Cartridge case and method for application of protective coating onto its surface

FIELD: production of cartridges of small arms of various designation, can be realized mainly for production steel cartridge cases of live cartridges of small arms.

SUBSTANCE: the steel cartridge case with a protective coating consists of successively applied layers: a zinc-phosphate layer in the form of a polymeric compound based on the polymer of polyorganosiloxane and the copolymer of butadiene with styrene and a polymer and/or oligomer modifying it, forming with the polyorganosiloxame of sale spatially joined structure of polymeric coating. The method for application of the protective coating onto the surface of a steel cartridge case includes a success forming of the zinc-phosphate layer serving as a prime coat, polymeric layer that is applied by a treatment of the cartridge case in one bath in an aqueous solution of the polymer of polyorganosiloxane and copolymer of butadiene with styrene and polymer and/or oligomer modifying it, or by a continuous successive treatment of the case in two baths, the cartridge case treatment in the first bath is conducted in an aqueous solution of the polymer of polyorganosiloxane and copolymer of butadiene with styrene, and it the second bath-in an aqueous solution of modifying polymer and/or oligomer, forming of the polymeric protective coating is conducted by hardening of the modified polymeric layer applied in the process of the thermal treatment up to forming of a sole spatially joined structure of the polymeric compound.

EFFECT: enhanced resistance to corrosion of the cartridge case coating and resistance of the given coating to attrition.

13 cl, 3 ex

 

The invention relates to the production of small arms ammunition for various purposes and can be implemented mainly for the manufacture of steel cartridge cases of small arms ammunition, shells construction of ammo and is similar to steel parts.

Known cartridge sleeve, made of steel and having a coating based on water-soluble polymer polyorganosiloxane and a copolymer of butadiene with styrene (water-soluble composition FPSM-51) on the second version of the utility model certificate on the Russian Federation No. 6441, MPK F42B 5/26, 16.04.98, water-Soluble composition for applying this coating is non-toxic, does not require special protection personnel, and the process of applying the coating on already made a simple sleeve.

The disadvantages of this liner can be attributed to the fact that the protective coating has an oily light character with the effect of the buildup. This drawback leads to the fact that in the process of manufacturing the entire product - cartridge: kapsulirovanie cartridge, the cartridge Assembly, sealing, transportation operations, etc. on the surface of the liner sticks dust consisting mainly of particles of the coating. During operation of the cartridges with the dirty sleeve of the hand of the user, as well as the shutter weapons, reducing its operational properties.

Known cartridge sleeve on the first independently researched and is independent of the claim for patent of the RF No. 2246684, MPK7 F42B 5/26; B21D 51/54, SS 22/12; SS 28/00, publ. 20.02.2005, which is selected as the closest analogue to declare the sleeve. This sleeve is made of steel and has a composite coating consisting of a consistently applied incoporates layer, polymeric layer and the outer film layer derived from a water-soluble film-forming substances.

This coating has a corrosion resistance that allows you to use it only floor liner ammo hunting and sporting destination with a guaranteed shelf life of at least 5 years and does not allow the use of cartridges of ammunition destination, requested a guaranteed shelf life of at least 25 years.

There is a method of applying a protective coating on the external surface of the metal hunting cartridge in its manufacture according to the patent of Russian Federation №2062166, MPK B21D 51/54, publ. 20.06.96, According to paragraph 2 of the present invention on the surface of the stamped in the size of the liner is applied metallic coating by chemical copper coating at room temperature for 3...5 min in a solution of sulfuric acid and copper sulfate. The disadvantages of this method include the fact that it is applicable only for sleeves, made of steel, plated with tombac. In addition, this technology relates to the harmful plants, and requires special tools the protection of personnel and special equipment.

