CN115230258A

CN115230258A - Waterproof coiled material prepared from amorphous alloy foil and preparation method

Info

Publication number: CN115230258A
Application number: CN202110651503.5A
Authority: CN
Inventors: 白文新
Original assignee: Jiangsu Kejing Intelligent Technology Co ltd
Current assignee: Jiangsu Kejing Intelligent Technology Co ltd
Priority date: 2021-04-24
Filing date: 2021-06-11
Publication date: 2022-10-25
Anticipated expiration: 2041-06-11
Also published as: CN115233117A; CN115233118B; CN115233118A; CN115233117B; CN215440644U; CN215283773U; CN115230258B

Abstract

The application discloses waterproof coiled material prepared from amorphous alloy foil and a preparation method, which comprises the following steps: the amorphous alloy foil is an iron-nickel-chromium-based alloy foil prepared from an iron-nickel-chromium-based alloy, the iron-nickel-chromium-based alloy comprises an iron element, a chromium element, a nickel element, a phosphorus element, a boron element and impurity elements, wherein the weight parts of the iron element, the chromium element, the nickel element, the phosphorus element, the boron element and the impurity elements are respectively expressed by a, b, f, c, d and e according to the total 100 parts by weight, and the amorphous alloy foil meets the following requirements: a + f is more than or equal to 66 and less than or equal to 86, f is more than or equal to 6 and less than or equal to 60, b is more than or equal to 6 and less than or equal to 21, c is more than or equal to 5 and less than or equal to 12, d is more than or equal to 0.1 and less than or equal to 1.8, c +3d is more than or equal to 8 and less than or equal to 13, e is less than or equal to 5. The waterproof coiled material has the characteristics of strong light irradiation resistance, high temperature resistance, acid and alkali resistance, wear resistance, flame retardance, corrosion resistance, ageing resistance and root puncture resistance, and has good weather resistance.

Description

Waterproof coiled material prepared from amorphous alloy foil and preparation method

Technical Field

The invention relates to the technical field of waterproof coiled materials, in particular to a waterproof coiled material prepared from amorphous alloy foil and a preparation method of the waterproof coiled material.

Background

The waterproof coiled material is mainly used for building walls, roofs, tunnels, highways, refuse landfills and the like, can be curled into a roll-shaped flexible building material product for resisting external rainwater and underground water leakage, is a waterproof first barrier of the whole project, and plays a vital role in the whole project.

The waterproof roll needs to be subjected to weather tests for a long time, such as illumination, cold and hot, wind and rain, bacteria and the like, so that the comprehensive damage caused by the weather tests is very easy to cause the aging and the property degradation of the waterproof roll. In the prior art, in order to enhance the characteristics of the waterproof roll material such as strength, heat insulation performance, root puncture resistance, oxidation resistance and the like, a layer of metal foil (such as aluminum foil, nickel foil, cobalt foil, copper foil and the like, wherein the aluminum foil is the most common) is usually added during the preparation of the waterproof roll material, or a protective layer is further arranged on the metal foil, and a PET film is usually used as a protective layer for exposing the metal foil, so that the manufacturing cost of the waterproof roll material is increased, the heat reflection effect of the metal foil is weakened, particularly, the temperature of the waterproof roll material is easily increased under the high-temperature strong light irradiation in summer, the aging of the waterproof roll material is accelerated, the durability of the waterproof roll material in the prior art is still low, and the waterproof roll material is often cracked and aged after being used for more than three years, and cannot be subjected to various climate tests for a long time.

Therefore, there is a need to develop a waterproof roll with reasonable design, simple structure, low cost, temperature change resistance, corrosion resistance and high strength.

Disclosure of Invention

The invention provides an iron-nickel-chromium alloy and a preparation method thereof, which comprises the following implementation modes:

embodiment 1, a method of making an iron nickel chromium based alloy foil, comprising:

a melting step: smelting stainless steel, ferrophosphorus and ferroboron together to form an alloy melt, wherein the mass of the phosphorus element accounts for c,5 & ltc & gt & lt 12 & gt, such as 7 & ltc & lt 10 & gt, the mass of the boron element accounts for d,0.1 & ltd & lt 1.8, such as 0.6 & ltd & lt 1.2, and 8 & ltc +3 & ltd & lt 13 & gt are satisfied, the content of impurities is controlled to be lower than 1 part by weight, and the melting temperature of the alloy melt is 1150 ℃, such as 1050 ℃, such as 1000 ℃ or lower, calculated by total 100 parts by weight;

an ejection step: ejecting the alloy melt onto a chill roll at a temperature between 1000 ℃ and 1220 ℃ (e.g., between 1100 ℃ and 1220 ℃) and at least 50 ℃ above the melting temperature of the alloy melt (e.g., at least 100 ℃ above the melting temperature of the alloy melt), forming an iron-nickel-chromium-based alloy foil.

Embodiment 2, the method of embodiment 1, wherein the stainless steel is selected from one or more stainless steels of any of the following grades: 201. 201L, 202, 204, 301, 302, 303se, 304L, 304N1, 304N2, 304LN, 309S, 310S, 316L, 316N, 316J1L, 317.

Embodiment 3, the method of embodiment 1, wherein the stainless steel is recycled stainless steel.

Embodiment 4 the method of embodiment 1, wherein the mass of manganese in the alloy melt is less than 2 parts by weight, such as less than 1, such as less than 0.2; alternatively, the melting step includes a demanganizing step, after demanganizing, the mass of manganese element in the alloy melt being less than 2 parts by weight, such as less than 1, such as less than 0.2.

Embodiment 5 the method of embodiment 1, wherein the melting step comprises refining the alloy melt at a temperature 100 to 200 ℃ above the melting temperature, such that the elements in the alloy melt are thoroughly mixed; the impurities refer to other elements which do not obviously influence the properties of the iron-nickel-chromium alloy within the content range.

Embodiment 6, an iron-nickel-chromium-based alloy foil prepared by the method of any one of the preceding claims.

Embodiment 7 is an iron-nickel-chromium-based alloy containing an iron element, a chromium element, a nickel element, a phosphorus element, a boron element, and an impurity element, wherein the iron element is represented by a part by weight and the chromium element is represented by b part by weight, based on 100 parts by weight in total, the weight portion of the nickel element is f, the weight portion of the phosphorus element is c, the weight portion of the boron element is d, the weight portion of the impurity element is e, 66-86 a + f-60 f, 6-60 b-21, 5-12 c, 0.1-1 d-1.8 c +3 d-13 e-5.

Embodiment 8 the iron-nickel-chromium-based alloy according to embodiment 7, wherein 76. Ltoreq. A + f. Ltoreq.85, 7. Ltoreq. B.ltoreq.11, 7. Ltoreq. C.ltoreq.10, 0.6. Ltoreq. D.ltoreq.1.2, and when Mn is contained in the impurity elements, the mass part of the Mn element is less than 2.

Embodiment 9 the iron-nickel-chromium-based alloy according to embodiment 7, having a HV hardness of greater than 800, a maximum magnetic induction Bm and a remanence Br of the iron-nickel-chromium-based alloy measured under the same conditions of less than 70% of the values measured for 1k101 (standard iron-based amorphous soft magnetic alloy strip), for example less than 62% of the values measured for 1k101 (standard iron-based amorphous soft magnetic alloy strip), and a 180 ° half-fold toughness (which may also be referred to as 180 ° half-fold no-break number) of 2 or more, for example 3 or more.

Embodiment 10, an iron-nickel-chromium-based alloy foil made from the iron-nickel-chromium-based alloy of any one of embodiments 7-9, having a thickness of 10 to 98 micrometers, or a thickness of 20 to 40 micrometers, or a thickness of 30 to 50 micrometers, or a thickness of 20 to 65 micrometers, or a thickness of 25 to 60 micrometers.

Embodiment 11 the iron-nickel-chromium-based alloy foil of embodiment 10, having a width greater than 30mm, a width greater than 60mm, a width greater than 100mm, a width greater than 200mm, a width greater than 280mm, or a width greater than 350 mm.

Embodiment 12 the iron-nickel-chromium-based alloy foil according to embodiment 10, having an HV hardness of more than 800 as measured according to GB/T4340.1-1999, a maximum magnetic induction Bm and a remanence Br of the iron-nickel-chromium-based alloy measured under the same conditions of less than 70% of the values measured for 1k101 (standard iron-based amorphous magnetically soft alloy strip), such as less than 62% of the values measured for 1k101 (standard iron-based amorphous magnetically soft alloy strip), and a 180 ° half-fold toughness of 2 or more, such as 3 or more.

Embodiment 13 is an iron-nickel-chromium-based alloy foil composite material including at least two metal foils attached to each other with an adhesive layer interposed therebetween, wherein at least one of the metal foils is the iron-nickel-chromium-based alloy foil according to any one of embodiments 10 to 12.

Embodiment 14, the iron-nickel-chromium-based alloy foil composite of embodiment 13, wherein the adhesive layer is any one selected from the group consisting of: thermosetting adhesives such as epoxy resins, polyurethanes, silicones, and polyimides; thermoplastic adhesives such as polyacrylates, polymethacrylates, and methanol; phenol-epoxy type adhesives.

Embodiment 15, the composite of embodiment 13, having a width greater than 350mm, or having a width greater than 500 mm.

