WO1990001527A1 - Melange contenant du verre soluble et du laitier de haut fourneau - Google Patents

Melange contenant du verre soluble et du laitier de haut fourneau Download PDF

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Publication number
WO1990001527A1
WO1990001527A1 PCT/FI1989/000143 FI8900143W WO9001527A1 WO 1990001527 A1 WO1990001527 A1 WO 1990001527A1 FI 8900143 W FI8900143 W FI 8900143W WO 9001527 A1 WO9001527 A1 WO 9001527A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
waterglass
weight
slag
blast
Prior art date
Application number
PCT/FI1989/000143
Other languages
English (en)
Inventor
Markku Leino
Bob Talling
Original Assignee
Oy Partek Ab
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 Oy Partek Ab filed Critical Oy Partek Ab
Publication of WO1990001527A1 publication Critical patent/WO1990001527A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J1/00—Adhesives based on inorganic constituents
    • C09J1/02—Adhesives based on inorganic constituents containing water-soluble alkali silicates
    • 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
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
    • B32B2315/08—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2317/00—Animal or vegetable based
    • B32B2317/18—Cellulose, modified cellulose or cellulose derivatives, e.g. viscose
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2317/00—Animal or vegetable based
    • B32B2317/20—Starch

Definitions

  • the invention relates to a composition serving as a coating or adhesive in a product and at the same time protecting the product from fire as a layer which inhibits the trans ⁇ fer of fire and ignition and above all remains cohesive in a fire situation, as specified in greater detail in the preamble of accompanying Claim 1.
  • a fireproofed prod ⁇ uct is most commonly a board such as a building board, insulation board or cladding board, or a sandwich building panel.
  • the composition may, however, be used together with any material or structure, for example on mineral, con ⁇ crete, metal, wood, plastic, mineral-wool and paper sur ⁇ faces and on plastic-based insulation surfaces.
  • the insulative capacity of known fire-resistant boards or panels is based primarily on the resistance of the material to ignition and secondarily on its heat insulating power. Such materials function rather well in terms of fire, but their structure is brittle so that the protective power is effective for a rather short time only, and thereafter the material can no longer withstand shock, compression or bending.
  • paint-like coatings are used which are applied with a brush or sprayed onto the desired surface.
  • some non-combustible filler such as fine crushed stone, slag, asbestos, fiber, or the like, is added to the coat ⁇ ing.
  • Such coatings do increase the so-called protection time of the coated products, but they are not capable of heat insulation, and thermal damage is caused in the pro ⁇ tected surface relatively rapidly as the protective struc ⁇ ture collapses.
  • protection time is meant the time in minutes that it takes for heat to be transferred through the test specimen in a burning test before the opposite surface has reached a certain temperature.
  • coatings the purpose of which is to prevent fire damage due to high temperatures.
  • Such coatings have, in addition to fire damping properties, also insulat ⁇ ing properties.
  • insulating component it is known to use as a filler in the coating for example waterglass, vermiculite, clay, etc. , which is pre-expanded and owing to its porous structure will retard the transfer of heat through the coating.
  • Such a coating does increase the protection time of the product to be protected, but the structure of this coating, also, is broken and brittle in a fire situation, and thus it cannot serve effectively as a heat-insulating layer for a long time, because it collapses rapidly.
  • the object of the present invention is to provide a fire- proofing which increases the resistance to ignition and the heat-insulating power of a product and, above all, at the same time provides a high strength for the burned struc ⁇ ture, activating these properties only upon the occurrence of a fire situation.
  • this is achieved by giving for the composition serving as a coating or an adhesive the characteristics set forth in the characterizing clause of Claim 1.
  • proportioning the amounts of waterglass and blast-furnace slag or corresponding slag in the composition serving as a coating or an adhesive so that the proportion of waterglass in the composition is 65 - 99 % by weight and the proportion of blast-furnace slag 0.5 - 30 % by weight pores which are completely closed and regulatable in size are produced in a fire situation in the coating of a prod ⁇ uct or in the adhesive layer or layers of a product.
