CN215283773U

CN215283773U - Waterproof roll containing amorphous alloy foil

Info

Publication number: CN215283773U
Application number: CN202121305551.0U
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: 2021-12-24
Anticipated expiration: 2031-06-11
Also published as: CN115233117A; CN115230258A; CN115233118B; CN115233118A; CN115233117B; CN215440644U; CN115230258B

Abstract

The application discloses waterproofing membrane containing metallic glass foil, it includes: the amorphous alloy thin film 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 has a thickness of 15-98 micrometers and a width larger than or equal to 100 mm. The waterproof coiled material has the characteristics of high temperature resistance, acid and alkali resistance, wear resistance, flame retardance, corrosion resistance, ageing resistance, root puncture resistance and scratch resistance, and has good weather resistance.

Description

Waterproof roll containing amorphous alloy foil

Technical Field

The utility model relates to a waterproofing membrane technical field especially involves a waterproofing membrane who contains metallic glass foil.

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 climate 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 climate tests is easy to cause the aging and the property deterioration of the waterproof roll. Conventionally, in order to enhance the properties of the waterproof roll, such as strength, heat insulation performance, root penetration resistance, and oxidation resistance, a metal foil (for example, an aluminum foil, a nickel foil, a cobalt foil, a copper foil, and the like, which are most common) is additionally provided when the waterproof roll is manufactured, or a protective layer is further provided on the metal foil, thereby increasing the manufacturing cost of the waterproof roll. However, even in this case, the durability of the waterproof roll in the prior art is still low, and after the waterproof roll is used for more than three years, cracking and aging often occur, and the waterproof roll cannot withstand the test of various climates 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.

SUMMERY OF THE UTILITY MODEL

The utility model discloses an aspect provides a waterproofing membrane containing metallic glass foil, including following embodiment:

embodiment 1. a waterproof roll comprising an amorphous alloy foil, comprising: the amorphous alloy thin film 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 has a thickness of 15-98 micrometers and a width larger than or equal to 100 mm.

Embodiment 2. the waterproof sheet according to embodiment 1, wherein the amorphous alloy foil is an iron-based amorphous alloy foil, a nickel-based amorphous alloy foil, a cobalt-based amorphous alloy foil, or an iron-chromium-nickel-based amorphous alloy foil.

Embodiment 3. the waterproof roll as claimed in embodiment 1, wherein the amorphous alloy foil has a thickness of 30 to 65 micrometers, or a thickness of 35 to 50 micrometers.

Embodiment 4. the waterproof roll as claimed in embodiment 1, wherein the amorphous alloy foil has a width of more than 200mm, a width of more than 280mm, or a width of more than 350 mm.

Embodiment 5. the roll of waterproofing according to any one of embodiments 1 to 4, 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 6. the waterproof roll material according to embodiment 1, wherein a release film layer is further disposed on a side of the waterproof substrate layer away from the amorphous alloy foil.

Embodiment 7. the waterproofing membrane according to embodiment 1, wherein the thickness of the waterproofing substrate layer is 0.5 to 3 mm or 1 to 3 mm, for example, 1.2 to 2.8 mm, for example, 1.8 to 2.5 mm.

The utility model also provides an iron-nickel-chromium alloy and a preparation method thereof, including the following implementation mode:

embodiment 8, 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 9 the method of embodiment 8, wherein the stainless steel is selected from one or more stainless steels having any of the following grades: 201. 201L, 202, 204, 301, 302, 303se, 304L, 304N1, 304N2, 304LN, 309S, 310S, 316L, 316N, 316J1, 316J1L, 317.

Embodiment 10, the method of embodiment 8, wherein the stainless steel is recycled stainless steel.

Embodiment 11 the method of embodiment 8, 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 12 the method of embodiment 8, wherein the melting step comprises refining the alloy melt at a temperature 100 to 200 ℃ above the melting temperature so that the elements in the alloy melt 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.

Embodiment 13, an iron-nickel-chromium-based alloy foil prepared by the method of any one of the preceding claims.