Embodiment 16, a method of making the iron-nickel-chromium-based alloy foil of any one of embodiments 10 to 12, comprising the steps of:

step one, smelting and melting ingredients to obtain an alloy melt, wherein the ingredients are calculated by total 100 parts by weight, and the weight parts of the ingredients are respectively as follows: the weight portion of the iron element is a, the weight portion of the chromium element is b, the weight portion of the nickel element is f, the weight portion of the phosphorus element is c, the weight portion of the boron element is d, the weight portion of the impurity element is e,66 is more than or equal to a + f is less than or equal to 86,6 is more than or equal to f is less than or equal to 60,6 is more than or equal to b is less than or equal to 21,5 is more than or equal to c is less than or equal to 12,0.1 is more than or equal to d is less than or equal to 1.8, 8 is more than or equal to c +3d is less than or equal to 13, e is less than or equal to 5, preferably e is less than or equal to 3, or e is less than or equal to 1,

and step two, enabling the alloy melt to pass through a nozzle slot at a temperature of between 1000 and 1220 ℃ (such as between 1100 ℃ and 1220 ℃) and at least 50 ℃ higher than the melting temperature of the alloy melt (such as at least 100 ℃ higher than the melting temperature of the alloy melt), and rapidly cooling the alloy melt through the surface of a cooling roller under the traction of a traction roller to obtain the iron-nickel-chromium-based alloy foil.

Embodiment 17 the method of embodiment 16, wherein the nozzle slot has a width of 0.2mm to 0.8mm and a length of 6mm to 500mm, such as 200mm to 350mm, such as 250mm to 320mm.

Embodiment 18, the method of embodiment 16, wherein the furnish comprises at least one of stainless steel, ferrophosphorus, and ferroboron.

Embodiment 19, the method of embodiment 18, wherein the stainless steel is selected from one or more stainless steels of any of the following grades: 201. 201L, 202, 204, 301, 302, 303se, 304L, 304N1, 304N2, 304LN, 309S, 310S, 316L, 316N, 316J1L, 317.

Embodiment 20 is a waterproof roll made of an amorphous alloy foil, which includes an iron-nickel-chromium-based alloy foil made of the iron-nickel-chromium-based alloy described in embodiment 7, and a waterproof substrate layer provided on one side of the iron-nickel-chromium-based alloy foil.

Embodiment 21 and the waterproof sheet material according to embodiment 20, wherein the iron-nickel-chromium-based alloy contains the following elements in parts by weight: a plus f is more than or equal to 76 and less than or equal to 85, b is more than or equal to 7 and less than or equal to 11, c is more than or equal to 7 and less than or equal to 10, d is more than or equal to 0.6 and less than or equal to 1.2, and when the impurity elements contain Mn, the mass of the Mn element accounts for less than 2 parts by weight.

Embodiment 22 the waterproofing membrane according to embodiment 20, wherein the iron-nickel-chromium-based alloy has a HV hardness of more than 800, a maximum magnetic induction Bm and a remanence Br of less than 70% of a value measured at 1k101 (standard iron-based amorphous soft magnetic alloy strip), such as less than 62% of a value measured at 1k101 (standard iron-based amorphous soft magnetic alloy strip), and a 180 ° half-fold toughness of 2 or more, such as 3 or more.

Embodiment 23 the waterproofing membrane of embodiment 20 wherein the amorphous alloy foil has a thickness of 10 to 98 microns, or a thickness of 20 to 40 microns, or a thickness of 30 to 50 microns, or a thickness of 20 to 65 microns, or a thickness of 25 to 60 microns.

Embodiment 24, the waterproofing membrane according to embodiment 20, wherein the amorphous alloy foil has a width of greater than 30mm, a width of greater than 60mm, a width of greater than 100mm, a width of greater than 200mm, a width of greater than 280mm, or a width of greater than 350 mm.

Embodiment 25 and the waterproof sheet according to embodiment 20, wherein the amorphous alloy foil has a 180 ° double fold toughness of 2 times or more, for example, 3 times or more.

Embodiment 26 of the waterproof sheet according to embodiment 20, wherein the raw material for preparing the iron-nickel-chromium-based alloy foil includes at least one of stainless steel, ferrophosphorus, and ferroboron.

Embodiment 27, the waterproof roll according to any one of embodiments 20 to 26, wherein the waterproof substrate layer is made of at least one material selected from the group consisting of: asphalt, polyurethane, plastic, butyl rubber, epoxy, and the like.

Embodiment 28 and the waterproof roll material according to embodiment 27, wherein a release film layer is disposed on one side of the waterproof substrate layer away from the amorphous alloy foil.

Embodiment 29, the waterproofing membrane according to embodiment 27, wherein the thickness of the waterproofing substrate layer is 0.5 to 3mm or 1 to 3mm, for example 2 to 3 mm.

Embodiment 30, a method for manufacturing a waterproofing membrane according to any one of the preceding embodiments, comprising the steps of:

arranging a waterproof substrate layer on the amorphous alloy foil to prepare the waterproof coiled material, wherein the waterproof substrate layer is made of at least one material selected from the following materials: asphalt, polyurethane, plastic, butyl rubber, epoxy, and the like.

Embodiment 31 is the method of manufacturing a waterproof roll according to embodiment 30, further including, before the waterproof substrate layer is provided, the steps of:

overlapping at least two amorphous alloy foils prepared by adopting an adhesive with a width of more than 3mm in the transverse direction, wherein the adhesive is selected from any one of the following: thermosetting adhesives such as epoxy resins, polyurethanes, silicones, and polyimides; thermoplastic binders such as polyacrylates, polymethacrylates, and methanol; phenol-epoxy type adhesives.

Embodiment 32, the method of manufacturing a waterproof sheet according to embodiment 30, wherein the amorphous alloy foil is manufactured by:

a melting step: smelting stainless steel, ferrophosphorus and ferroboron together to form an alloy melt, wherein the weight part of the phosphorus element is c,5 ≦ c ≦ 12, such as 7 ≦ c ≦ 10, the weight part of the boron element is d,0.1 ≦ d ≦ 1.8, such as 0.6 ≦ d ≦ 1.2, and satisfies 8 ≦ c +3 × d ≦ 13, the impurity content is controlled to be less than 1 weight part, and the melting temperature of the alloy melt is 1150 ℃ or less, such as 1050 ℃ or less, such as 1000 ℃ or less, calculated on the total 100 weight parts;

an ejection step: ejecting the alloy melt onto a cooling roller at a temperature of between 1000 ℃ and 1220 ℃ (for example, between 1100 ℃ and 1220 ℃) and at least 50 ℃ higher than the melting temperature of the alloy melt (for example, at least 100 ℃ higher than the melting temperature of the alloy melt), and forming the iron-nickel-chromium-based alloy foil, namely the amorphous alloy foil.

The invention provides an iron-based alloy and a preparation method thereof, which comprises the following scheme:

scheme 1 discloses an iron-based alloy, which comprises iron element, chromium element, phosphorus element, boron element and impurity element, wherein the iron element accounts for a part by weight, the chromium element accounts for b part by weight, the phosphorus element accounts for c part by weight, the boron element accounts for d part by weight, the impurity element accounts for e part by weight, 66 is equal to or less than or equal to 86,6 is equal to or less than or equal to 21,5 is equal to or less than or equal to 12,0.1 is equal to or less than or equal to 1.8, 8 is equal to or greater than c +3d is equal to or less than 13, and e is equal to or less than 1, calculated by total 100 parts by weight.

Scheme 2, the iron-based alloy of scheme 1, wherein a is more than or equal to 76 and less than or equal to 85, b is more than or equal to 7 and less than or equal to 11, c is more than or equal to 7 and less than or equal to 10, and d is more than or equal to 0.6 and less than or equal to 1.2.

Scheme 3, the iron-based alloy according to scheme 1, having an HV hardness of more than 800, measured according to GB/T4340.1-1999, a maximum magnetic induction Bm and a remanence Br of less than 70% of the values measured for 1k101 (standard iron-based amorphous soft magnetic alloy strip), such as less than 62% of the values measured for 1k101 (standard iron-based amorphous soft magnetic alloy strip), and a 180 ° half-fold toughness of 2 or more, such as 3 or more, measured under the same conditions.

Scheme 4, an iron-based alloy foil prepared from the iron-based alloy of any one of schemes 1-3, having a thickness of 10 to 98 microns, or a thickness of 20 to 40 microns, or a thickness of 30 to 50 microns, or a thickness of 20 to 65 microns.

Scheme 5, the iron-based alloy foil according to scheme 4, having a width greater than 30mm, a width greater than 60mm, a width greater than 100mm, a width greater than 200mm, a width greater than 280mm, or a width greater than 350 mm.

Scheme 6, according to the iron-based alloy foil of scheme 4, the 180-degree folding toughness is more than or equal to 2 times and more than or equal to 3 times.

Scheme 7, the iron-based alloy foil composite material comprises at least two layers of metal foils stuck to each other in a staggered manner through adhesive layers, wherein at least one layer of metal foil is the iron-based alloy foil according to any one of schemes 4 to 6.

Scheme 8 the iron-based alloy foil composite of scheme 7, wherein the adhesive layer is any one selected from the group consisting of: thermosetting adhesives such as epoxy resins, polyurethanes, silicones, and polyimides; thermoplastic binders such as polyacrylates, polymethacrylates, and methanol; phenol-epoxy type adhesives.

Scheme 9 the composite of scheme 7 having a width greater than 350mm having a width greater than 500 mm.