There is a method of coating the surface of the cartridge case according to the second independent claim in the patent RF №2246684, MPK7 F42B 5/26; B21D 51/54, SS 22/12; SS 28/00, publ. 20.02.2005, which is taken as a prototype to the present method of applying a protective coating on the external surface of the cartridge. The method involves the initial formation on the outer surface of the steel cartridge case incoporates layer, followed by application of a polymer layer by processing the sleeve for at least 1 minute in an aqueous solution based polyorganosiloxane and a copolymer of butadiene with styrene concentration of 80...140 g/l at a temperature of 15...30°and the final formation of the protective coating by treating the liner in an aqueous solution of film-forming substance, after which the resulting coating is dried at a temperature of 160...220°C. the Main disadvantage of this sleeve - low corrosion resistance of the coating, providing a warranty period of storage of ammunition this sleeve without deterioration of their performance properties up to 5 years, which limits the scope of application of these cartridge cases for ammunition only sports and/or hunting purposes.

The present invention solves the problem of increasing the corrosion resistance of the coating cartridge case, increasing the resistance of the coating to the East is Rania, that will allow the use of this protective anti-corrosion coatings not only for hunting and sporting ammunition, but also to protect the sleeves of military small arms ammunition, adopted for service in the Russian army with a guaranteed shelf life of at least 25 years. In addition, the invention solves the problem of simplifying the technology of applying a protective coating on the cartridge case, made of steel, and the reduction of harm associated with the process. The invention solves the above problem without deteriorating external decorative appearance of the processed products.

The problem is solved in that the cartridge sleeve, made of steel and have a protective coating, characterized by the fact that the protective coating consists of sequentially deposited layers: incoporating layer that acts as a ground, and a polymer layer in the form of polymer-polymer complex based polymer polyorganosiloxane and a copolymer of butadiene with styrene and modifying its polymer and/or oligomer forming with polyorganosiloxanes single spatial crosslinked structure of the polymer coating.

At the same time as the modifying polymer used is a copolymer of butyl acrylate, methyl methacrylate and methacrylic acid, as well as modifying oligomer use of water-soluble modificatory the basis of phenol-formaldehyde, epoxy, polyester or alkyd resins.

When implementing the proposed method of applying a protective coating to the surface of the cartridge steel sleeve, initially on the outer surface of the cartridge case is formed incoporates layer that acts as a primer, and then form a polymer layer and carry out the heat treatment of the formed polymer layer of the protective coating. New in the proposed method is that the polymer layer is applied by treating the liner in an aqueous solution of the basic polymer-based polymer polyorganosiloxane and a copolymer of butadiene with styrene (the technical name for this water-soluble composition: PPSM-51, (TU 2149-054-10964029-2005) and its modifier based polymer or oligomer, or a mixture thereof, and the formation of a polymeric protective coating is carried out by curing the applied modified polymer layer during the heat treatment at a temperature selected from the range of 170 to 220°With in a period of time not less than 7 minutes, before the formation of a single spatial stitched patterns polymer-polymer complex.

Preferably, immediately after applying incoporates layer to perform its passivation of corrosion inhibitor on bichromates the basis of, for example, "Fascon 485" or "Fascon 486", (TU 2149-063-10964029-2004) with concentric is her solution 0,5...3 g/l at a temperature of 20...45° C.

Alternatively, the protective polymer layer can be applied in a continuous process by sequential processing of the case two baths. In the first bath to the surface of the sleeve causing the base polymer by treating the liner in an aqueous solution of the polymer polyorganosiloxane and a copolymer of butadiene with styrene total concentration is 5.0...to 12.0%. Directly after application to the surface of the sleeve main polymer process it in the second bath in an aqueous solution of modifier polyorganosiloxane-based polymer or oligomer, or a mixture thereof with a total concentration of 2.0...of 6.0%. As the modifying polymer polyorganosiloxane can be used an aqueous solution of a copolymer of butyl acrylate, methyl methacrylate and methacrylic acid, as well as modifying oligomer can be used aqueous solutions of modifiers based on phenol-formaldehyde or epoxy, or polyester or alkyd resins. This option after processing cartridges aqueous solution of the basic polymer is possible that sequential processing of shells in aqueous solutions of different modifiers in different baths.