Embodiment 14 is an iron-nickel-chromium-based alloy including an iron element, a chromium element, a nickel element, a phosphorus element, a boron element, and an impurity element, wherein the iron element is a part by weight, the chromium element is b part by weight, the nickel element is f part by weight, the phosphorus element is c part by weight, the boron element is d part by weight, the impurity element is e part by weight, 66 a + f is 86 or more, and f is 6 or less and 60 or less, b is 6 or less and 21 or less, c is 5 or less and 12 or less, d is 0.1 or less and 1.8 or less, c +3d is 8 or less and 13 or less, and e is 5 or less, based on 100 parts by weight in total.

Embodiment 15 provides the iron-nickel-chromium-based alloy according to embodiment 14, 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 element, the mass part of the Mn element is less than 2.

Embodiment 16 the iron-nickel-chromium-based alloy of embodiment 14, 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), 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 (which may also be referred to as 180 ° half-fold no-break count) of greater than or equal to 2 times, such as greater than or equal to 3 times.

Embodiment 17, an iron-nickel-chromium-based alloy foil made from the iron-nickel-chromium-based alloy of any one of embodiments 14-16, 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 18, the iron-nickel-chromium-based alloy foil of embodiment 17, 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 19 the iron-nickel-chromium-based alloy foil according to embodiment 17, having 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), and a 180 ° half-fold toughness of 2 or more, such as 3 or more.

Embodiment 20, an iron-nickel-chromium-based alloy foil composite comprising at least two metal foils attached to each other with an adhesive layer interleaved 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 21 the iron-nickel-chromium-based alloy foil composite of embodiment 20, 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.

Embodiment 22, the composite of embodiment 20, having a width greater than 350mm, or having a width greater than 500 mm.

Embodiment 23, a method of making the iron-nickel-chromium-based alloy foil of any one of embodiments 17 to 19, 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 24 the method of embodiment 23, 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 320 mm.

Embodiment 25 the method of embodiment 23, wherein the furnish comprises at least one of stainless steel, ferrophosphorus, and ferroboron.

Embodiment 26 the method of embodiment 25, wherein the stainless steel is selected from one or more stainless steels having any of the following grades: 201. 201L, 202, 204, 301, 302, 303se, 304L, 304N1, 304N2, 304LN, 309S, 310S, 316L, 316N, 316J1, 316J1L, 317.

The utility model discloses an aspect provides an iron-based metallic glass and preparation method thereof, including following scheme:

scheme 1 discloses an iron-based amorphous alloy, which comprises iron, chromium, phosphorus, boron and impurity, wherein the iron comprises a, the chromium comprises b, the phosphorus comprises c, the boron comprises d, the impurity comprises e, 66 is equal to or greater than 86, 6 is equal to or less than 21, 5 is equal to or less than 12, 0.1 is equal to or less than 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, based on 100 parts by weight.

Scheme 2, the iron-based amorphous alloy according to 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 amorphous alloy according to scheme 1, having HV hardness of more than 800 as 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 180 ° half-fold toughness of 2 or more, such as 3 or more, as measured under the same conditions.

Scheme 4, an iron-based amorphous alloy foil prepared from the iron-based amorphous 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 amorphous alloy foil according to scheme 4, which 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.

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

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

Scheme 8, the iron-based amorphous alloy foil composite of scheme 7, wherein the binder 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 and the method for preparing the iron-based amorphous alloy foil according to any one of schemes 4 to 6, wherein the method comprises the following steps:

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, and e is less 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 amorphous 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 320 mm.

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.

The utility model discloses technical scheme's effect is: 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 200mm) by using a single-roll continuous method at low cost. The utility model discloses a metal foil can also be through laminating preparation thickness bigger and the wideer composite metal foil of width, its performance is excellent, and is with low costs, can be used for multiple application field that requires high to corrosion resistance, 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 is superposed with the waterproof substrate to prepare the waterproof coiled material, so that the waterproof coiled material is simple in structure, low in cost and convenient to construct. 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, root puncture resistance and scratch 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 amorphous alloy foil;

fig. 2 is the utility model discloses a broad width face metallic glass waterproofing membrane sketch map.

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 any 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 in the same sense.