  • the composition serves as an adhesive by means of which a sandwich structure can be produced.
  • the adhesive layers of such a sandwich structure expand in the same manner as when used as a coat ⁇ ing, and owing to their unbroken homogeneous structure they enhance the strength of the sandwich structure for a con ⁇ siderable time.
  • the invention is thus based on adding a controlled amount of blast-furnace slag or corresponding slag to a water- glass, either a potassium-containing or a sodium-containing waterglass, the slag being at room temperature inert with the said waterglass.
  • a controlled amount of blast-furnace slag or corresponding slag to a water- glass, either a potassium-containing or a sodium-containing waterglass, the slag being at room temperature inert with the said waterglass.
  • the waterglass foams in this composition and, because of the presence of the slag, the composition strengthens the structure consisting of the product and the composition spread as a coating or as intermediate layers.
  • the insulating and strength effects are regulated by means of the amount of slag used so that the pores formed in a fire situation will not explode and break the protective layer.
  • a board coated or a sandwich structure bound using the composition according to the invention thus expands con ⁇ siderably in a fire situation but, nevertheless, retains its dense and strong structure for a rather long time.
  • the size of the pores in the expanded layer is optimized with respect to expansion and strength, and are in their size and distribution homogeneous throughout the entire insulat ⁇ ing layer. The pores are closed and the walls between them can withstand even high stresses.
  • the structure expanded in a controlled manner at the same time provides a rather long travel path for and a good convection and radiation barrier to the transfer of heat.
  • the expanded insulating structure will not generate any toxic gases during a fire, as known protective coatings commonly do.
  • a coated board or a sandwich structure does not differ from a board coated with a conventional composition or from a sandwich structure bound using a conventional adhesive layer.
  • the proportion of blast-furnace slag in the composition is 0.5 - 15 % by weight, specifically 4 - 8 % by weight.
  • the expanding ca ⁇ pacity of the composition decreases while its adhesive effect increases; this requires controlled proportioning in order to achieve the optimum effect.
  • the composition preferably contains a hygrostatic agent, but, because of the moisture content of waterglass, it also works without a hygrostatic agent.
  • the hygrostatic agent is added in order to accomplish an even drying process and to improve the thixotropy of the composition.
  • the hygrostatic agent used is preferably 0 - 5 % by weight cellulose or a cellulose derivative, or respectively 0 - 20 % by weight starch.
  • the molar ratio of waterglass which means its SiC>2 content in proportion to its a2 ⁇ 0 or K2O content, is preferably between 2.0 and 4.5. Waterglass begins to expand when its molar ratio exceeds 0.5. The expansion can be made use of only after the molar ratio exceeds 1.5, and it is at its most advantageous at the value 2.5. When the molar ratio is greater than 3.0, the moisture resistance is good.
  • the slag to be added to the waterglass is preferably ground, granulated slag. It must be at least partly vitreous.
  • the slag is ground preferably to a fineness of 250 - 400 m-Vkg.
  • Granulated slag becomes activated when the temperature rises above approximately 50 °C, and when the temperature rises further, it reacts by becoming activated non-linearly. This reaction can be controlled so that the waterglass expands in a controlled manner and the matrix in its entirety is reinforced by the reaction products of the slag, forming a homogeneous, optimally porous structure.
  • the dry matter content of the waterglass is to be such that it can be spread.
  • Waterglass having a molar ratio of 3.2 - 3.4 usually has a dry matter content of 37 %. Approximately 1 - 3 months after coating the dry matter content of the waterglass layer will be approximately 70 %.
  • the composition is spread preferably by spraying, applying with a brush or with a spatula.
  • the applicability of the composition with a brush can be affected by regulating the dry matter content of the waterglass, which affects the viscosity of the composition, and by increasing or decreas ⁇ ing the amount of hygrostatic agent, which affects the thixotropy of the composition.