Scheme 10, a method of preparing the iron-based alloy foil according to any one of schemes 4 to 6, comprising the steps of:

step one, smelting and melting ingredients to obtain an alloy melt, wherein the ingredients are calculated by total 100 parts by weight, and the weight parts of the ingredients are respectively as follows: the weight portion of the iron element is a, the weight portion of the chromium element is b, the weight portion of the phosphorus element is c, the weight portion of the boron element is d, the weight portion of the impurity element is e,66 is more than or equal to a and less than or equal to 86,6 is more than or equal to b and less than or equal to 21,5 is more than or equal to c and less than or equal to 12,0.1 is more than or equal to d and less than or equal to 1.8, 8 is more than or equal to c +3d and less than or equal to 13, e is more than or equal to 1,

and secondly, enabling the alloy melt to quickly pass through a nozzle gap under pressure, and quickly cooling the alloy melt through the surface of a cooling roller under the traction of a traction roller to obtain the iron-based alloy foil.

Scheme 11 the method of scheme 10, wherein the nozzle slot has a width of 0.2mm to 0.8mm and a length of 6mm to 500mm, such as 200mm to 350mm, such as 250mm to 320mm.

Scheme 12, the method of scheme 10, wherein step two is performed at a temperature between 1000 ℃ and 1220 ℃ and at least 50 ℃ above the melting temperature of the alloy melt, for example step two is performed at a temperature between 1100 ℃ and 1220 ℃ and at least 100 ℃ above the melting temperature of the alloy melt.

Scheme 13 the method of scheme 10, wherein the batch material comprises at least one of pure iron, pure chromium, ferrophosphorus, ferroboron.

Scheme 14, a waterproofing membrane made from amorphous alloy foil, comprising: the amorphous alloy foil comprises an amorphous alloy foil and a waterproof substrate layer arranged on one side of the amorphous alloy foil, wherein the amorphous alloy foil is an iron-based alloy foil prepared from an iron-based alloy, the iron-based alloy comprises an iron element, a chromium element, a phosphorus element, a boron element and an impurity element, wherein the iron element accounts for a part by weight of a b element, the phosphorus element accounts for a part by weight of a c element, the boron element accounts for a part by weight of a d element, the impurity element accounts for a part by weight of e,66 is more than or equal to a 86,6 is more than or equal to b and less than or equal to 21,5 is more than or equal to c and less than or equal to 12,0.1 is more than or equal to d and less than or equal to 1.8, and 8 is more than or equal to c +3d and less than or equal to 13, and e is more than or equal to 1.

Scheme 15, according to the waterproofing membrane of scheme 14, wherein, the parts by weight of each element in the iron-based alloy satisfies: a is more than or equal to 76 and less than or equal to 85, b is more than or equal to 7 and less than or equal to 11, c is more than or equal to 7 and less than or equal to 10, and d is more than or equal to 0.6 and less than or equal to 1.2.

Scheme 16. The waterproofing membrane according to scheme 14, wherein the HV hardness of the iron-based alloy is greater than 800, the maximum magnetic induction Bm and the remanence Br of the iron-nickel-chromium-based alloy measured under the same conditions are lower than 70% of the values measured at 1k101 (standard iron-based amorphous magnetically soft alloy strip), for example lower than 62% of the values measured at 1k101 (standard iron-based amorphous magnetically soft alloy strip), and the 180 ° half-fold toughness is 2 times or more, for example 3 times or more.

Scheme 17, the waterproofing membrane of scheme 14, wherein the metallic glass foil has a thickness of 10 microns to 98 microns, or a thickness of 20 to 40 microns, or a thickness of 30 to 50 microns, or a thickness of 20 microns to 65 microns, or a thickness of 25 to 60 microns.

Scheme 18, the waterproofing membrane of scheme 14, wherein the metallic glass foil has a width of more than 30mm, a width of more than 60mm, a width of more than 100mm, a width of more than 200mm, a width of more than 280mm, or a width of more than 350 mm.

Scheme 19 and the waterproof roll according to scheme 14, wherein the 180 ° double-fold toughness of the amorphous alloy foil is 2 times or more, for example 3 times or more.

The waterproof roll according to claim 20 or 14 to 19, wherein the waterproof substrate layer is made of at least one material selected from the group consisting of: asphalt, polyurethane, plastic, butyl rubber, epoxy, and the like.

Scheme 21, according to scheme 20 waterproofing membrane, wherein, the waterproof substrate layer is kept away from one side of metallic glass foil is provided with from the type rete.

Scheme 22, the waterproofing membrane of scheme 20, wherein the thickness of the waterproofing substrate layer is 0.5 to 3mm or 1 to 3mm, for example 2 to 3 mm.

Scheme 23, a method for preparing the waterproof roll material according to any one of the preceding schemes, comprising the following steps:

coating a waterproof substrate layer on the amorphous alloy foil to prepare the waterproof coiled material, wherein the waterproof substrate layer is prepared from at least one of the following materials: asphalt, polyurethane, plastic, butyl rubber, epoxy, and the like.

Scheme 24. The method for producing a waterproof roll according to scheme 23, wherein

The amorphous alloy foil is prepared as follows:

step one, smelting and melting ingredients to obtain an alloy melt, wherein the ingredients are calculated by total 100 parts by weight, and the weight parts of the ingredients are respectively as follows: the weight portion of the iron element is a, the weight portion of the chromium element is b, the weight portion of the phosphorus element is c, the weight portion of the boron element is d, the weight portion of the impurity element is e,66 is more than or equal to a and less than or equal to 86,6 is more than or equal to b and less than or equal to 21,5 is more than or equal to c and less than or equal to 12,0.1 is more than or equal to d and less than or equal to 1.8, 8 is more than or equal to c +3d and less than or equal to 13, e is less than or equal to 1,

secondly, enabling the alloy melt to quickly pass through a nozzle gap under pressure, and quickly cooling the alloy melt through the surface of a cooling roller under the traction of a traction roller to obtain the iron-based alloy foil, namely the amorphous alloy foil; the second step is carried out at a temperature between 1000 ℃ and 1220 ℃ and at least 50 ℃ above the melting temperature of the alloy melt, for example the second step is carried out at a temperature between 1100 ℃ and 1220 ℃ and at least 100 ℃ above the melting temperature of the alloy melt.

Scheme 25, the method for preparing a waterproof roll according to scheme 23, further comprising the following steps before coating a waterproof substrate layer on the amorphous alloy foil:

overlapping at least two prepared amorphous alloy foils with each other in the transverse direction by a width of more than 3mm by using an adhesive, wherein the adhesive is selected from any one of the following: thermosetting adhesives such as epoxy resins, polyurethanes, silicones, and polyimides; thermoplastic binders such as polyacrylates, polymethacrylates, and methanol; phenol-epoxy type adhesives.

The technical scheme of the invention has the following effects: the metal alloy of the present application has a low melting temperature (less than 1150 ℃, for example less than 1050 ℃), has suitable melt fluidity, and is suitable for preparing corrosion-resistant metal foil with high thickness (more than 35 microns to less than 65 microns) and large width (more than 200 mm) by using a single-roll continuous method at low cost. The metal foil can also be used for preparing a composite metal foil with larger thickness and wider width by laminating, has excellent performance and low cost, and can be used in various application fields with high requirements on corrosion resistance and toughness. It should be noted that the alloy of the present application has poor soft magnetic properties, is not a soft magnetic alloy, and is therefore particularly suitable for applications where low requirements for magnetic properties are required.

The amorphous alloy foil is prepared from the metal alloy, and the amorphous alloy foil and the waterproof substrate layer are superposed to prepare the waterproof coiled material. The waterproof performance is good, and the waterproof paint has the characteristics of strong light irradiation resistance, high temperature resistance, acid and alkali resistance, wear resistance, flame retardance, corrosion resistance, ageing resistance and root puncture resistance. Because expose metallic glass foil and have good weatherability, need not additionally to set up the protective layer, make waterproofing membrane possesses excellent heat reflection effect under high temperature strong light shines, has further slowed down waterproofing membrane thermal ageing under summer high temperature, does not have obvious ageing, fracture phenomenon more than using three years, has good weatherability.

Drawings

To more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings in the specification will be briefly described below, and it should be apparent that the drawings in the following description are only related to some embodiments of the present disclosure, and do not limit the present disclosure.

FIG. 1 is a schematic view of a single roll apparatus for producing an alloy foil according to the present invention;

fig. 2 is a schematic view of the wide amorphous alloy waterproof roll of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present disclosure more apparent, the technical solutions of the embodiments of the present disclosure will be described clearly and completely with reference to the drawings of the embodiments of the present disclosure. It is to be understood that the described embodiments are only a few embodiments of the present disclosure, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the disclosure without inventive step, are within the scope of protection of the disclosure.

In the present application, each term has a meaning generally understood in the art, unless otherwise indicated or a different meaning can be derived from the context.

In the present application, unless otherwise specified, "melting temperature" and "melting point" are used synonymously.

In the present application, unless otherwise specified, "molten steel" and "alloy melt" are used synonymously.

In the present application, unless otherwise specified, "foil" is used in the same sense as "amorphous alloy foil".