To improve the anticorrosion properties of the protective coating processing liners in the last bath (second bath) can be carried out with the addition of corrosion inhibitor nor the Rita sodium in an amount of 0.1...0.5 g/l

As a variant of the protective polymer layer can be applied by treating the sleeves in the same tank in an aqueous solution of the mixture of the basic polymer polyorganosiloxane and a copolymer of butadiene with styrene concentration of a solution of 2.0...6,0%, and modifying its polymer or oligomer, or a mixture thereof with a total concentration of the solution, choose from a range of 2.0...of 6.0%. At the same time as the modifying polymer used is a copolymer of butyl acrylate, methyl methacrylate and methacrylic acid, as well as modifying oligomer use water-soluble modifiers based on phenol-formaldehyde, epoxy, polyester or alkyd resins. This treatment can be repeated by processing the sleeves in the second bath of similar composition. It is also possible that sequential processing of cartridges in a variety of baths, each of which is a mixture of the basic polymer and different modifier.

In the case of application of the modified polymer coating on the liner separately in different baths: application of the primary polymeric coating in the first tub, and processing cartridge in a solution of the modifier in the second tub (in subsequent baths), the concentration of the basic polymer in the first tub increase, compared with its concentration in the solution when handling cartridges is carried out in a mixture of the basic polymer and its option is Katara. This is due to the fact that the processing of the sleeves in the second tub (in subsequent baths) in the solution of the modifier portion of the previously deposited polymer layer of the basic polymer is washed off.

The formation of polymer-polymer complex of the applied modified polymer layer in the heat treatment process is carried out in a fairly narrow range of temperatures and should not deviate from the reference temperature by more than ±10°C. the Choice of base temperature is determined by the type of modifier. In any case, the temperature at which carry out thermal treatment applied modified polymer coating, choose from a range of values of the temperatures of 170 to 220°C. For the formation of protective polymer coatings enough thermal treatment should be made within 7 minutes.

In fact, the process of forming a protective polymeric coating occurs in three stages:

- phosphating surface;

- applied to the prepared surface of the modified polymer composition based on polymer polyorganosiloxane and a copolymer of butadiene with styrene (water-soluble composition FPSM-51);

the drying and curing the applied modified polymer coating by thermal processing.

Increase the protective properties of the formed polymer in which rite can be explained as follows.

An aqueous solution of polyorganosiloxane is fluid, easy analgilasa in water, reacts with the active functional groups of the polymers and oligomers of modifiers, mainly hydroxyl, carboxyl, epoxy and methyl.

In the process of heat treatment applied during curing of the modified polymer coating reactions occur leading to the formation of the polymer film consisting of polymer molecules linear structure. In addition to the formation of polymer chains linear structure, due to the reactions of interaction between functional groups of the modifier (in the case of acrylate carboxylic groups) with terminal hydroxyl groups polyorganosiloxane the formation of the so-called "oxygen bridges", i.e. there is a binding macromolecules in the transverse direction. As a result of crosslinks are formed spatially extensive custom made mesh structure, so-called polymer-polymer complexes, which, having a low permeability, become a reliable barrier to the penetration of aggressive ions to the surface of the substrate, i.e. to the metal surface of the sleeve.

The choice of ways of applying the modified polymer layer due to the desired properties of the formed coating, and hence the choice according to stuudio modifying solution, which gives forming polymer coating certain properties: chemical resistance to aggressive environment, corrosion resistance, water resistance, mechanical strength, abrasion resistance, heat resistance, etc.

