CN115011912A - Carbon/metal co-cementation-based throwing type glass breaking ball and manufacturing method and application thereof - Google Patents

Carbon/metal co-cementation-based throwing type glass breaking ball and manufacturing method and application thereof Download PDF

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CN115011912A
CN115011912A CN202210670104.8A CN202210670104A CN115011912A CN 115011912 A CN115011912 A CN 115011912A CN 202210670104 A CN202210670104 A CN 202210670104A CN 115011912 A CN115011912 A CN 115011912A
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glass breaking
throwing type
type glass
manufacturing
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CN115011912B (en
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张国栋
龚寅卿
周怡成
李孟钊
汪昌顺
银航
肖亚东
杨兵
李成林
梅青松
薛龙建
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Wuhan University WHU
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
    • C23C8/62—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes only one element being applied
    • C23C8/64—Carburising
    • C23C8/66—Carburising of ferrous surfaces
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
    • A62B3/00—Devices or single parts for facilitating escape from buildings or the like, e.g. protection shields, protection screens; Portable devices for preventing smoke penetrating into distinct parts of buildings
    • A62B3/005—Rescue tools with forcing action
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/34—Methods of heating
    • C21D1/44—Methods of heating in heat-treatment baths
    • C21D1/50—Oil baths
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/04—Hardening by cooling below 0 degrees Celsius
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
    • C23C10/20—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions only one element being diffused
    • C23C10/24—Salt bath containing the element to be diffused
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
    • C23C10/26—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions more than one element being diffused
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

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  • Metallurgy (AREA)
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Abstract

The invention provides a manufacturing method of a throwing type glass breaking ball based on carbon/metal co-infiltration, which comprises the following steps: firstly, smearing a carburizing agent on the surface of a matrix with edges after grinding and polishing, and then packing the matrix with aluminum foil paper to obtain a product A; secondly, putting the product A into a borax molten salt bath, heating and preserving heat for a certain time to obtain a product B; thirdly, performing primary cooling treatment on the product B, and then performing cryogenic treatment for a certain time to obtain a product C; and finally, soaking the product C in acid-containing boiling water, taking out, putting the product C into oil for tempering, and performing surface post-treatment to obtain the carbon/metal co-cementation-based throwing type glass breaking ball. The manufacturing method has the advantages of simple and efficient process, higher finished product rate and low comprehensive manufacturing cost, and the hardness of the surface coating of the prepared throwing type glass breaking ball is far higher than that of a glass breaking ball product with a ceramic structure, so that the method has wide popularization and application prospects in the fields of fire fighting, emergency disaster relief, breaking and dismantling and the like.

Description

Carbon/metal co-cementation-based throwing type glass breaking ball and manufacturing method and application thereof
Technical Field
The invention belongs to the technical field of additive manufacturing, and particularly relates to a carbon/metal co-infiltration-based throwing type glass breaking ball and a manufacturing method and application thereof.
Background
Along with the development of science and technology, toughened glass has obtained extensive application in daily life, has also put forward new requirements to broken glass instrument and fire control broken glass rescue work. Mainstream glass breaking tools in the existing market are handheld glass breaking tools, and the glass breaking distance is short, so that the glass breaking tools are not beneficial to overhead operation. The glass breaking ball is rapidly favored by the market due to the characteristics of easy carrying, high hardness and separation from short-distance constraint, and becomes a new hotspot for research on glass breaking tools.
Chinese patent application No. 201810972122.5 discloses a throwing type glass breaking ball which is manufactured by adopting a structure of 10 wt.% to 30 wt.% zirconia toughened by 70 wt.% to 90 wt.% alumina ceramic. In the manufacturing process of the glass breaking ball, zirconium oxide is unevenly dispersed in a matrix, and the likeA problem, inevitably leading to a lower final yield; in addition, the manufacturing method of mold-opening casting also results in higher production cost. Further, the hardness of the broken glass ball is generally maintained at 1500HV 0.1 Left and right sides, can once only break glass thickness and be thinner, the pottery has the shortcoming that the fragility is big simultaneously, and life is short, can't satisfy market demand.