The iron-based alloy comprises iron, chromium, phosphorus, boron and impurity elements, wherein the iron element accounts for a parts by weight, the chromium element accounts for b parts by weight, the phosphorus element accounts for c parts by weight, the boron element accounts for d parts by weight, the impurity element accounts for e parts by weight, 66 is greater than or equal to 86,6 is greater than or equal to 21,5 is greater than or equal to 12,0.1 is greater than or equal to d and less than or equal to 1.8, and 8 is greater than or equal to c +3d is less than or equal to 13, and e is less than or equal to 1, calculated by total 100 parts by weight. Although the impurity element in the alloy can be nickel, the iron-based alloy does not contain a large amount of expensive nickel element, has low cost and low melting point, and is easy to spray out metal foil. In the present application, an iron-based alloy refers to an alloy having an iron content of more than 60 parts by weight, based on 100 parts by weight of the total alloy weight. The impurity element means an element which does not significantly affect the properties of the iron-based alloy within a specified content range. The metal alloy of the present application has a low melting temperature (below 1150 ℃, for example below 1050 ℃), has suitable melt flowability, and is suitable for preparing corrosion-resistant metal foil with high thickness (more than 35 microns to less than 65 microns) and large width (more than 200 mm) by using a single-roll continuous method at low cost. The metal foil can also be used for preparing a composite metal foil with larger thickness and wider width by laminating, has excellent performance and low cost, and can be used in various application fields with high requirements on corrosion resistance and toughness. It should be noted that the alloy of the present application has poor soft magnetic properties, is not a soft magnetic alloy, and is therefore particularly suitable for applications where low requirements for magnetic properties are required.

The range of the elements Fe, cr, P, B in the alloy is only required to be within the above range, but in some embodiments, 76. Ltoreq. A.ltoreq.85, 7. Ltoreq. B.ltoreq.11, 7. Ltoreq. C.ltoreq.10, 0.6. Ltoreq. D.ltoreq.1.2 in the iron-based alloy. Within these ranges, the iron-based alloy has a lower melting point, enabling more stable production of corrosion resistant metal foils of higher thickness (greater than 35 microns to less than 65 microns) and greater width (greater than 200 mm) using a single roll continuous process at lower cost.

In some embodiments, the fe-based alloy has a HV hardness of greater than 800 as measured according to GB/T4340.1-1999, a maximum induction Bm and a remanence Br of less than 70% of the values measured for 1k101 (standard fe-based amorphous soft magnetic alloy strip), such as less than 62% of the values measured for 1k101 (standard fe-based amorphous soft magnetic alloy strip), measured under the same conditions (maximum induction Bm of less than 0.6T measured by scanning, and remanence Br of less than 0.3T), and a 180 ° half-fold toughness of greater than or equal to 2 times, such as greater than or equal to 3 times. The properties of the iron-based alloy are determined by the alloy foil produced, and therefore the definition of the properties also applies to alloy foils produced from the alloy. The alloy foil is different from common amorphous soft magnetic alloy, has the maximum magnetic induction intensity Bm and the remanence Br which are obviously lower than those of standard soft magnetic alloy, has good 180-degree folding toughness, and has hardness which is far higher than that of stainless steel (the HV hardness of the stainless steel foil is usually about 500). Without being limited by theory, it is believed that the alloys described herein have poor soft magnetic properties due to the higher content of chromium, and the alloy foils of the present application, as prepared by the single roll process described herein, are made by rapid cooling of the alloy melt, and thus have the excellent toughness and high HV hardness of amorphous alloys, without the brittleness of crystalline alloys.

The present application also provides an iron-based alloy foil prepared from the iron-based alloy of any one of the preceding claims, having a thickness of 10 to 98 microns, or a thickness of 20 to 65 microns, or a thickness of 25 to 50 microns. The iron-based alloy foil has the advantages of excellent performances of corrosion resistance, flame retardance, high temperature resistance, electromagnetic shielding, high strength, scratch resistance, light weight, low cost and the like. Because the melting point of the alloy of the present application is low, the ejection temperature can be correspondingly low (usually about 1220 ℃ or lower, and even as low as 1100 ℃ or lower), and the cooling capacity required for cooling to a solid is lower than that of an alloy without phosphorus and boron, so when a foil is prepared by a single-roll method, the cooling efficiency provided by a single roll can rapidly cool a thicker melt to a solid, and a thicker thickness can be prepared. In the case that the foil has a relatively thick thickness, the foil can have relatively high strength, such as hardness, toughness, and the like, so that the foil has a wider application space.

In some embodiments, the iron-based alloy foil has a width greater than 30mm, a width greater than 60mm, a width greater than 100mm, a width greater than 200mm, a width greater than 280mm, or a width greater than 350 mm. Alloy foils with wide widths cannot be prepared by other methods for preparing amorphous materials such as a single-roll cooling method, so that the application of foils with amorphous properties is greatly limited. The foil has a wide width and can be used in more application fields. The width described here means a dimension in a direction perpendicular to the machine direction.

In some embodiments, the fe-based alloy foil has an HV hardness of greater than 800 as measured according to GB/T4340.1-1999, a maximum induction Bm and a remanence Br of less than 70% of the values measured for 1k101 (standard fe-based amorphous soft magnetic alloy strip), such as less than 62% of the values measured for 1k101 (standard fe-based amorphous soft magnetic alloy strip), measured under the same conditions (maximum induction Bm of less than 0.6T measured by scanning, and remanence Br of less than 0.3T), and a 180 ° half-fold toughness of greater than or equal to 2 times, such as greater than or equal to 3 times.

The application also provides an iron-based alloy foil composite material, which comprises at least two layers of metal foils which are mutually stuck in a staggered way through adhesive layers, wherein at least one layer of metal foil is the iron-based alloy foil. Through the composition, the size limitation of the alloy foil can be completely eliminated, the strength of the foil is further increased, and the alloy foil without size limitation is prepared, so that the application field of the alloy foil can be expanded.

The adhesive layer used in the present application is not particularly limited as long as sufficient adhesion can be secured on the metal foil. In some embodiments the adhesive layer is any one selected from the group consisting of: thermosetting adhesives such as epoxy resins, polyurethanes, silicones, and polyimides; thermoplastic binders such as polyacrylates, polymethacrylates, and methanol; phenolic-epoxy type adhesives, and the like. The selection of the binder can be made by the person skilled in the art according to the actual need.

In some embodiments, the composite has a width greater than 350mm, or has a width greater than 500 mm. The composite material can enlarge the width of the composite material to any appropriate size as required due to the fact that the two layers of metal foils are compounded.

Another aspect of the invention provides a method for preparing an iron-based alloy foil according to any one of the preceding claims, comprising the steps of:

and secondly, enabling the alloy melt to quickly pass through a nozzle gap under pressure, and quickly cooling the alloy melt through the surface of a cooling roller under the traction of a traction roller to obtain the iron-based alloy foil. In some embodiments, step two is performed at a temperature between 1000 ℃ and 1220 ℃ and at least 50 ℃ above the melting temperature of the alloy melt, for example step two is performed at a temperature between 1100 ℃ and 1220 ℃ and at least 100 ℃ above the melting temperature of the alloy melt.

In some embodiments, the method wherein the nozzle slot has a width of 0.2mm to 0.8mm and a length of 6mm to 500mm, such as 200mm to 350mm, such as 250mm to 320mm. The width of the cooling roller corresponding to the nozzle slot is more than or equal to the length of the nozzle slot. The width and length of the nozzle slit can be appropriately selected according to the thickness and width of the alloy foil required, and can be made by those skilled in the art as needed.

In some embodiments, the furnish includes at least one of pure iron, pure chromium, ferrophosphorus, ferroboron.

Another aspect of the present invention provides a method of preparing an iron nickel chromium based alloy foil, comprising:

a melting step: smelting stainless steel, ferrophosphorus and ferroboron together to form an alloy melt, wherein the mass c of phosphorus is 5-12 parts by weight, such as 7-10 parts by weight, the mass d of boron is 0.1-1.8 parts by weight, such as 0.6-1.2 parts by weight, calculated on the total 100 parts by weight, and the mass d of boron satisfies 8 ≦ c +3 ≦ d 13, the content of impurities is controlled to be less than 1 part by weight, and the melting temperature of the alloy melt is 1150 ℃ or less, such as 1050 ℃ or less, such as 1000 ℃ or less;

The inventors of the present application have unexpectedly found that by using a method of adding phosphorus and boron to stainless steel, an alloy can be prepared that has a lower melting point (below 1150 ℃, such as below 1050 ℃, such as below 1000 ℃) and better fluidity at lower temperatures (between 1000 ℃ and 1220 ℃), which enables the preparation of alloy foils with higher thickness and wider width by the single roll process described herein. The alloy foil has excellent properties such as corrosion resistance, flame retardancy, high temperature resistance, electromagnetic shielding property, high strength, scratch resistance, low cost, light weight and the like.

In some embodiments, the stainless steel is selected from one or more stainless steels of any of the following grades: 201. 201L, 202, 204, 301, 302, 303se, 304L, 304N1, 304N2, 304LN, 309S, 310S, 316L, 316N, 316J1L, 317. In other embodiments, the stainless steel is recycled stainless steel. The choice of stainless steel in the present application is not limited and any stainless steel of the prior art may be used to make the iron-nickel-chromium-based alloy foils described herein, and in a preferred embodiment, recycled stainless steel may be used to substantially reduce manufacturing costs.

In some embodiments, the method wherein the alloy melt has a manganese content of less than 2 parts by weight, such as less than 1 part by weight, such as less than 0.2 part by weight. The high manganese content is not beneficial to the forming of the iron-nickel-chromium-based alloy foil, so that the sprayed foil is brittle and has no toughness, and the foil cannot be continuously sprayed and prepared.

The mass ratios of various elements in stainless steels of different grades are different, the manganese element content in some stainless steels is higher, and the manganese element content in other stainless steels is lower.

Table 1 shows the mass ratios of the various elements in several different grades of stainless steel.