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

The application provides a waterproofing membrane who contains metallic glass foil, it includes: the amorphous alloy thin film 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 has a thickness of 15-98 micrometers and a width larger than or equal to 100 mm. 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 application of amorphous materials is also limited by the fact that the amorphous strips in the prior art are narrow and thin. The inventor of the application finds that the amorphous alloy foil with certain thickness and width is used as the waterproof coiled material, so that the application field of the amorphous alloy material is widened, and the waterproof coiled material has the excellent characteristics of the amorphous alloy material. In the present application, the alloy composition and the preparation method of the amorphous alloy foil are not particularly limited as long as the thickness and width thereof are within the desired ranges and have the desired mechanical and chemical properties. 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 the present application, it is required that the amorphous alloy foil has a width of 100mm or more because too narrow a width causes an excessive number of adjacent lines to be processed at the time of laying. The facing material described herein has excellent properties in the following respects: acid and alkali resistance, corrosion resistance, strong light irradiation resistance, root puncture resistance, flame retardance, high temperature resistance, antibacterial property, electromagnetic shielding, high strength, wear resistance, scratch resistance and low cost. The method for preparing the waterproof coiled material is not particularly limited, and only the amorphous alloy foil and the prefabricated waterproof substrate layer are attached and hot-melted, or the waterproof substrate is coated on the amorphous alloy foil to form the waterproof substrate layer.

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 interchangeably.

In the present application, there is no particular limitation on the material selection of the amorphous alloy foil. In some embodiments, the amorphous alloy foil is an iron-based amorphous alloy foil, a nickel-based amorphous alloy foil, a cobalt-based amorphous alloy foil, or an iron-chromium-nickel-based amorphous alloy foil. The iron-based amorphous alloy foil is made of raw materials containing more than 60 wt% of iron elements. The cost of the iron-based amorphous alloy foil is low. The nickel-based amorphous alloy foil is characterized in that the weight content of nickel element in the amorphous alloy foil is higher than that of other elements. The nickel-based amorphous alloy foil has the best acid corrosion resistance. The cobalt-based amorphous alloy foil is made of raw materials containing more than 50 wt% of cobalt. The cobalt-based amorphous alloy foil has excellent soft magnetic characteristics. The Fe-Cr-Ni-based amorphous alloy foil is prepared from raw materials, wherein the content of each Fe-Cr-Ni element is not less than 3 wt%, and the total content of the three elements is not less than 60 wt%. The Fe-Cr-Ni-based amorphous alloy foil has good corrosion resistance and is not easy to be oxidized.

In some embodiments, the amorphous alloy foil has a thickness of 30 to 65 microns, or 35 to 50 microns. 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 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 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 has been widely used to replace asphalt with an environmental protection name.

In some embodiments, a release film layer is further disposed on a side of the waterproof substrate layer away from the amorphous alloy foil. From the type rete can provide the protection to waterproof substrate layer, can take off when laying the coiled material.

In some embodiments, the thickness of the waterproof substrate layer is 0.5 to 3 millimeters or 1 to 3 millimeters, such as 1.8 to 2.8 millimeters. The thickness of the waterproof coiled material is too small to influence the waterproof performance, 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 and 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.

In some embodiments, the amorphous alloy waterproof roll is prepared by: and refining the ingredients according to the proportion of alloy elements, melting to obtain an alloy melt, and enabling the alloy melt to quickly pass through a nozzle seam under pressure and quickly cool the surface of a cooling roller under the traction of a traction roller to obtain the amorphous alloy foil. Coating a waterproof substrate on the amorphous alloy foil to obtain the waterproof coiled material, wherein the waterproof substrate is made of at least one material selected from the following materials: asphalt, polyurethane, plastic, butyl rubber, epoxy, and the like. In some embodiments, the prepared different amorphous alloy foils are overlapped with each other to have an arbitrarily expanded breadth, and the prepared different amorphous alloy foils can be adhered with each other by using an adhesive to have an arbitrarily expanded breadth.

The application also provides an iron-based amorphous 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 larger than or equal to a, 86 is larger than or equal to a, 6 is larger than or equal to b, 21 is larger than or equal to 5 is larger than or equal to c, 12 is larger than or equal to 0.1 and smaller than or equal to d, 1.8 is larger than or equal to 8 and larger than or equal to c +3d, and 13 is larger than or equal to e and smaller 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 amorphous 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, the iron-based amorphous alloy means 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 amorphous 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 200mm) by using a single-roll continuous method at low cost. The utility model discloses a metal foil can also be through laminating preparation thickness bigger and the wideer composite metal foil of width, its performance is excellent, and is with low costs, can be used for multiple application field that requires high to corrosion resistance, 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 of Fe, Cr, P and B in the alloy can be within the above range, but in some embodiments, the iron-based amorphous alloy has 76-85 a, 7-11 b, 7-10 c and 0.6-1.2 d. Within these ranges, the fe-based amorphous alloy has a lower melting point, enabling more stable production of corrosion resistant metal foils with higher thickness (greater than 35 to less than 65 microns) and larger width (greater than 200mm) using a single roll continuous process at lower cost.