The carbide of metals such as chromium, niobium, vanadium, tantalum and the like has higher hardness than the ceramic phase, and the highest hardness can reach 3500HV 0.1 The molten salt metal infiltration method (TD method) is a common method for preparing carbide coatings of metals such as chromium, niobium, vanadium and tantalum on the surface of high-carbon steel. However, in the process of preparing the carbide coating by adopting an aluminum powder reduction method in the TD method, because the volume of the broken glass ball is small and the activity of the aluminum powder is high, splashing and small-range explosion are easy to occur, and the safety of operators is easy to threaten; meanwhile, the direct metal infiltration mode easily causes the lower part of the coating to generate a carbon-poor area to influence the overall performance, and if the mode of firstly carburizing and then infiltrating metal is adopted, the quality of the coating can be improved, but the defects of more complicated process, high energy consumption and the like exist. Due to the factors, the popularization and the application of carbides of metals such as chromium, niobium, vanadium, tantalum and the like in the field of manufacturing of glass breaking balls are limited.
Therefore, how to provide a broken glass ball with higher hardness, simplify the process flow of broken glass ball manufacturing, reduce energy consumption and cost, and improve the operation safety of the manufacturing process is a technical problem to be solved urgently.
Disclosure of Invention
One of the purposes of the invention is to provide a manufacturing method of the throwing type glass breaking ball, which has higher hardness, simple preparation process, high safety and lower energy consumption and cost.
The second purpose of the invention is to provide a throwing type glass breaking ball which has high hardness, low brittleness, low cost, good ductility and convenient carrying.
The technical scheme adopted by the invention for realizing one of the purposes is as follows: the manufacturing method of the throwing type glass breaking ball based on carbon/metal co-infiltration comprises the following steps:
s1, smearing a carburizing agent on the surface of the polished matrix with the edges, and packing the matrix with the edges by using aluminum foil paper to obtain a product A; the material of the ribbed substrate is selected from steel with carbon content higher than 0.4%;
s2, putting the product A into a borax molten salt bath, heating and preserving heat for a certain time to obtain a product B; the borax molten salt bath contains 9-14 wt% of metal and/or corresponding oxide of the metal, wherein the metal comprises one or more of titanium, niobium, vanadium, chromium and tantalum;
s3, cooling the product B to 200-300 ℃ in a furnace, taking out, carrying out primary cooling treatment in a water bath for 1-1.5 h, and carrying out cryogenic treatment at-80-100 ℃ for 30-60 min to obtain a product C;
and S4, soaking the product C in acid-containing boiling water, taking out, tempering in oil, and performing surface post-treatment to obtain the carbon/metal co-cementation-based throwing type glass breaking ball.
The general idea of the invention for manufacturing the throwing type glass breaking ball by adopting the method is as follows:
on one hand, aiming at the defects of the glass breaking ball integrally manufactured by the existing ceramics, a method for manufacturing the glass breaking ball by adopting a metal infiltration additive manufacturing mode is provided. The method forms the carbide coating corresponding to titanium, niobium, vanadium, chromium or tantalum on the surface of the carbon-containing steel substrate, so that the process is simpler, the price is lower, the hardness of the obtained metal carbide coating is higher, the ductility is better compared with that of ceramic, the brittleness is low, and the carrying is more convenient.
On the other hand, aiming at the problems of dangerousness of using aluminum powder in the molten salt bath metal infiltration method, high energy consumption and low efficiency in the process of firstly carburizing and then infiltrating metal and the like, the invention provides a new improvement scheme: the aluminum foil paper is used for separating the carburizing and metal infiltration processes of the broken glass ball, and the carburizing and metal infiltration process can be realized in one step in the molten salt bath; meanwhile, the melted aluminum foil can be used as a reducing agent to participate in the metal infiltration process, and compared with the method of directly adding aluminum powder, the method is safer, greatly simplifies the process flow and energy consumption, and has lower cost and higher efficiency.
Furthermore, in order to consolidate the performance of the coating, ensure better bonding property with the matrix and improve the yield, the invention also adds a series of post-treatment steps, including the step quenching operation of the product of the borax molten salt bath and the cryogenic treatment operation. The furnace cooling to 200-300 ℃ ensures the uniformity of the surface diffusion of the coating, and the water bath standing for 1-1.5 h can be used for secondary quenching to obtain a large amount of high-strength and high-toughness martensite and can also be used for primary cooling treatment, so that the cracking of the coating in the subsequent cryogenic treatment can be effectively prevented; the subzero treatment is carried out for 30-60 min at the temperature of-80 to-100 ℃, so that the toughness of the workpiece can be obviously improved and the service life of the workpiece can be prolonged under the condition of not reducing the strength and the hardness of the workpiece. Then, the acid-containing boiling water treatment and the tempering operation are carried out, and the surface post-treatment is carried out on the product, so that the surface of the product has certain plasticity, and the product is more convenient to carry.