Thus, by modifying the original polymer copolymers of acrylic number of achieved improvement of gloss, chemical resistance, and resistance to abrasion. The use of modifiers based on phenol-formaldehyde resin provides improved adhesion, mechanical strength and water resistance of the coating. Coating with epoxy groups possess high anti-corrosion properties. To make the coating of complex properties, modification of the basic polymer is carried out with the use of multiple modifiers simultaneously or sequentially, for example, acrylates and phenol-formaldehyde oligomers, etc. As shown by studies, modifiers based on acrylates having a polar carboxyl group, provided giving a polymer-coated cylinder liners on the basis of polyorganosiloxane the following properties:

- increased corrosion resistance;

- elimination of the "stickiness" of coverage;

significant mechanical reinforcement film (through the creation of extensive retinal patterns) and the exclusion of marriage "scrapes".

Similar properties b is obtained as a result of modification of the polymer composition FPSM-51 water-soluble modifiers based oligomer - phenol-formaldehyde resin rezol type, which is a linear polymer structure with integral functional methylol groups,- CH2HE is. The presence in the resin composition rezol free methylol groups allow the resin to samootverzhenij and interact during heat treatment with various hydroxyl - and hydrogen-containing compounds polyorganosiloxane. The resulting interaction of spatial cross-linked polymer structures provide the coverage specified protective properties.

Example 1

The surface of the cylinder liner, made of steel WA, pre-prepared for the application of protective coatings based on the following technologies:

- to remove dirt from the surfaces of the cylinder liners were they degreasing in alkaline detergent preparation, such as PTS-5 (Fascon 205", THE 2149-067-10964029-97 mixture of surfactants in combination with salts of inorganic acids), with a concentration of 20...60 g/l at a temperature of the working solution of 40...65°followed by rinsing in warm water;

- to remove from the surface of the liner oxidized films was performed by chemical etching the surface of the cylinder liner in sulfuric acid with a concentration of 50...90 ml/l and a temperature of 40...60°With subsequent washing in running cold water.

To avoid protravlivanija met is the lia and reduce sliming in the etching solution was added inhibitor etching, for example, TSC-A1 (TU 2458-002-48875050-2001) with a concentration of 1 to 2 ml/L.

The process of degreasing and etching may be performed separately in different baths, and together in the same tank, which allows to reduce the process of preparing a surface for application of a protective coating. In this case, a solution consisting of sulfuric acid, and the composition containing biodegradable surfactants, for example the song "Ecomet-S" (a mixture of sulfuric acid and sodium chloride, THE 2499-101-32441906-06) with a concentration of 45...60 ml/L.

To activate the surface of the liner before phosphotyrosine, with the aim of reducing the time phosphating, as well as the weight and size of the crystals of the phosphate layer, leading to an increase in the continuity of the coating and reduce its porosity, it is recommended to perform the processing cartridge in a solution of the activator phosphating, such as drug Foscan 471 (TU 2149-095-10964029-2002), consisting of a mixture of inorganic salts with a concentration of 1...2 g/l and a temperature of 20...30°C.

To improve the corrosion protection of the surface of the liner and increase the adhesion of the protective coating phosphating recommended in incoporates concentrate CCF-1 (Fascon 26", THE 113-08-428-89) with a concentration of 50...100 ml/l followed by rinsing in cold water.

To enhance the corrosion protection of the formed coating in malpercio the hydrated retention period, formed phosphate layer Passepartout in a solution of bichromate of potash with a concentration of 5...10 g/l and a temperature of 50...70°or in the preparation Foscan 486", which consists of a mixture of voorspelling corrosion inhibitors and contains no toxic salts of chromium, with a concentration of 1...2 g/l and a temperature of 20...45°C.