In some embodiments, the fe-based amorphous 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 ribbon), such as less than 62% of the values measured for 1k101 (standard fe-based amorphous soft magnetic alloy ribbon), measured under the same conditions (maximum induction Bm of less than 0.6T and remanence Br of less than 0.3T as 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-based amorphous alloy are determined by the prepared alloy foil, so the definition of the properties also applies to the alloy foil prepared by 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 application also provides an iron-based amorphous alloy foil prepared from the iron-based amorphous alloy in any one of the preceding claims, and having a thickness of 10-98 microns, or a thickness of 20-65 microns, or a thickness of 25-50 microns. The iron-based amorphous 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 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 iron-based 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. 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 fe-based amorphous alloy foil 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 and remanence Br of less than 0.3T as 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 application also provides an iron-based amorphous alloy foil composite material which comprises at least two layers of metal foils which are mutually stuck in a staggered manner through adhesive layers, wherein at least one layer of metal foil is the iron-based amorphous alloy foil. Through the compounding, 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; 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 present invention provides a method for preparing the iron-based amorphous alloy foil, 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 amorphous 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 320 mm. 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 for 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 satisfies 8 ≦ c +3 ≦ d ≦ 13, the impurity content 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 applicants have unexpectedly found that by using a process of adding phosphorus and boron to stainless steel, an alloy can be prepared which has a relatively low melting point (below 1150 ℃, e.g., below 1050 ℃, e.g., below 1000 ℃) and which has good flow properties at relatively low temperatures (between 1000 ℃ and 1220 ℃), which enables the preparation of alloy foils having a relatively high thickness and a relatively wide 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, 316J1, 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 to prepare the foil.

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 manganese content of the 304 stainless steel is lower, the alloy melt has a lower manganese content and can be not 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 used₂O₃Two 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 impurities in the alloy melt are not any elements, and the impurity elements refer to other elements which do not significantly affect the properties of the iron-nickel-chromium alloy within the content range, such as 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 iron-nickel-chromium-based alloy comprises iron element, chromium element, nickel element, phosphorus element, boron element and impurity element, wherein 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 larger than or equal to a + f is smaller than or equal to 86, 6 is larger than or equal to f is smaller than or equal to 60, 6 is larger than or equal to b is smaller than or equal to 21, 5 is larger than or equal to c is smaller than or equal to 12, 0.1 is larger than or equal to d is smaller than or equal to 1.8, 8 is larger than or equal to c +3d is smaller than or equal to 13, and e is smaller 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 of greater than 800, 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), measured under the same conditions (maximum magnetic induction Bm of less than 0.6T, remanence Br of less than 0.3T, measured by scanning), and a 180 ° half-fold toughness of greater than or equal to 2, such as greater than or equal to 3. 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 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, which are prepared by rapid cooling of the alloy melt as a result of the single roll process described herein, have the excellent toughness and high HV hardness of amorphous alloys without the brittleness of crystalline alloys, and have further improved toughness and prospects for large-scale production applications due to the addition of nickel relative to the iron-based amorphous 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 amorphous alloy foil has excellent performances of corrosion resistance, flame retardance, high temperature resistance, electromagnetic shielding, high strength, scratch resistance, light weight and the like, and can obtain remarkably 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 iron-nickel-chromium-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 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 less than 70% of the values measured for 1k101 (standard iron-based amorphous soft magnetic alloy strip), e.g. less than 62% of the values measured for 1k101 (standard iron-based amorphous soft magnetic alloy strip), measured under the same conditions (maximum magnetic induction Bm of less than 0.6T and remanence Br of less than 0.3T as measured by scanning), and a 180 ° double fold toughness of 2 or more times, e.g. 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 manner through adhesive layers, 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 therefore the application field of the alloy foil can be expanded.

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

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 batch material includes at least one of stainless steel, ferrophosphorus, and ferroboron.