In step S1, the aluminum-foil paper is further subjected to the following pretreatment operations: and soaking the aluminum foil paper in the nano alumina slurry for 10-60 min, taking out and air-drying. In the invention, the aluminum foil is pretreated to form a layer of aluminum oxide high-melting-point coating on the surface of the aluminum foil, so that the time of the aluminum foil in the molten salt bath can be prolonged, and the carburization process in the aluminum foil can be smoothly finished. Preferably, the aluminum foil paper is coated outside the ribbed matrix in a layered wrapping mode. In some preferred embodiments, the aluminum foil paper has a single layer thickness of 0.025mm, 8 wrapping layers and a total thickness of 0.02 mm.
In some preferred embodiments, the carburizing agent consists of 64 wt.% carbon powder (0.154mm, 100 mesh), 6 wt.% sodium carbonate, 6 wt.% sodium acetate, 12 wt.% yellow blood salt, and 12 wt.% flour. The carburizing agent has the characteristic of rapid carburization, and can rapidly complete the carburization process before the aluminum foil is melted.
In the step S2, the heating temperature in the borax molten salt bath is 1000 +/-50 ℃, and the heat preservation time is 3-6 h. Further, the borax molten salt bath also comprises 80-83 wt.% of Na 2 B 4 O 7 1 to 3 wt.% of B 2 O 3 And 4-6 wt.% of calcium silicate powder. In the invention, safer calcium silicate powder is adopted as a reducing agent in the molten salt bath, so that the operation safety is ensuredMeanwhile, part of silicon and carbon migrated to the surface can form high-hardness silicon carbide, so that the surface coating prepared by the post-treatment process is more compact and uniform.
In some preferred embodiments, in step S3, the method of cryogenic treatment includes: and (3) putting the product B subjected to primary cooling treatment into a treatment tank filled with a mixture of liquid nitrogen and dry ice, starting ultrasonic stirring, and carrying out cryogenic treatment for 30-60 min. According to the invention, the cryogenic environment formed by matching liquid nitrogen and dry ice is utilized, and an ultrasonic stirring mode is assisted, so that the uniform temperature of each surface of the product in the cryogenic treatment process is ensured, the generation of surface stress is greatly reduced, the product is effectively prevented from cracking, and the formed coating has higher adhesive force and better stability.
In the step S4, the composition of the acid-containing boiling water includes 5 wt.% of H 2 SO 4 10 wt.% urotropin and 85 wt.% water; the temperature of the acid-containing boiling water is 60-80 ℃, and the soaking time is 30-60 min. Further, the oil temperature of the tempering treatment is 200-500 ℃, and the time of the tempering treatment is 1-3 hours.
Further, in step S4, the surface post-treatment specifically includes: and cleaning dirt on the surface of the product by using a laser cleaning agent and then spraying paint.
The second technical scheme adopted for achieving the purpose of the invention is as follows: providing a throwing type glass breaking ball prepared by the manufacturing method according to one object of the invention, wherein the throwing type glass breaking ball comprises a prism substrate and a hard surface coating on the surface of the prism substrate; the thickness of the hard surface coating is 0.05-1 mm.
In the present invention, the prism-carrying substrate is a regular-shaped polyhedron such as a regular tetrahedron, a regular hexahedron, a regular octahedron, a regular dodecahedron, a regular icosahedron, or the like. Preferably, the ribbed substrate is a regular dodecahedron, and it has been verified that the ribbed substrate of this shape has the best crushing effect under the same manufacturing conditions.
Furthermore, the overall hardness of the throwing type glass breaking ball is 2600-2800 HV 0.1 The maximum hardness is 3300-3500 HV 0.1 。
The throwing type glass breaking ball prepared by the invention can be used for remotely breaking toughened glass with the thickness of 25-30 mm. The glass breaking device can break toughened glass with the thickness of more than 30mm with the assistance of an ejection mechanism, has the performance far higher than that of a throwing type glass breaking ball made of ceramics, better meets the market demand, and has wide popularization and application prospects in the field of high-altitude rescue operation (such as fire-fighting glass breaking rescue).