  • the composition may also be in a dry form, in which case the waterglass content is in a dry form, usually in a spray dried form.
  • the dry form of the composition is a suitable commercial article. Water is added to the composition at the time of use.
  • Additives enhancing fireproofing and other properties can advantageously be added to the composition.
  • the fireproof ⁇ ing properties can further be enhanced by means of, for example, vollanstonite, limestone, perlite, vermiculite and various fibrous substances and other fire-retardants.
  • the elasticity and adhesive properties of the material and its resistance to water are also rather freely modifiable, as are its rheologic properties.
  • the composition is prepared by mixing the blast-furnace slag and possible other dry substances together and by adding the thus formed mixture to waterglass.
  • composition according to the invention is described below in greater detail with reference to the accompanying figures, which depict the properties of the composition as various functions.
  • Figure 1 is a graphical illustration of the principle of the mean result of the tests, indicating the order of ex ⁇ pansion as a function of the slag: aterglass ratio for different quantities of waterglass per surface unit;
  • Figure 2 is a graphical representation of the increase of the temperature of the surface to be protected, as a func ⁇ tion of time, when the surface is coated with the composi- tion according to Embodiment Example 3;
  • Figure 3 (prior art) is a graphical representation of the increase of the temperature of the surface to be protected, as a function of time, when the surface has been coated with a known fireproofing paint with the composition ac ⁇ cording to Embodiment Example 4.
  • the invention does not work, i.e. a product coated with a composition such as this does not survive in a fire situation. Large non-homogeneous pores are formed in the surface, and the matrix is brittle.
  • the invention works, but closer to a slag content of 30 % by weight its practical value is rather insignificant. Even with slag contents of over 15 % by weight, the expansion will decrease so much that the insulating properties decrease to an insignificant level.
  • a high slag content provides a very strong matrix, since slag reacts drastically with waterglass in a fire situation.
  • the slag content improves the adhesive properties of water- glass, i.e. improves adhesion and resistance to moisture.
  • Range D within which the slag content is between 4.0 and 8.0 % by weight, is the most advantageous range of the invention.
  • the order of magnitude of expansion is 9-fold, dropping to 6-fold when the slag content is 8 % by weight.
  • Respectively the order of expansion is with the higher waterglass amount (4 kg/m 2 board) and with the lower value of the slag ratio 18-fold, dropping to the value 14 when the slag content is 8 " % by weight.
  • Curve 2 in Figure 2 shows the rate at which the temperature of a board coated with a coating according to the invention rises in a fire situation. In approximately 3 minutes the temperature rises to 100 °C, but within the next 3 minutes the temperature does not rise significantly. After this stop in the rising of the temperature, the temperature rises rather sharply and reaches a level of 300 °C at 20 minutes, calculated from the beginning of the experiment. The said stop is due to the swelling of the composition, which at the same time increases the insulating power of the composition.
  • the three different curves depicted in the figure indicate temperature values measured at three different points on the "cold surface" of the test specimen.
  • the curves in Figure 3 depict the same as the curves in Figure 2. However, the measurements were obtained using a test specimen coated with a known fireproofing paint. In this test specimen the temperature of 100 °C is reached in approximately 2 minutes, and at 3 minutes the temperature is approximately 110 °C, whereafter it rises considerably more sharply than in the previous case and reaches a level of 300 °C at slightly less than 9 minutes.
  • composition according to the invention is advantageous- ly used as an adhesive between boards to produce a strong sandwich panel.
  • Suitable boards include fiber cement, gyp ⁇ sum cement and other such boards and various substrates such as mineral, concrete, metal, wood, plastic, mineral wool, plastic-based insulation surfaces and paper surfaces.
  • substrates such as mineral, concrete, metal, wood, plastic, mineral wool, plastic-based insulation surfaces and paper surfaces.