TABLE 1 mass ratio of each element in stainless steel of different grades

In some embodiments, the alloy melt has a lower manganese content and does not need to be subjected to additional demanganization, for example, the stainless steel in the batch is 304 stainless steel, and because the stainless steel 304 has a lower manganese content, the alloy melt may not be subjected to demanganization; in other embodiments, the alloy melt has a higher manganese content and requires additional demanganization, for example, the stainless steel in the batch is 202 stainless steel, and because the manganese content of the 202 stainless steel is higher and the manganese content of the alloy melt is higher, the manganese content can be effectively reduced by selecting a suitable demanganization agent for demanganization. The demanganizing agent is selected by selecting a suitable oxidizing agent. Iron oxide is an economical and relatively effective demanganizing agent, and iron oxides such as FeO and Fe can be used ₂ O ₃ Two forms or a combination thereof.

In some embodiments, the melting step comprises refining the alloy melt at a temperature of 100 ℃ to 200 ℃ above the melting temperature so that the elements in the alloy are well mixed; the impurities refer to other elements which do not obviously influence the properties of the iron-nickel-chromium alloy within the content range. The method of refining the alloy melt is not limited, and those skilled in the art can select the method according to actual conditions. However, the impurity in the alloy melt is not any element, and the impurity element refers to other elements which do not significantly affect the properties of the iron-nickel-chromium alloy within the content range, for example, elements other than iron-nickel-chromium-phosphorus-boron, such as manganese.

The present application also provides an iron-nickel-chromium alloy foil prepared according to the method of any one of the preceding claims.

The application also provides an iron-nickel-chromium-based alloy which comprises iron element, chromium element, nickel element, phosphorus element, boron element and impurity element, wherein the weight part of the iron element is a, the weight part of the chromium element is b, the weight part of the nickel element is f, the weight part of the phosphorus element is c, the weight part of the boron element is d, the weight part of the impurity element is e,66 is less than or equal to a + f is less than or equal to 86,6 is less than or equal to f is less than or equal to 60,6 is less than or equal to b is less than or equal to 21,5 is less than or equal to c is less than or equal to 12,0.1 is less than or equal to d is less than or equal to 1.8, and 8 is less than or equal to c +3d is less than or equal to 13, and e is less than or equal to 5, wherein the total 100 parts by weight. The iron-nickel-chromium-based alloy can be prepared by smelting stainless steel, ferrophosphorus and ferroboron together, can adopt recycled stainless steel, and has the advantages of low preparation cost, low melting point of the alloy, and easy ejection for preparing metal foil with large thickness and width. The term "iron-nickel-chromium-based alloy" as used herein refers to an alloy having a content of three elements of iron and nickel and chromium of more than 60 parts by weight based on 100 parts by weight of the total alloy.

In some embodiments, the iron-nickel-chromium-based alloy has a composition of 76. Ltoreq. A + f. Ltoreq.85, 7. Ltoreq. B.ltoreq.11, 7. Ltoreq. C.ltoreq.10, 0.6. Ltoreq. D.ltoreq.1.2, and when Mn is contained in the impurity elements, the Mn content is less than 2 parts by weight, for example less than 1 part by weight, for example less than 0.2 part by weight.

In some embodiments, the iron-nickel-chromium-based alloy has a HV hardness greater than 800, a maximum magnetic induction Bm and a remanence Br of less than 70% of values measured for 1k101 (standard iron-based amorphous magnetically soft alloy ribbon), such as less than 62% of values measured for 1k101 (standard iron-based amorphous magnetically soft alloy ribbon), measured under the same conditions (maximum magnetic induction Bm less than 0.6T and remanence Br less than 0.3T measured by scanning), and a 180 ° half-fold toughness of greater than or equal to 2 times, such as greater than or equal to 3 times. The properties of the iron-nickel-chromium-based alloy are determined by the alloy foil produced, and therefore the definition of the properties also applies to alloy foils produced from the alloy. The alloy foil is different from common amorphous soft magnetic alloy, has the maximum magnetic induction Bm and the remanence Br which are obviously lower than those of standard soft magnetic alloy, has good 180-degree folding toughness, and has hardness which is far higher than that of stainless steel (the HV hardness of the stainless steel foil is usually about 500). Without being limited by theory, it is believed that the alloys described herein have poor soft magnetic properties due to their higher content of chromium, and the alloy foils of the present application, as prepared by the single roll process described herein, have excellent toughness and high HV hardness of amorphous alloys without brittleness of crystalline alloys due to rapid cooling of the alloy melt, and have further improved toughness and prospects for large-scale production applications due to the addition of nickel relative to the iron-based alloys described herein.

Yet another aspect of the present application provides an iron-nickel-chromium-based alloy foil, prepared from the iron-nickel-chromium-based alloy of any one of the preceding claims, having a thickness of from 10 microns to 98 microns, or from 20 microns to 65 microns, or from 25 to 60 microns. The iron-based alloy foil has excellent performances of corrosion resistance, flame retardance, high temperature resistance, electromagnetic shielding, high strength, scratch resistance, lightness and thinness and the like, and can obtain obviously reduced cost if recycled stainless steel is adopted as a raw material. Because the melting point of the alloy of the present application is relatively low, the ejection temperature can be correspondingly low (usually about 1220 ℃ or lower, and even as low as 1100 ℃ or lower), and the cooling capacity required for cooling to a solid is lower than that of an alloy without phosphorus and boron, so that when a foil is prepared by a single-roll method, the cooling efficiency provided by a single roll can rapidly cool a thicker melt to a solid, and a thicker thickness can be prepared. In the case that the foil has a relatively thick thickness, the foil can have relatively high strength, such as hardness, toughness, and the like, so that the foil has a wider application space.

In some embodiments, the foil of iron-nickel-chromium-based alloy has a width greater than 30mm, a width greater than 60mm, a width greater than 100mm, a width greater than 200mm, a width greater than 280mm, or a width greater than 350 mm. Alloy foils with wide widths cannot be prepared by other methods for preparing amorphous materials such as a single-roll cooling method, so that the application of foils with amorphous properties is greatly limited. The foil of the present application has a wider width and can be used in more application areas. The width described here means a dimension in a direction perpendicular to the machine direction.

In some embodiments, the foil of the iron-nickel-chromium-based alloy has a HV hardness of more than 800 as measured according to GB/T4340.1-1999, a maximum magnetic induction Bm and a remanence Br of the iron-nickel-chromium-based alloy measured under the same conditions of less than 70% of the values measured for 1k101 (standard iron-based amorphous soft magnetic alloy strip), such as less than 62% of the values measured for 1k101 (standard iron-based amorphous soft magnetic alloy strip), (the maximum magnetic induction Bm measured by scanning method is less than 0.6T, the remanence Br is less than 0.3T), and a 180 ° double fold toughness of 2 or more times, such as 3 or more times.

The application also provides an iron-nickel-chromium-based alloy foil composite material, which comprises at least two layers of metal foils which are mutually stuck in a staggered way through an adhesive layer, wherein at least one layer of metal foil is the iron-nickel-chromium-based alloy foil. Through the composition, the size limitation of the alloy foil can be completely eliminated, the strength of the alloy foil is further increased, the alloy foil without size limitation is prepared, and thus the application field of the alloy foil can be expanded.

The adhesive layer used in the present application is not particularly limited as long as sufficient adhesion can be secured on the metal foil. In some embodiments the adhesive layer is any one selected from the group consisting of: thermosetting adhesives such as epoxy resins, polyurethanes, silicones, and polyimides; thermoplastic binders such as polyacrylates, polymethacrylates, and methanol; phenol-epoxy type adhesives, and the like. The selection of the binder can be made by the person skilled in the art according to the actual need.

In some embodiments, the composite has a width greater than 350mm, or has a width greater than 500 mm. The composite material of the application can increase the width of the composite material to any suitable size according to the requirement due to the fact that the two layers of metal foils are compounded.

Another aspect of the invention provides a method of making an iron-nickel-chromium-based alloy foil as described in any one of the preceding claims, comprising the steps of:

step one, smelting ingredients, and melting to obtain an alloy melt, wherein the ingredients are calculated by total 100 parts by weight, and the weight parts of all elements are respectively as follows: the weight portion of the iron element is a, the weight portion of the chromium element is b, the weight portion of the nickel element is f, the weight portion of the phosphorus element is c, the weight portion of the boron element is d, the weight portion of the impurity element is e,66 is more than or equal to a + f is less than or equal to 86,6 is more than or equal to f is less than or equal to 60,6 is more than or equal to b is less than or equal to 21,5 is more than or equal to c is less than or equal to 12,0.1 is more than or equal to d is less than or equal to 1.8, 8 is more than or equal to c +3d is less than or equal to 13, e is less than or equal to 5, preferably e is less than or equal to 3, or e is less than or equal to 1,

and step two, enabling the alloy melt to pass through a nozzle slot at a temperature of between 1000 and 1220 ℃ (such as between 1100 and 1220 ℃) and at least 50 ℃ (such as at least 100 ℃) higher than the melting temperature of the alloy melt, and rapidly cooling the alloy melt through the surface of a cooling roller under the traction of a traction roller to obtain the iron-nickel-chromium-based alloy foil.

In some embodiments, the method wherein the nozzle slot has a width of 0.2mm to 0.8mm and a length of 6mm to 500mm, such as 200mm to 350mm, such as 250mm to 320mm. The width of the cooling roller corresponding to the nozzle slot is greater than or equal to the length of the nozzle slot. The width and length of the nozzle slit can be appropriately selected according to the thickness and width of the alloy foil required, and can be made by those skilled in the art as needed.

In some embodiments, the batch material includes at least one of stainless steel, ferrophosphorus, and ferroboron.

Reference may also be made to CN1781624A and CN101445896 for a method for making alloy foil by the single roll method, which are incorporated by reference into the present application as part of the present application, and which, although not intended for making alloy foil, are similar to the present application in some specific operations and equipment set-up.