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with the mode of manufacturing the broken glass ball by integrally opening the die of the ceramic structure in the prior art, the method does not need to open the die and does not consider the problem of uneven distribution of surface components caused by aggregation of fine powder in the casting process, the method directly prepares the metal carbide hard surface coating on the surface of the steel substrate by adopting the mode of infiltrating metal by melting borax, the process is simpler and more efficient, the final finished product rate is higher, and the comprehensive manufacturing cost is obviously reduced.
(2) The carbon/metal co-cementation process method adopted in the invention realizes the process of carburizing and cementation metal in the molten salt bath, and compared with the traditional process, the process has the advantages of simpler operation and higher efficiency while ensuring the quality. The hard surface coating on the surface of the broken glass ball adopts one or more of carbides of titanium, niobium, vanadium, chromium and tantalum, the hardness of the hard surface coating is obviously higher than that of ceramics such as alumina, and the hardness of the finally obtained broken glass ball surface coating can reach the integral hardness of 2700HV 0.1 The highest hardness can reach 3500HV 0.1 The multifunctional fire-fighting emergency rescue breaking device can break 25mm of toughened glass at one time (namely the thickest toughened glass used in the market can be broken easily), can break more than 30mm of toughened glass by adopting an ejection mechanism, and has wide application prospect in the field of breaking and dismantling in fire-fighting emergency rescue.
(3) The invention adopts metal with better plasticity and toughness and alloy thereof to replace ceramic with larger brittleness, has more convenient assembly process and higher yield, is not easy to damage in the transportation and carrying processes, and greatly prolongs the service life of the product.
Drawings
FIG. 1 is a schematic view of the overall structure of a throwing type glass breaking ball obtained in example 1 of the present invention;
FIG. 2 is a microstructure diagram of a throwing type glass breaking ball obtained in example 1 of the present invention;
FIG. 3 is a graph of hardness properties near the glass ball fusion line of the slingshot type made in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described below clearly and completely in conjunction with the embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Example 1
A carbon/metal co-carburized throwing type glass breaking ball specifically comprises the following steps:
(1) GCr15 steel, Nb powder, Ta powder and Ta are selected for the embodiment 2 O 5 The powder was subjected to the production of a glass-breaking ball.
(2) Polishing and grinding the processed matrix with the edges, uniformly coating a carburizing agent on the surface of the matrix with the edges, and wrapping the matrix with treated aluminum foil paper.
(3) Preparing a molten borax bath, and adding 80 wt.% of Na in advance 2 B 4 O 7 And 3 wt.% of B 2 O 3 After the materials are melted, 5 wt.% of calcium silicate powder and 12 wt.% of Nb powder, Ta powder and Ta are added 2 O 5 And fully stirring the powder, putting the powder into the treated broken glass balls after the powder is completely melted, quickly heating to 1000 ℃, preserving the temperature for 3h, cooling to 200 ℃ along with the furnace, taking out the powder, and putting the powder into a water bath for standing for 1 h.
(4) And (3) putting the broken glass balls into a cold treatment tank at the temperature of-80 ℃, wherein the treatment tank is a mixture of dry ice and liquid nitrogen, and the cold treatment process is accompanied by ultrasonic stirring for 60 min.
(5) Placing the glass breaking ball after cold treatment into 80 ℃ acid-containing boiling water for standing for 30min, and then tempering in 200 ℃ oil for 3 h;
(6) after the broken glass ball is cooled, the surface of the broken glass ball is subjected to laser cleaning and then is painted, and a perfect final finished product can be obtained.
Fig. 1 is a schematic diagram of an overall structure of a finished product of a throwing type glass breaking ball according to the embodiment, and a regular dodecahedron-shaped prism substrate is adopted for manufacturing the glass breaking ball.
FIG. 2 is a microstructure diagram of a finished product of a throwing type glass breaking ball of the embodiment; wherein, the coating is niobium and tantalum carbide, and the weld line is the boundary line between the carbide coating and the parent metal. As can be seen from FIG. 2, the weld line of the finished product is clear and straight, which represents that the coating and the base material are well combined, and provides a precondition for the finished product to have higher hardness.
FIG. 3 shows the hardness of the cast glass-breaking ball prepared by the present example near the weld line, and when the coating thickness is 0.4-0.6 mm, the maximum hardness can reach 3500HV 0.1 And the hardness is far higher than that of the glass breaking ball integrally manufactured by the existing ceramics.
Example 2
A carbon/metal co-carburized throwing type glass breaking ball specifically comprises the following steps:
(1) in the example, T12 steel, Ti powder, V powder and Nb powder are selected for manufacturing the glass breaking ball.