  • the range of application of the invention is very wide.
  • the adhesive will expand 2- to 40-fold, depending on its slag:waterglass ratio and its original layer thickness.
  • the protection time thus increases up to five-fold.
  • the board structure is still cohesive.
  • the expanded layer consists of small, closed and evenly distributed pores. Their size and number is dependent on the slag to waterglass ratio. The pore structure is thus precisely controllable between the extreme slag content values shown in Figure 1.
  • the composition When spread as a coating on the surface to be protected, the composition works in the same manner as when used as an adhesive. It binds well the filler added to it, which fil ⁇ ler may be, depending on the intended use, for example pigment, fine crushed stone, various pozzolanas, fibers.
  • the filler reinforces the surface, provides the desired outer appearance and does not prevent the layer from ex ⁇ panding in a fire situation.
  • the thickness of the coating increases about 5- to 10-fold, and the pro ⁇ tection time increases about 3- to 4-fold.
  • the burned sur ⁇ face layer has small pores and cannot be easily removed by scratching.
  • a sandwich structure was prepared which consisted of two cellulose cement boards (LUJA board) 60x60x4 mm in size and of a mixture placed between these boards as an adhesive, having the following composition:
  • the thickness of the structure in the normal state was 9.3 mm, i.e. the thickness of the adhesive layer was 1.3 mm.
  • the structure was burned according to standards SFS 4193 and NT FIRE 003. As a result of the burning it was noted that the protection time was 33 min and the thickness of the structure varied within a range of 16 - 22 mm.
  • the sandwich structure was cohesive and had so high a strength that it was able to withstand the weight of one person.
  • a fireproofing combination was prepared in which a mixture having the following composition was applied to one of the large sides of a cellulose cement board 60x60x4 mm in size:
  • Figure 2 shows, as a function of the burning time, the temperature rise of the surface of this board.
  • Example 3 For comparison, an experiment according to Example 3 was carried out in which the coating used was a commercially available fireproofing paint, the consumption being 0.72 kg m*-- . board
  • Thickness of the coating before the burning 0.5 mm
  • Thickness of the coating after the burning not determin- able
  • Figure 3 shows, as a function of the burning time, the temperature rise of the surface of this test board.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Building Environments (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention se rapporte à une composition qui sert d'enduit ou d'adhésif dans un produit et qui protège le produit du feu sous la forme d'une couche empêchant le transfert de chaleur et l'inflammation et restant surtout cohésive. La composition contient des composants, verre soluble et laitier de haut fourneau, connus en soi pour cette application. En réglant de façon appropriée les proportions du verre soluble et du laitier de haut fourneau, on obtient une ignifugation qui, en situation d'incendie, augmente la résistance du produit à l'inflammation ainsi que son pouvoir calorifuge et qui surtout rend très résistante la structure exposée au feu. Selon la présente invention, la proportion de verre soluble est de 65 à 99 % en poids et la proportion de laitier de haut fourneau de 0,5 à 30 % en poids. La proportion de laitier de haut fourneau n'est de préférence que de 0,5 à 15 % en poids et idéalement de 4 à 8 % en poids. Des petites quantités de cellulose, d'amidon et d'autres additifs peuvent être ajoutées à la composition. Avec une petite proportion de laitier, la couche d'enduit gonfle relativement plus, alors que la matrice reste plus faible. Avec une proportion élevée de laitier, la couche se dilate peu et des petits pores homogènes se forment dans la composition, ce qui rend la matrice très solide. En modulant la proportion de laitier dans la composition et la quantité de verre soluble utilisée par rapport à la surface, il est possible de réguler de façon contrôlée le degré de gonflement de la couche de ladite composition et la résistance de la matrice, ainsi que la vitesse d'accroissement de la température.
PCT/FI1989/000143 1988-08-05 1989-08-04 Melange contenant du verre soluble et du laitier de haut fourneau WO1990001527A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI883678A FI86738C (fi) 1988-08-05 1988-08-05 Aktivbrandskyddsmedel
FI883678 1988-08-05