The invention also provides a waterproof roll prepared from the amorphous alloy foil, which comprises the following components: the waterproof coiled material comprises an amorphous alloy foil and a waterproof base material layer arranged on one side of the amorphous alloy foil, wherein the amorphous alloy foil is an iron-nickel-chromium-based alloy foil prepared from the iron-nickel-chromium-based alloy, and the waterproof coiled material has excellent performance in the following aspects: strong light irradiation resistance, high temperature resistance, acid and alkali resistance, corrosion resistance, high strength, wear resistance, scratch resistance, low cost, high heat dissipation, aging resistance and root puncture resistance, and has good weather resistance. The amorphous alloy has a long-range disordered structure, shows many excellent mechanical properties different from those of the crystalline alloy, such as high yield strength, high hardness, low Young modulus, higher fracture toughness, good wear resistance, stable chemical properties and excellent corrosion resistance. However, the amorphous alloy has no macroscopic plastic behavior, which severely restricts the application of the amorphous material in real life. The applicant has unexpectedly found that the metal alloy of the present application has a low melting temperature (below 1150 ℃, for example below 1050 ℃), has suitable melt flowability, is suitable for preparing corrosion-resistant metal foil with high thickness (more than 35 microns to less than 65 microns) and large width (more than 200 mm) by using a single-roll continuous method at low cost, and has excellent characteristics of amorphous alloy materials. Waterproofing materials are typically purchased and sold in roll form and are therefore also commonly referred to as waterproofing rolls or rolls, and in this application, the terms "waterproofing material", "waterproofing roll" and "roll of waterproofing" are used synonymously and interchangeably.

In some embodiments, the amorphous alloy foil is an iron-based alloy foil made of the iron-based alloy of any one of the preceding claims.

In some embodiments, the amorphous alloy foil has a thickness of 10 to 98 microns, or a thickness of 20 to 40 microns, or a thickness of 30 to 50 microns, or a thickness of 20 to 65 microns, or a thickness of 25 to 60 microns. Generally, the method for preparing the amorphous alloy foil is a melt rapid quenching method. In the present application, the amorphous alloy foil is required to have a thickness of 15 to 98 μm because too thin amorphous foil is not strong enough and too thick amorphous foil is difficult to prepare. In such a thickness range the alloy foil has an HV hardness of more than 800 measured according to GB/T4340.1-1999 and is easy to manufacture. The amorphous alloy foil with the thickness higher than 65 microns needs a larger cooling speed in preparation.

In some embodiments, the amorphous alloy foil has a width greater than 30mm, a width greater than 60mm, a width greater than 100mm, a width greater than 200mm, a width greater than 280mm, or a width greater than 350 mm. The larger width is convenient for lay, reduces the adjacent line of waterproof construction face, and the alloy foil of preparing through the fuse-element cold quenching method can be coiled and placed, when preparing waterproofing membrane, can overlap joint amorphous alloy foil each other, obtains suitable width and prepares into waterproofing membrane.

In some embodiments, the raw material for preparing the iron-nickel-chromium-based alloy foil comprises at least one of stainless steel, ferrophosphorus and ferroboron. The choice of stainless steel in the present application is not limited and any stainless steel of the prior art may be used to make the iron-nickel-chromium-based alloy foils described herein, and in preferred embodiments, recycled stainless steel may be used to substantially reduce manufacturing costs.

In some embodiments, the waterproof substrate layer is made of at least one material selected from the group consisting of: asphalt, polyurethane, plastic, butyl rubber, epoxy, and the like. The waterproof substrate layer is preferably made of a material having good heat resistance, oxidation resistance and corrosion resistance. The materials used as the waterproof substrate in the present application, such as asphalt, polyurethane, plastic, butyl rubber, epoxy resin, and the like, can be obtained from ordinary commercially available sources, and those skilled in the art can select them according to actual needs without particular limitation. Among them, butyl rubber is one of synthetic rubbers, and is synthesized from isobutylene and a small amount of isoprene. Are generally used for manufacturing tires. In the field of building waterproofing, butyl rubber is comprehensively popularized and replaces asphalt with an environment-friendly name.

In some embodiments, a release film layer is disposed on a side of the waterproof substrate layer away from the amorphous alloy foil. The release film layer can provide protection for the waterproof substrate layer and can be taken off when the coiled material is laid.

In some embodiments, the thickness of the waterproof substrate layer is 0.5 to 3 millimeters or 1 to 3 millimeters, for example 2 to 3 millimeters. The waterproof performance is influenced by the fact that the thickness of the waterproof coiled material is too small, and the stress is gathered when the too thick coiled material is laid, so that the coiled material is easy to warp and degum when being adhered to the internal and external corners and the concave-convex surfaces of the building roof. The coiled material with moderate thickness has moderate stress when being formed, and has better soft and conformable property when being pasted with the internal and external corners and the concave and convex surfaces of the building roof, and is not easy to warp and degum.

The present application also provides a process for preparing a waterproofing membrane according to any of the preceding claims, comprising the steps of:

arranging a waterproof substrate layer on the amorphous alloy foil to prepare the waterproof coiled material, wherein the waterproof substrate layer is made of at least one material selected from the following materials: asphalt, polyurethane, plastic, butyl rubber, epoxy, and the like. The waterproof substrate layer can be arranged in a coating mode.

In some embodiments, the preparation method of the waterproof roll further comprises the following steps before the waterproof substrate layer is arranged: and overlapping at least two prepared amorphous alloy foils with each other in the transverse direction by a width of more than 3mm by using an adhesive so as to form an expanded breadth, wherein the overlapping areas can be bonded by using the adhesive. The binder is selected from any one of the following: thermosetting adhesives such as epoxy resins, polyurethanes, silicones, and polyimides; thermoplastic binders such as polyacrylates, polymethacrylates, and methanol; phenol-epoxy type adhesives.

In some embodiments, the amorphous alloy foil is prepared by:

Another aspect of the present invention provides a finishing material comprising: the alloy foil (iron-based alloy foil or iron-chromium-nickel-based alloy foil) comprises the alloy foil and an adhesive coated on one side of the amorphous metal foil. The facing material has excellent properties in the following respects: corrosion resistance, flame retardance, high temperature resistance, antibacterial property, electromagnetic shielding, high strength, scraping resistance and low cost.

In some embodiments, the facing material wherein the adhesive is selected from any one of the following: thermosetting adhesives such as epoxy resins, polyurethanes, silicones, and polyimides; thermoplastic adhesives such as polyacrylates, polymethacrylates, and methanol; phenolic-epoxy type adhesives, and the like. The selection of the binder can be made by the person skilled in the art according to the actual need.

Another aspect of the invention provides a composite material comprising an alloy foil according to any one of the preceding claims or a facing material according to any one of the preceding claims, a base structure to which the facing material or alloy foil is attached. The composite material has excellent properties in the following respects: corrosion resistance, flame retardance, high temperature resistance, electromagnetic shielding, high strength, scratch resistance and low cost.

In some embodiments, in the composite material, the material of the base structure is at least one selected from the group consisting of: non-metallic materials, metallic materials.

In some embodiments, the composite material wherein the base structure comprises at least one member selected from the group consisting of: pipes, plates, concrete substrates.

Another aspect of the invention provides a pipe or sheet having at least one layer made from the alloy of any one of the preceding claims. The pipe or plate has excellent properties in the following respects: corrosion resistance, flame retardance, high temperature resistance, electromagnetic shielding, high strength, scraping resistance and low cost.

Another aspect of the present invention provides an electromagnetic shield comprising the alloy foil according to any one of the preceding claims. The electromagnetic shielding case has excellent performance in the following aspects: corrosion resistance, flame retardance, high temperature resistance, electromagnetic shielding, high strength, scratch resistance and low cost.

Another aspect of the present invention provides an article, such as a conference room, a house, or the like, employing the electromagnetic shield of any of the preceding claims.

Another aspect of the invention provides a cable of core-sheath construction, wherein at least one layer of the sheath comprises or consists of an alloy foil as defined in any one of the preceding claims. The cable of the core-sheath structure has excellent properties in the following respects: corrosion resistance, flame retardance, high temperature resistance, electromagnetic shielding, high strength, toughness and low cost.

Another aspect of the invention provides an article comprising the amorphous alloy of any one of the preceding claims, the alloy foil of any one of the preceding claims, or the facing material of any one of the preceding claims.

Another aspect of the invention provides a fire resistant roller blind comprising an amorphous metal foil according to any one of the preceding claims. The fire-proof rolling shutter has excellent performances in the following aspects: corrosion resistance, flame retardance, high temperature resistance and high strength.

In some embodiments, in the fire-proof rolling shutter, the amorphous metal foil is disposed between or laid on the inorganic fiber cloth.

The ranges described above may be used alone or in combination. The present application can be more easily understood by the following examples.

Examples

The raw materials and sources used in the examples of the present application are shown in table 2 below, and other materials not listed in the table are all commercially available products.

TABLE 2 raw materials and sources

Example 1 (preparation of iron-based alloy foil)

The method comprises the following steps of mixing industrial pure iron, chromium, phosphorus iron and ferroboron according to the mass percentage shown in the following table, smelting the mixture with the total amount of 10 kilograms in each experiment into an alloy melt in a vacuum furnace, and ejecting the alloy melt onto a cooling roller at the temperature of between 1000 and 1220 ℃ and at least 50 ℃ higher than the melting temperature of the alloy melt to form the iron-based alloy foil.