The polymer layer was applied by treating the shells in two baths. In the first bath by dipping and turning sleeves in a period of time not less than 3 min in an aqueous solution of organosilicon polymer solution polyorganosiloxane and a copolymer of butadiene with styrene (composition FPSM-51) with the concentration of the solution is 5.0...to 12.0%at a temperature of 18...25°on the surface of the shells struck the core polymer layer. Directly after application to the surface of the cartridge main polymer layer, they were processed in the second bath by dipping and turning in a period of time not less than 3 min in an aqueous solution of a polymeric modifier based on polyacrylate, the technical name for this solution "Ruzin 16" (acrylic emulsion, THE 2241-006-57845504-2003), with the concentration of the solution of 2.0...6,0%, at a temperature of 18...25°C. processing the sleeves in the second tub conducted with the addition of corrosion inhibitor sodium nitrite in an amount of 0.1...0.5 g/l

The final formation of the polymer coating was carried out by curing the applied m definerowana polymer layer at a temperature of 185± 5°C for 7 min before the formation of a single spatial cross-linked structure of the polymer-polymer complex. Heat treated liner was cooled to room temperature.

Example 2

The surface of the cylinder liner, made of steel WA, pre-prepared for applying a protective coating on the similar technology as described in example No. 1.

The polymer layer was applied by processing the sleeves in the same tank. The aqueous solution contained organosilicon polymer solution polyorganosiloxane and a copolymer of butadiene with styrene (composition FPSM-51) with a concentration of 2.0...6,0%, and as a modifier used water-soluble modifier additive e-MD-5A-based oligomeric epoxy modifier (TU 2251-01-34875572-2006), which was added to the same bath with a concentration of 2.0...of 6.0%. The total concentration of the solution did not exceed 11%. Processing cartridges conducted at a temperature only solution is 15...25°by dipping and turning sleeves in a period of time not less than 3 minutes, the Final formation of the polymer coating was carried out by curing the applied modified polymer layer at a temperature of 215±5°With in a period of time not less than 7 min before the formation of a single spatial cross-linked structure of the polymer-polymer complex. Heat treated sleeve Oh what was Adali to room temperature.

Example 3

The surface of the cylinder liner, made of steel WA, pre-prepared for applying a protective coating on the similar technology as described in example No. 1.

The polymer layer was applied by processing the sleeves in the same tank. Aqueous solution in the bath contained a mixture of organosilicon polymer solution polyorganosiloxane and a copolymer of butadiene with styrene (composition FPSM-51) with a concentration of 2.0...6,0% and two modifiers: modifier of water-soluble additives uh-MD-1a based on oligomeric phenol-formaldehyde modifier (TU 2251-01-34875572-2006), with a concentration of 2.0...4.0 percent, and the polymer modifier is an acrylic emulsion "Ruzin-16C" with a concentration of 2.0...4.0 percent. When this process was controlled by the total concentration of the solution, which should not exceed 11%.

The processing cartridge cases were when the temperature of the whole solution, equal to 15...25°With, by dipping and turning sleeves a period of time not less than 3 minutes

The final formation of the polymer coating was carried out by curing the applied modified polymer layer at a temperature of 205±5°With in a period of time not less than 7 min before the formation of a single spatial cross-linked structure of the polymer-polymer complex. Heat treated liner was cooled to room temperature.

Sawlani the cartridge case with a two-layer not "sticky" polymer coating was produced at the Tula cartridge plant, in particular, the above technologies, and were subjected to the tests on the corrosion properties and the stability of the coating to abrasion and reliability of weapons, ammunition with the stated case. Industrial tests have shown that martial and performance characteristics declared cartridge case is not inferior to the standard, and anti-corrosion properties and wear resistance far exceeds the cartridge case of the prototype. In addition, the claimed technology of applying a protective polymer coating is environmentally friendly and significantly reduces the production of cartridges for cartridges with the stated polymer coating. The results of the State tests to simulate a 25-year warranty period of storage cartridges with the stated case confirmed that the claimed coating the surface of the liner ensures fulfillment of requirements for small arms ammunition, corrosion protection and persistence of the tactical-technical characteristics of ammo in long-term storage for at least 25 years.