Publications (1)

Publication Number Publication Date
WO1990001527A1 true WO1990001527A1 (fr) 1990-02-22

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WO (1) WO1990001527A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995004792A1 (fr) * 1993-08-10 1995-02-16 Rautaruukki Oy Formulation de revetement ignifugeant
DE4330770A1 (de) * 1993-09-10 1995-03-16 Fraunhofer Ges Forschung Mehrkomponenten-Klebesystem
WO1995028531A1 (fr) * 1994-04-13 1995-10-26 Geoffrey Crompton Panneaux d'isolation legers
EP1242561A1 (fr) * 1999-12-14 2002-09-25 Novio Phenolic Foam Pty Ltd. Compositions ignifuges
CN103897611A (zh) * 2013-11-01 2014-07-02 东南大学 一种人造板无醛环保黏合剂的制备原料及方法
CN106752477A (zh) * 2016-12-20 2017-05-31 公安部天津消防研究所 具有耐候性能及耐火性能的水性膨胀防火涂料及制备方法
CN109135365A (zh) * 2018-07-27 2019-01-04 佛山市雨禾电器制造有限公司 一种耐高温和耐腐蚀的硒涂层的加工方法
CN115181437A (zh) * 2022-07-29 2022-10-14 攀钢集团研究院有限公司 一种重轨钢坯防脱碳涂料及其制备和应用方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2603905A1 (de) * 1976-02-02 1977-08-04 Gruenzweig Hartmann Glasfaser Verfahren zur herstellung einer mit einer metallfolie kaschierten mineralfaserplatte
GB1525212A (en) * 1976-06-04 1978-09-20 Battelle Memorial Institute Composition for forming a fire-proof coating

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2603905A1 (de) * 1976-02-02 1977-08-04 Gruenzweig Hartmann Glasfaser Verfahren zur herstellung einer mit einer metallfolie kaschierten mineralfaserplatte
GB1525212A (en) * 1976-06-04 1978-09-20 Battelle Memorial Institute Composition for forming a fire-proof coating

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DERWENT'S ABSTRACT No. 77-17701Y/10; & SU,A,512225. *
DERWENT'S ABSTRACT No. 87-319489/45; & SU,A,1293149. *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995004792A1 (fr) * 1993-08-10 1995-02-16 Rautaruukki Oy Formulation de revetement ignifugeant
DE4330770A1 (de) * 1993-09-10 1995-03-16 Fraunhofer Ges Forschung Mehrkomponenten-Klebesystem
WO1995028531A1 (fr) * 1994-04-13 1995-10-26 Geoffrey Crompton Panneaux d'isolation legers
EP1242561A1 (fr) * 1999-12-14 2002-09-25 Novio Phenolic Foam Pty Ltd. Compositions ignifuges
EP1242561A4 (fr) * 1999-12-14 2008-12-10 Novio Phenolic Foam Pty Ltd Compositions ignifuges
CN103897611A (zh) * 2013-11-01 2014-07-02 东南大学 一种人造板无醛环保黏合剂的制备原料及方法
CN106752477A (zh) * 2016-12-20 2017-05-31 公安部天津消防研究所 具有耐候性能及耐火性能的水性膨胀防火涂料及制备方法
CN109135365A (zh) * 2018-07-27 2019-01-04 佛山市雨禾电器制造有限公司 一种耐高温和耐腐蚀的硒涂层的加工方法
CN115181437A (zh) * 2022-07-29 2022-10-14 攀钢集团研究院有限公司 一种重轨钢坯防脱碳涂料及其制备和应用方法

Also Published As

Publication number Publication date
FI86738C (fi) 1992-10-12
FI86738B (fi) 1992-06-30
FI883678A0 (fi) 1988-08-05
FI883678A (fi) 1990-02-06

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