The preparation method comprises the following steps:

the same single roll apparatus as in fig. 1 (in fig. 1, 1 is an alloy melt, 2 is a nozzle, 3 is a nozzle slit, 4 is a high-frequency coil, 5 is a cooling roll, 6 is a stripping gas nozzle, 7 is a pulling roll, and 8 is an alloy foil) was used to manufacture an alloy foil having a width of 200mm by spraying an alloy melt composed of the ingredients in the mass percentages shown in the following table from a nozzle made of ceramics mainly composed of silicon nitride onto a Cu — Be alloy cooling roll having an outer diameter of 800 mm. The melting temperature and ejection temperature of the alloy and the preparation results are shown in the following table. The gap of the nozzle was 200mm by 0.7mm, and the gap between the nozzle and the cooling roll was 120 μm. An alloy foil having a width of 200mm and a thickness of 35 μm was obtained.

In this example, three groups were tested, and the numbers of each group were experiment 1-1 to experiment 1-5, experiment 2-1 to experiment 2-6, and experiment 3-1 to experiment 3-7, respectively.

TABLE 3 alloy compositions for the first set of experiments

Number of	Fe content	Cr and Cr content	P phosphorus content	B content
					Experiment 1-1	85	6	8	1
Experiment 1 to 2	78	13	8	1
					Experiments 1 to 3	75	16	8	1
Experiments 1 to 4	70	21	8	1
					Experiments 1 to 5	65	26	8	1

TABLE 4 preparation of the first set of experiments

TABLE 5 alloy compositions of the second set of experiments

Number of	Fe content	Cr and Cr content	P phosphorus content	B content
					Experiment 2-1	81	10	8	1
Experiment 2-2	79	10	10	1
					Experiment 2 to 3	77	10	12	1
Experiments 2 to 4	74	10	15	1
					Experiments 2 to 5	84	10	5	1
Experiments 2 to 6	86	10	3	1

TABLE 6 preparation of the second set of experiments

TABLE 7 alloy composition of the third set of experiments

Number of	Fe content	Cr and Cr content	P phosphorus content	B content
					Experiment 3-1	82.5	8.5	8	1
Experiment 3-2	81.5	8.5	8	2
					Experiment 3-3	80.5	8.5	8	3
Experiment 3 to 4	79.5	8.5	8	4
					Experiments 3 to 5	77.5	8.5	8	6
Experiment 3 to 6	81.7	8.5	8	1.6
					Experiments 3 to 7	83	8.5	8	0.5

TABLE 8 preparation of the third set of experiments

From the first set of experiments above, it can be seen that the Cr content cannot exceed 26 wt% and that the higher the melting point of the alloy, the less the thick foil is produced and the brittleness of the produced foil is increased.

From the above second and third set of experiments, it can be seen that the mass content of P in the alloy can be between 5% and 12%, and the mass content of B can be between 0.1% and 1.8%, but the condition to be satisfied at the same time is that the sum of the boron content 3 times and the phosphorus content is between 8% and 13%. When the P content exceeds 12%, the melting point of the alloy is low, the material is not melted, the master alloy turns red, and a foil cannot be produced; when P is less than 5%, the alloy has a high melting point but a high viscosity, and a foil cannot be produced. The mass percentage content of B in the alloy is less than 2 percent, when the mass percentage content of B is more than or equal to 2 percent, the melting point of the alloy is increased on the contrary, the fluidity is deteriorated, the hole blocking phenomenon is generated, the foil is brittle, and the foil is broken on a traction roller, so that the foil cannot be continuously produced. Phosphorus and boron are used together in this application to adjust the melting point and the fluidity of the alloy, so that there is also a mutual proportion between phosphorus and boron, i.e. the sum of the boron content, which is 3 times the sum of the phosphorus content, is between 8% and 13%, beyond which it is still impossible to produce acceptable foils.

Example 2 (preparation of iron-nickel-chromium-based alloy foil)

The method comprises the following steps of mixing 304 stainless steel, phosphorus iron and boron iron according to the mass percentages shown in the following table, wherein the total amount of the mixture in each experiment is about 10 kilograms, smelting the mixture into an alloy melt in a vacuum furnace, and spraying the alloy melt onto a cooling roller at the temperature of between 1000 and 1220 ℃ and at least 50 ℃ higher than the melting temperature of the alloy melt to form the iron-nickel-chromium-based alloy foil.

The preparation method comprises the following steps:

The specific composition employed in this example is as follows.

The specific compositions of the alloys in the experiments of tables 9 and fourth group are as follows

TABLE 10 preparation of fourth set of experiments

From the fourth set of experiments it can be seen that by adding P and B to the stainless steel material, which content is similar to the properties in the first set of experiments, an excellent foil can be formed by the method of the invention, which foil has a good shiny appearance and has excellent toughness and corrosion resistance. However, when the Mn content is too high, no foil can be formed, and in experiment 4-4, the Mn content is reduced to about 2 parts by weight (based on 100 parts by weight of the molten alloy) by adding a step of removing Mn using iron oxide, and thus an alloy foil of acceptable quality can be discharged. Therefore, the manganese content in the alloy needs to be controlled to be less than or equal to 2 parts by weight, preferably in a lower range. The product prepared by the preparation method of the foil changes waste into valuable, the stainless steel waste is adopted, the inherent chromium and nickel elements in the stainless steel are introduced into the alloy, the chromium is beneficial to improving the corrosion resistance of the alloy, the nickel is an expensive element and can improve the toughness of the alloy, the formed foil not only has high corrosion resistance, but also improves the acid resistance, and meanwhile, the production cost is low, and is even lower than that of the first group to the third group.

It is further noted that phosphorus and boron are the elements that are avoided as much as possible in the preparation process of stainless steel, because the presence of phosphorus and boron can greatly reduce the toughness of stainless steel, and make the steel brittle. In the present application, however, the inventors of the present application have unexpectedly found that the addition of phosphorus and boron elements to stainless steel alloys can significantly reduce the melting temperature of the steel, enabling the alloys to be used to continuously produce alloy foils of greater thickness and greater width using a single roll process. Without being bound by theory, it is believed that the alloy foils produced in the present application have an amorphous composition, undergo rapid cooling during the manufacturing process, do not form crystals, and thus have better hardness and toughness, are isotropic, and have excellent properties that crystalline alloys such as stainless steel do not have.

Comparative example 1 (comparative example, preparation of ordinary Fe-based amorphous alloy foil)

In a similar manner to that of example 1, except that a general iron-based amorphous material was used to prepare the alloy foil, the alloy had a composition of, by mass, 80 parts by weight of Fe,16 parts by weight of Si, and 4 parts by weight of B. It was found that foils with a thickness above 30 micrometers and a width exceeding 200mm could not be formed.

Performance testing

The foils obtained in the above examples were tested for the following properties.

The test methods for various properties are as follows:

HV hardness was measured using a Shenzhen Shenyu instruments Vickers hardness tester, senyu instruments Limited.

Bm (T), br (T) and Hc (A/m) were measured using an industrial magnetic test apparatus of Oerson technologies, inc., of Hunan province.

The toughness of the material (referred to as 180-degree folding toughness or 180-degree folding non-breaking times) is measured by folding the foil 180 degrees, and the specific test method comprises the following steps of folding and flattening the foil 180 degrees (for the first time), then reversely folding and flattening the foil 180 degrees along the same folding line (for the second time), repeating the steps until the foil is broken, and recording the folding times.

The test results are shown in table 11.

TABLE 11 test results

Discussion of results

The method of the invention obtains the amorphous metal foil with excellent performance, and particularly has the following excellent properties: flame retardant, high temperature resistant, electromagnetic shielding, high strength, scratch resistance, low cost, light weight; the coating has good bright appearance, and has excellent toughness and corrosion resistance; high corrosion resistance, high acid resistance, better hardness and toughness, isotropy and excellent properties which do not exist in crystalline alloys such as stainless steel and the like.

Example 3

The embodiment provides a wide-width amorphous alloy foil and a waterproof coiled material prepared from the wide-width amorphous alloy foil. With the foils prepared in examples 1 and 2, as shown in fig. 2, 21 is an amorphous alloy foil, 22 is a waterproof substrate layer, and by adjoining the amorphous alloy foils to each other, a wide amorphous alloy foil with a width of more than 1 m is obtained. The seam can be prevented from water leakage by overlapping another narrow waterproof roll, and can also be sealed by weather-resistant glue to keep the seam waterproof.

Coating a waterproof substrate layer on the amorphous alloy foil, thereby preparing the wide-width amorphous alloy waterproof coiled material with the width exceeding 1 m, wherein the waterproof substrate layer is prepared from at least one material selected from the following materials: asphalt, polyurethane, plastic, butyl rubber, epoxy, and the like.

Example 4

The embodiment provides a waterproofing membrane by amorphous alloy foil preparation, it includes: the amorphous alloy film comprises an amorphous alloy foil and a waterproof substrate layer arranged on one side of the amorphous alloy foil; the amorphous alloy foil is an iron-based amorphous alloy foil prepared from an iron-based alloy, the composition of the iron-based alloy is consistent with that of experiment 1-1 in example 1, and the iron-based amorphous alloy foil (the thickness is 35 μm) is prepared according to the method in example 1. The waterproof base material is butyl rubber, and the thickness of the waterproof base material is 1.2 mm.