(2) Polishing and grinding the processed matrix with the edges, uniformly coating a carburizing agent on the surface of the matrix with the edges, and wrapping the matrix with treated aluminum foil paper.
(3) Preparing a molten borax bath, and adding 80 wt.% of Na in advance 2 B 4 O 7 And 3 wt.% of B 2 O 3 Adding 5 wt.% of calcium silicate powder and 12 wt.% of Ti powder, V powder and Nb powder after the materials are melted, fully stirring the materials, putting the materials into a treated glass breaking ball after the materials are completely melted, quickly heating the materials to 950 ℃, keeping the temperature for 6 hours, cooling the materials to 250 ℃ along with a furnace, taking the materials out, and putting the materials into a water bath for standing for 1 hour.
(4) And (3) putting the broken glass balls into a cold treatment tank at the temperature of-100 ℃, wherein the treatment tank is a mixture of dry ice and liquid nitrogen, and the cold treatment process is accompanied by ultrasonic stirring for 30 min.
(5) Placing the glass breaking ball after cold treatment into acid-containing boiling water at 60 ℃, standing for 60min, and immediately tempering in oil at 500 ℃ for 1 h;
(6) after the broken glass ball is cooled, the surface of the broken glass ball is subjected to laser cleaning and then is painted, and a perfect final finished product can be obtained.
Example 3
A carbon/metal co-carburized throwing type glass breaking ball specifically comprises the following steps:
(1) the steel T12, Cr powder, Ta powder and Cr are selected for the embodiment 2 O 3 The powder was subjected to the production of a glass-breaking ball.
(2) Polishing and grinding the processed matrix with the edges, uniformly coating a carburizing agent on the surface of the matrix with the edges, and wrapping the matrix with treated aluminum foil paper.
(3) Preparing a molten borax bath, and adding 80 wt.% of Na in advance 2 B 4 O 7 And 3 wt.% of B 2 O 3 After the materials are melted, 5 wt.% of calcium silicate powder and 12 wt.% of Cr powder, Ta powder and Cr powder are added 2 O 3 And fully stirring the powder, putting the powder into the treated broken glass ball after the powder is completely melted, quickly heating to 950 ℃, preserving the temperature for 6 hours, then cooling to 250 ℃ along with the furnace, taking out the powder, and putting the powder into a water bath for standing for 1 hour.
(4) And (3) putting the broken glass balls into a cold treatment tank at the temperature of-100 ℃, wherein the treatment tank is a mixture of dry ice and liquid nitrogen, and the cold treatment process is accompanied by ultrasonic stirring for 40 min.
(5) Placing the glass breaking ball after cold treatment into acid-containing boiling water at 70 ℃, standing for 50min, and immediately tempering in oil at 400 ℃ for 2 h;
(6) after the broken glass ball is cooled, the surface of the broken glass ball is subjected to laser cleaning and then is painted, and a perfect final finished product can be obtained.
Application example
The throwing type glass breaking balls prepared in examples 1 to 3 were subjected to tests of the overall hardness, the maximum hardness, the coating thickness and the breaking thickness, wherein the breaking thickness is the maximum thickness of tempered glass which can be broken by throwing once.
The relevant data are as follows in table 1:
TABLE 1
Figure BDA0003692971540000081
As can be seen from the above table, the total hardness of the throwing type glass breaking ball prepared in the embodiments 1-3 of the present invention is 2600-2800 HV 0.1 The maximum hardness is 3300-3500 HV 0.1 . The breaking thickness of the toughened glass reaches 30mm, which is far higher than that of the glass breaking ball with a ceramic structure in the prior art.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.

Claims (10)

1. A manufacturing method of a throwing type glass breaking ball based on carbon/metal co-infiltration comprises the following steps:
s1, smearing a carburizing agent on the surface of the polished matrix with the edges, and packing the matrix with the edges with aluminum foil paper to obtain a product A, wherein the material of the matrix with the edges is selected from steel with carbon content higher than 0.4%;
s2, putting the product A into a borax molten salt bath, heating and preserving heat for a certain time to obtain a product B; the borax molten salt bath contains 9-14 wt.% of metal and/or corresponding oxide of the metal, wherein the metal comprises one or more of titanium, niobium, vanadium, chromium and tantalum;
s3, cooling the product B to 200-300 ℃ in a furnace, taking out, carrying out primary cooling treatment in a water bath for 1-1.5 h, and carrying out cryogenic treatment at-80-100 ℃ for 30-60 min to obtain a product C;
and S4, soaking the product C in acid-containing boiling water, taking out, putting the product C into oil for tempering, and performing surface post-treatment to obtain the carbon/metal co-cementation-based throwing type glass breaking ball.