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

Another aspect of the present invention provides a finishing material, which includes: the alloy foil (iron-based amorphous alloy foil or iron-chromium-nickel-based alloy foil) comprises an 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 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.

Another aspect of the present invention provides a composite material, which comprises the alloy foil or the facing material, and a base structure connected to the facing material or the alloy foil. The composite material has excellent properties in the following aspects: corrosion resistance, flame retardance, high temperature resistance, electromagnetic shielding, high strength, scraping 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 plate having at least one layer made from the alloy of any 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, which comprises the alloy foil according to any one of the above aspects. The electromagnetic shielding case has excellent performance in the following aspects: corrosion resistance, flame retardance, high temperature resistance, electromagnetic shielding, high strength, scraping resistance and low cost.

Another aspect of the present invention provides a product, such as a conference room, a house, etc., using the electromagnetic shield of any one of the above.

Another aspect of the invention provides a cable of core-sheath construction, wherein at least one layer of the sheath comprises or consists of the alloy foil of 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 present invention provides an article comprising the amorphous alloy of any one of the above, the alloy foil of any one of the above, or the finishing material of any one of the above.

Another aspect of the present 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 this example are shown in Table 2 below, and other materials not shown in the Table are all commercially available products.

TABLE 2 raw materials and sources

Example 1 (preparation of Fe-based amorphous 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 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-based amorphous 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 the present example, three groups were tested in total, 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

Numbering	Fe content	Cr and Cr content	P phosphorus content	B content
					Experiment 1-1	85	6	8	1
Experiment 1-2	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

Numbering	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
Experiment 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

Numbering	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
					Experiment 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 that the sum of the boron content 3 times and the phosphorus content is between 8% and 13% needs to be satisfied at the same time. 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 the 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 percent of B in the alloy is less than 2%, when the mass percent of B is more than or equal to 2%, 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 matching ratio between phosphorus and boron, i.e. the sum of the boron content, which is 3 times that of the phosphorus content, and the phosphorus content is between 8% and 13%, beyond which a satisfactory foil cannot be produced.

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 Table 9 and the fourth set of experiments 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, a good foil can be formed by the method of the present invention, which foil has a good bright appearance and has excellent toughness and corrosion resistance, wherein the content of P and B is similar to the properties in the first set of experiments. 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 substantially reduce the melting temperature of the steel, enabling the alloys to be used to continuously produce thicker and wider alloy foils 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 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 microns 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 Senyu instrument Vickers hardness tester from Senyu instruments and Equipment 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 (called 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 steps of folding and flattening the foil 180 degrees (for the first time), then reversely folding and flattening the foil 180 degrees (for the second time) along the same folding line, 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 utility model discloses a method has obtained the excellent amorphous metal foil of performance, especially has excellent following property: flame retardant, high temperature resistant, electromagnetic shielding, high strength, scratch resistance, low cost and 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 the amorphous alloy foils are overlapped with each other to obtain a wide amorphous alloy foil with a breadth of more than 1 m.

Coating a waterproof substrate layer with the thickness of about 2mm on the amorphous alloy foil, thereby preparing a wide-width amorphous alloy waterproof coiled material with the width of more than 1 m, 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.

Example 4

The embodiment provides a waterproofing membrane by amorphous alloy foil preparation, it includes: the amorphous alloy foil is an iron-based amorphous alloy foil prepared from an iron-based amorphous alloy, the composition of the iron-based amorphous alloy is consistent with that of experiment 2-1 in embodiment 1, and the iron-based amorphous alloy foil (the thickness of the iron-based amorphous alloy foil is 35 microns) is prepared according to the method in embodiment 1. The waterproof base material is butyl rubber, and the thickness of the waterproof base material is 1.8 mm.

Example 5

The embodiment provides a waterproofing membrane by amorphous alloy foil preparation, it includes: the amorphous alloy foil is an iron-based amorphous alloy foil prepared from an iron-based amorphous alloy, the composition of the iron-based amorphous alloy is consistent with that of experiment 2-1 in embodiment 1, and the iron-based amorphous alloy foil (the thickness of the iron-based amorphous alloy foil is 35 microns) is prepared according to the method in embodiment 1. The waterproof base material is epoxy resin, and the thickness of the waterproof base material is 1.8 mm.

