement articles.
  • the density of the fiber according to the present invention is greater than 0.9 g / cc, preferably between 0.91 and 1.0 g / cc, more preferably between 0.92 and 1.0 g / cc.
  • the PET monofilament fiber blended with PET using a long chain polymeric compatibilizing material comprising a polar group, preferably maleic anhydride grafted polypropylene has unexpected advantages, such as increase of the properties of mechanical resistance and flexural strength of fiber cement articles using a lower concentration of fibers, besides having a shorter length.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Civil Engineering (AREA)
  • Artificial Filaments (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

La présente invention concerne une fibre de haute ténacité pour renforcement de fibrociment, cette fibre étant un monofilament mélangé comprenant un homopolymère de polypropylène, un homopolymère de polyéthylène téréphtalate et un agent de compatibilité polymère polyoléfinique renfermant un groupe polaire. L'invention concerne également un procédé de production de ces fibres, ainsi que des articles de fibrociment utilisation ces monofilaments. Lesdits articles présentent des avantages tels que l'augmentation des propriétés de résistance mécanique et de résistance à la flexion ou le maintien de ces propriétés avec des concentrations massiques de fibres réduites.
PCT/BR2018/050093 2017-12-26 2018-04-06 Fibre de renforcement de fibrociment, procédé de production de cette fibre et article de fibrociment Ceased WO2019126847A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
MX2020006766A MX2020006766A (es) 2017-12-26 2018-04-06 Monofilamento mezclado pp/pet de alta tenacidad, no co-extrudido para refuerzo de materiales de cemento, y, articulo de fibrocemento.
BR112020012722-1A BR112020012722B1 (pt) 2017-12-26 2018-04-06 Fibra para reforço de fibrocimento, processo de produção da fibra, e, artigo de fibrocimento

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRBR1020170280853 2017-12-26
BR102017028085-3A BR102017028085A2 (pt) 2017-12-26 2017-12-26 Fibra para reforço de fibrocimento, processo de produção da fibra, e, artigo de fibrocimento

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WO2019126847A1 true WO2019126847A1 (fr) 2019-07-04

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PCT/BR2018/050093 Ceased WO2019126847A1 (fr) 2017-12-26 2018-04-06 Fibre de renforcement de fibrociment, procédé de production de cette fibre et article de fibrociment

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BR (1) BR102017028085A2 (fr)
MX (1) MX2020006766A (fr)
WO (1) WO2019126847A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115849777A (zh) * 2022-11-24 2023-03-28 南通龙哲混凝土制品有限公司 一种超疏水再生混凝土及其制备方法
US20230373855A1 (en) * 2020-09-15 2023-11-23 Kordsa Teknik Tekstil A.S. Microfibrous shotcrete mixture

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11255544A (ja) * 1998-03-09 1999-09-21 Tesac Corp セメント系材料用補強繊維及びそれを使用するセメント成型体
RU2007106761A (ru) * 2007-02-26 2008-09-10 Общество с ограниченной ответственностью "Си Айрлайд" (RU) Синтетическое волокно, способ его изготовления, цементный продукт, содержащий указанное волокно и способ изготовления указанного цементного продукта

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
JPH11255544A (ja) * 1998-03-09 1999-09-21 Tesac Corp セメント系材料用補強繊維及びそれを使用するセメント成型体
RU2007106761A (ru) * 2007-02-26 2008-09-10 Общество с ограниченной ответственностью "Си Айрлайд" (RU) Синтетическое волокно, способ его изготовления, цементный продукт, содержащий указанное волокно и способ изготовления указанного цементного продукта

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Title
FRIEDRICH, K. ET AL.: "Microfibrillar reinforced composites from PET/PP blends: processing, morphology and mechanical properties", COMPOSITES SCIENCE AND TECHNOLOGY, vol. 654, 2005, pages 107 - 116, XP004619378, doi:10.1016/j.compscitech.2004.06.008 *
JAYANARAYANAN, K. ET AL.: "Morphology and thermal properties of in-situ composites. ANTEC 2006", PROCEEDINGS OF THE 64TH SPE ANNUAL CONFERENCE, May 2006 (2006-05-01), pages 200 - 203, XP55623086 *
LI, W.J. ET AL.: "Influence of processing window and weight ratio on the morphology of the extruded and drawn PET/PP blends", POLYMER ENGINEERING AND SCIENCE, vol. 49, October 2009 (2009-10-01), pages 1929 - 1936, XP55623081 *
NONATO, R.C. ET AL.: "A study of PP/PET composiies: Factorial design, mechanical and thermal properties", POLYMER TESTING, vol. 56, December 2016 (2016-12-01), pages 167 - 173, XP55623082 *
SI , X.J. ET AL.: "Preparation and study of polypropylene/polyethylene terepht halate composite fibers", COMPOSITES SCIENCE AND TECHNOLOGY, vol. 68, November 2008 (2008-11-01), pages 2943 - 2947, XP55623080 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230373855A1 (en) * 2020-09-15 2023-11-23 Kordsa Teknik Tekstil A.S. Microfibrous shotcrete mixture
US12606484B2 (en) * 2020-09-15 2026-04-21 Afyon Cimento Sanayi Turk Anonim Sirketi Microfibrous shotcrete mixture
CN115849777A (zh) * 2022-11-24 2023-03-28 南通龙哲混凝土制品有限公司 一种超疏水再生混凝土及其制备方法
CN115849777B (zh) * 2022-11-24 2024-01-16 南通龙哲混凝土制品有限公司 一种超疏水再生混凝土及其制备方法

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BR102017028085A2 (pt) 2019-07-16
MX2020006766A (es) 2020-11-09
BR112020012722A2 (pt) 2020-12-01

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