2. The manufacturing method according to claim 1, wherein in step S1, the aluminum-foil paper is subjected to the following pretreatment operations: and soaking the aluminum foil paper in the nano alumina slurry for 10-60 min, taking out and air-drying.
3. The method according to claim 1, wherein the heating temperature in step S2 is 1000. + -. 50 ℃ and the holding time is 3-6 hours.
4. The production method according to claim 3, wherein the borax molten salt bath further comprises 80 to 83 wt.% Na 2 B 4 O 7 1 to 3 wt.% of B 2 O 3 And 4-6 wt.% of calcium silicate powder.
5. The manufacturing method according to claim 1, wherein in step S3, the method of cryogenic treatment includes: and (3) putting the product B subjected to primary cooling treatment into a treatment tank filled with a mixture of liquid nitrogen and dry ice, starting ultrasonic stirring, and carrying out cryogenic treatment for 30-60 min.
6. The manufacturing method according to claim 1, wherein in the step S4, the composition of the acid-containing boiling water includes 5 wt.% of H 2 SO 4 10 wt.% urotropin and 85 wt.% water; the temperature of the acid-containing boiling water is 60-80 ℃, and the soaking time is 30-60 min.
7. The manufacturing method according to claim 6, wherein the temperature of the oil for the tempering treatment is 200 to 500 ℃, and the time for the tempering treatment is 1 to 3 hours.
8. A throwing type glass breaking ball prepared by the preparation method according to any one of claims 1 to 7, wherein the throwing type glass breaking ball comprises a prismatic substrate and a hard surface coating on the surface of the prismatic substrate, and the thickness of the hard surface coating is 0.05-1 mm.
9. The tossed break ball of claim 8,characterized in that the overall hardness of the throwing type glass breaking ball is 2600-2800 HV 0.1 The maximum hardness is 3300-3500 HV 0.1 。
10. The application of the throwing type glass breaking ball prepared by the manufacturing method according to any one of claims 1 to 7 or the throwing type glass breaking ball according to claim 8 or 9 is characterized in that toughened glass with the thickness of 25-30 mm is remotely crushed by the throwing type glass breaking ball or toughened glass with the thickness of more than 30mm is crushed after an ejection device is additionally arranged.
CN202210670104.8A 2022-06-14 2022-06-14 Throwing type glass breaking ball based on carbon/metal co-permeation and manufacturing method and application thereof Active CN115011912B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2356213A (en) * 1999-11-12 2001-05-16 Allan Rhodes Glass breaking device
US20180264293A1 (en) * 2017-03-20 2018-09-20 Uniqative LLC Impact Tools
CN108796426A (en) * 2017-09-27 2018-11-13 深圳市金胜金属技术有限公司 A kind of superhard treatment process of metal surface boronising
CN109852924A (en) * 2019-02-28 2019-06-07 贾春德 A kind of nanometer, micron formula, preparation method and the steel with the textura epidermoidea of carbon material enhancing ultra-fine grain textura epidermoidea of receiving
CN209933870U (en) * 2018-08-23 2020-01-14 平裕（成都）科技有限公司 Throwing type glass breaking ball
US20220161063A1 (en) * 2020-11-24 2022-05-26 Shatter Tactical, Llc Window breaking device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2356213A (en) * 1999-11-12 2001-05-16 Allan Rhodes Glass breaking device
US20180264293A1 (en) * 2017-03-20 2018-09-20 Uniqative LLC Impact Tools
CN108796426A (en) * 2017-09-27 2018-11-13 深圳市金胜金属技术有限公司 A kind of superhard treatment process of metal surface boronising
CN209933870U (en) * 2018-08-23 2020-01-14 平裕（成都）科技有限公司 Throwing type glass breaking ball
CN109852924A (en) * 2019-02-28 2019-06-07 贾春德 A kind of nanometer, micron formula, preparation method and the steel with the textura epidermoidea of carbon material enhancing ultra-fine grain textura epidermoidea of receiving
US20220161063A1 (en) * 2020-11-24 2022-05-26 Shatter Tactical, Llc Window breaking device

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