Example 6

The embodiment provides a waterproofing membrane by amorphous alloy foil preparation, it includes: the amorphous alloy foil is an iron-nickel-chromium-based amorphous alloy foil prepared from an iron-nickel-chromium-based alloy, the composition of the iron-nickel-chromium-based alloy is consistent with that of experiment 4-2 in embodiment 2, and the iron-nickel-chromium-based amorphous alloy foil (the thickness of the iron-nickel-chromium-based amorphous alloy foil is 35 microns) is prepared according to the method in embodiment 2. The waterproof base material is butyl rubber, and the thickness of the waterproof base material is 1.8 mm.

Example 7

The embodiment provides a waterproofing membrane by amorphous alloy foil preparation, it includes: the amorphous alloy foil is an iron-nickel-chromium-based amorphous alloy foil prepared from an iron-nickel-chromium-based alloy, the composition of the iron-nickel-chromium-based amorphous alloy is consistent with that of experiment 4-2 in embodiment 2, and the iron-nickel-chromium-based amorphous alloy foil (the thickness of the iron-nickel-chromium-based amorphous alloy foil is 35 microns) is prepared according to the method in embodiment 2. The waterproof base material is epoxy resin, and the thickness of the waterproof base material is 1.8 mm.

Example 8

The embodiment provides a waterproofing membrane by amorphous alloy foil preparation, it includes: the amorphous alloy thin film comprises an amorphous alloy foil and a waterproof base material layer arranged on one side of the amorphous alloy foil. The waterproof base material is epoxy resin, and the thickness of the waterproof base material is 1.8 mm. The amorphous alloy foil is a cobalt-based amorphous alloy foil.

The cobalt-based amorphous alloy foil is prepared by a method consistent with that of the embodiment 1, the thickness of the foil is 20 micrometers, and the alloy raw materials are as follows: 8 wt% of Fe,8 wt% of Si,14 wt% of Ni, 69 wt% of Co and the balance of other elements. The cobalt-based amorphous alloy foil is a typical amorphous soft magnetic material known in the prior art, the soft magnetic property of the cobalt-based amorphous alloy foil is better than that of 1k101, the hardness HV of the cobalt-based amorphous alloy foil is 830, the folding toughness of the cobalt-based amorphous alloy foil is 2 times, and the manufacturing cost is high due to high raw material cost.

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 mu m, and the waterproof substrate is butyl rubber and has the thickness of 1.8 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 1.8 millimeters.

Comparative example 4

This embodiment provides a commercially available multilayer waterproofing membrane, and 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, the pH value of the solution is 6.8, and the salt spray sedimentation rate is 1.5mL/(80 cm)²H), assay time 92 h.

(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 stage²The 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 4 h.

(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 92 h.

(4) And (3) thermal aging: GB/T23457-;

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

(6) puncture resistance strength: according to appendix B in CJ/T234-;

(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 containing amorphous alloy foil is characterized by comprising: the amorphous alloy thin film 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 has a thickness of 15-98 micrometers and a width larger than or equal to 100 mm.

2. The waterproof roll according to claim 1, wherein the amorphous alloy foil is an iron-based amorphous alloy foil, a nickel-based amorphous alloy foil, a cobalt-based amorphous alloy foil, or an iron-chromium-nickel-based amorphous alloy foil.

3. The waterproofing membrane according to claim 1 wherein the amorphous alloy foil has a thickness of 30 to 65 microns, or a thickness of 35 to 50 microns.

4. A water-proof coiled material according to claim 1, wherein the amorphous alloy foil has a width greater than 200 mm.

5. The waterproof roll material according to any one of claims 1 to 4, wherein said waterproof substrate layer is made of one material selected from the group consisting of: asphalt, polyurethane, plastic, butyl rubber, epoxy resin.

6. The waterproof coiled material of claim 1, wherein a release film layer is further arranged on one side of the waterproof substrate layer away from the amorphous alloy foil.

7. The waterproof roll material according to claim 1, wherein the thickness of the waterproof substrate layer is 0.5 to 3 mm.

8. A water-proof coiled material according to claim 1, wherein the amorphous alloy foil has a width of more than 280 mm.

9. A water-proof coiled material according to claim 1, wherein the amorphous alloy foil has a width greater than 350 mm.

10. The waterproof roll material according to claim 7, wherein the thickness of the waterproof substrate layer is 1.2 to 2.8 mm.