Example 5

The embodiment provides a waterproofing membrane by amorphous alloy foil preparation, it includes: the amorphous alloy foil comprises an amorphous alloy foil and a waterproof substrate layer arranged on one side of the amorphous alloy foil; the amorphous alloy foil is an iron-based alloy foil prepared from an iron-based alloy, the composition of the iron-based alloy is consistent with that of experiment 1-1 in example 1, and the iron-based alloy foil (the thickness is 35 μm) is prepared according to the method in example 1. The waterproof base material is epoxy resin, and the thickness of the waterproof base material is 1.0 mm.

Example 6

The embodiment provides a waterproofing membrane by amorphous alloy foil preparation, it includes: the amorphous alloy film comprises an amorphous alloy foil and a waterproof substrate layer arranged on one side of the amorphous alloy foil; the amorphous alloy foil is an iron-nickel-chromium-based alloy foil prepared from an iron-nickel-chromium-based alloy, the composition of the iron-nickel-chromium-based alloy foil is consistent with that of experiment 4-3 in example 2, and the iron-nickel-chromium-based alloy foil (the thickness is 35 μm) is prepared by the method in example 2. The waterproof base material is butyl rubber, and the thickness of the waterproof base material is 1.2 mm.

Example 7

The embodiment provides a waterproofing membrane by amorphous alloy foil preparation, it includes: the amorphous alloy foil comprises an amorphous alloy foil and a waterproof substrate layer arranged on one side of the amorphous alloy foil; the amorphous alloy foil is an iron-nickel-chromium-based alloy foil prepared from an iron-nickel-chromium-based alloy, the composition of the iron-nickel-chromium-based alloy foil is consistent with that of experiment 4-3 in example 2, and the iron-nickel-chromium-based alloy foil (the thickness is 35 μm) is prepared by the method in example 2. The waterproof base material is epoxy resin, and the thickness of the waterproof base material is 1.0 mm.

Comparative example 2

The embodiment provides a waterproof roll, which comprises an aluminum foil and a waterproof substrate superposed with the aluminum foil, wherein the thickness of the aluminum foil is 70 μm, and the waterproof substrate is butyl rubber and has the thickness of 1.2 mm.

Comparative example 3

The embodiment provides a waterproof roll, which comprises a stainless steel foil and a waterproof substrate superposed with the stainless steel foil, wherein the thickness of the stainless steel foil is 80 microns, and the waterproof substrate is epoxy resin and has the thickness of 1.0 millimeter.

Comparative example 4

This embodiment provides a commercially available multilayer waterproofing membrane, it includes PET rete, aluminium foil layer, PE rete and hot melt adhesive layer in proper order.

Data detection

1. Detection index and detection basis

The waterproof coiled materials of the embodiments 4, 5, 6 and 7 and the comparative examples 2, 3 and 4 are sequentially detected for the indexes of high temperature resistance, acid and alkali resistance, corrosion resistance, ageing resistance, puncture resistance, strong light irradiation resistance and the like, and the specific detection indexes are as follows:

(1) Salt spray test: GBT10125-2012 artificial atmosphere corrosion test salt spray test; the test conditions were: the test temperature is 35 ℃, the concentration of the sodium chloride solution is 5 percent, and the sodium chloride solution is dissolvedThe pH value of the solution is 6.8, and the salt spray sedimentation rate is 1.5 mL/(80 cm) ² * h) Test time 92h.

(2) Ultraviolet aging: ASTM G154-2016 Standard practice for fluorescent Ultraviolet (UV) Lamp Equipment for Exposure of non-metallic materials; the test conditions were: irradiation intensity of 0.89W/m in irradiation stage ² The temperature of the blackboard is 60 ℃, the duration time is 8h, the temperature of the blackboard in the condensation stage is 50 ℃, and the duration time is 4h.

(3) High-temperature test: GB-T2423.2 environmental test second part of electrician electronic product: test methods test B: high temperature; the test temperature is 85 ℃, and the test time is 92h.

(4) And (3) thermal aging: GB/T23457-2017 pre-paved waterproof roll;

(5) Water impermeability: GB/T328.10-2007 test method 10 part of waterproof roll materials for buildings: the water impermeability of asphalt and polymer waterproof coiled materials;

(6) Puncture resistance strength: performed as appendix B of CJ/T234-2006;

(7) Corrosion resistance (chemical liquid resistance) GB T328.16-2007 test method for construction waterproofing coils part 16: the high-molecular waterproof coiled material is resistant to chemical liquid (including water); the specific test method comprises the following steps: the degree of change in appearance of the sample was observed after the sample was immersed in 10% sodium chloride solution (saline), 15% sodium hydroxide solution, 10% acetic acid solution, and 10% hydrochloric acid solution at room temperature for one week, and the degree of change in appearance was evaluated in order from the viewpoints of color, gloss, delamination, deformation, warpage, and the like: none, mild, moderate, severe.

(8) Temperature of the surface irradiated with intense light: and (3) providing strong light irradiation by adopting a 2000-watt lamp, keeping the position of the waterproof coiled material to be tested, which is close to the light source, at a distance of about 38 ℃, continuously irradiating and measuring the surface temperature of the waterproof coiled material until the surface temperature reaches a stable value, and recording the highest surface temperature as the surface temperature of the strong light irradiation.

2. The result of the detection

The standard value in the table is GB/T23457-2017 pre-paved waterproof coiled material. As can be seen from the table above, the amorphous alloy waterproof coiled material prepared by the technical scheme meets the relevant national standards in terms of performance indexes, is remarkably superior to a comparative example in aging resistance and puncture strength, shows excellent corrosion resistance, and still shows extremely high weather resistance even if a protective layer is not additionally arranged due to the excellent performance of the amorphous alloy foil.

The above description is intended to be exemplary of the present disclosure, and not to limit the scope of the present disclosure, which is defined by the claims appended hereto.

Claims

1. A waterproof roll material made of an amorphous alloy foil, comprising: the amorphous alloy foil is an iron-nickel-chromium-based alloy foil prepared from an iron-nickel-chromium-based alloy, the iron-nickel-chromium-based alloy comprises iron elements, chromium elements, nickel elements, phosphorus elements, boron elements and impurity elements, wherein the iron elements account for a part by weight, the chromium elements account for b part by weight, the nickel elements account for f part by weight, the phosphorus elements account for c part by weight, the boron elements account for d part by weight, the impurity elements account for e part by weight, 66 is more than or equal to a + f is less than or equal to 86, and 6 is more than or equal to f is less than or equal to 60,6 is more than or equal to b is less than or equal to 21,5 is less than or equal to c is less than or equal to 12,0.1 is more than or equal to d is less than or equal to 1.8, and 8 is more than or equal to c +3d is less than or equal to 13, and e is less than or equal to 5, calculated by total 100 parts by weight.

2. The waterproof roll material according to claim 1, wherein the iron-nickel-chromium-based alloy contains the following elements in parts by weight: a + f is more than or equal to 76 and less than or equal to 85, b is more than or equal to 7 and less than or equal to 11, c is more than or equal to 7 and less than or equal to 10, d is more than or equal to 0.6 and less than or equal to 1.2, and when the impurity elements contain Mn, the mass of the Mn element accounts for less than 2 parts by weight.

3. Waterproofing membrane according to claim 1, wherein the iron-nickel-chromium based alloy has a HV hardness of more than 800, a maximum magnetic induction Bm and a remanence Br of the iron-nickel-chromium based alloy measured under the same conditions of less than 70% of the values measured for 1k101 (standard iron-based amorphous soft magnetic alloy strip), such as less than 62% of the values measured for 1k101 (standard iron-based amorphous soft magnetic alloy strip), and a 180 ° half-fold toughness of 2 or more, such as 3 or more.

4. The waterproofing membrane according to claim 1, wherein the amorphous alloy foil has a thickness of 10 to 98 microns, or a thickness of 20 to 40 microns, or a thickness of 30 to 50 microns, or a thickness of 20 to 65 microns, or a thickness of 25 to 60 microns.

5. The waterproofing membrane according to claim 1, wherein the amorphous alloy foil has a width of more than 30mm, a width of more than 60mm, a width of more than 100mm, a width of more than 200mm, a width of more than 280mm, or a width of more than 350 mm.

6. The waterproof roll according to claim 1, wherein the 180 ° double fold toughness of the amorphous alloy foil is 2 times or more, for example 3 times or more.

7. The waterproofing membrane according to any one of claims 1 to 6, wherein the waterproofing substrate layer is made of at least one material selected from the group consisting of: asphalt, polyurethane, plastic, butyl rubber, epoxy, and the like.

8. The waterproof coiled material of claim 7, wherein a release film layer is arranged on one side of the waterproof substrate layer away from the amorphous alloy foil.

9. A waterproofing membrane according to claim 7 wherein the thickness of the waterproofing substrate layer is 0.5 to 3mm or 1 to 3mm, for example 2 to 3 mm.

10. A method for preparing a waterproofing membrane according to any preceding claim comprising the steps of:

the amorphous alloy foil is provided with a waterproof base material layer to prepare the waterproof coiled material, wherein the waterproof base material layer is prepared from at least one of the following materials: asphalt, polyurethane, plastic, butyl rubber, epoxy, and the like.

11. The method for producing a waterproof roll according to claim 10, further comprising the step of, before providing the waterproof substrate layer:

12. The production method of a waterproof roll according to claim 10, wherein the amorphous alloy foil is produced by:

an ejection step: ejecting the alloy melt onto a cooling roller at a temperature of between 1000 ℃ and 1220 ℃ (such as between 1100 ℃ and 1220 ℃) and at least 50 ℃ higher than the melting temperature of the alloy melt (such as at least 100 ℃ higher than the melting temperature of the alloy melt), and forming the iron-nickel-chromium-based alloy foil, namely the amorphous alloy foil.