1. Cartridge sleeve, made of steel and have a protective coating, characterized in that the protective coating consists of sequentially deposited layers - incoporates layer that acts as a ground, and a polymer layer is in the form of polymer-polymer complex based polymer polyorganosiloxane and a copolymer of butadiene with styrene and modifying its polymer and/or oligomer, forming with polyorganosiloxanes single spatial crosslinked structure of the polymer coating.

2. The sleeve according to claim 1, in which the modifying polymer used is a copolymer of butyl acrylate, methyl methacrylate and methacrylic acid.

3. The sleeve according to claim 1, in which the modifying oligomer use phenol-formaldehyde, epoxy, polyester or alkyd resins.

4. The method of applying a protective coating on the surface of the cartridge case made of steel, comprising the successive formation of incoporating layer, performing the role of the soil, application of a polymer layer by processing the liner in an aqueous solution of the polymer polyorganosiloxane and a copolymer of butadiene with styrene and heat treatment of the polymer layer, characterized in that the polymer layer is applied or by processing the sleeves in the same tank in an aqueous solution of a mixture of polymer polyorganosiloxane and a copolymer of butadiene with styrene and modifying its polymer and/or oligomer, or by continuous sequential processing liners in two baths, while handling the cartridges in the first tub is conducted in aqueous solution polymer and polyorganosiloxane copolymer of butadiene with styrene, and the second bath is in an aqueous solution of the modifying polymer and/or oligomer, and the formation of a polymeric protective coatings perform n is the hardening caused the modified polymer layer during the heat treatment before the formation of a single spatial cross-linked structure of the polymer-polymer complex.

5. The method according to claim 4, characterized in that the heat treatment applied polymer coating is carried out at a temperature selected from the range of 170 to 220°With in a period of time not less than 7 minutes

6. The method according to claim 4, characterized in that after application incoporates layer Passepartout a corrosion inhibitor on bichromates the basis of, for example, "Fascon 485" or "Fascon 486" with a concentration of 0.5 to 3 g/l at a temperature of 20...45°C.

7. The method according to claim 4, characterized in that during application of the polymer layer by processing the sleeves in the same tank using an aqueous solution of a mixture of polymer polyorganosiloxane and a copolymer of butadiene with styrene concentration of a solution of 2.0...6,0% and modifying its polymer and/or oligomer with a concentration selected from the range of 2.0...6,0%.

8. The method according to claim 7, characterized in that the modifying polymer used is a copolymer of butyl acrylate, methyl methacrylate and methacrylic acid.

9. The method according to claim 7, characterized in that modifying oligomer use of phenol-formaldehyde, epoxy, polyester or alkyd resins.

10. The method according to claim 4, characterized in that during application of the polymer layer in a continuous process by sequential processing of the case two bath, first bath using an aqueous solution of the polymer paliggenesia the dignity and copolymer of butadiene with styrene concentration of the solution, 5.0...to 12.0%, and the second bath using an aqueous solution of the modifying polymer and/or oligomer concentration of a solution of 2.0...6,0%.

11. The method according to claim 10, characterized in that the modifying polymer used is a copolymer of butyl acrylate, methyl methacrylate and methacrylic acid.

12. The method according to claim 10, characterized in that as modifying oligomer use of phenol-formaldehyde, epoxy, polyester or alkyd resins.

13. The method according to claim 10, characterized in that the processing cartridge in the second bath are with the addition of corrosion inhibitor sodium nitrite in an amount of 0.1...0.5 g/l



 

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18 cl, 3 dwg, 1 ex

FIELD: methods of production of surface-treated steel materials and liquids for the steel materials chemical conversion treatment.

SUBSTANCE: the invention is dealt with a method of chemical conversion treatment of a steel material, which is produced with usage of a method of a surface treatment and a liquid for the treatment, in particular, to surface-treated material having an excellent positive resistance to a galling. The surface-treated steel material contains a steel material and a chemical conversion film. At that the chemical conversion film contains potassium in amount of 0.1-1000 mg/m2 and has a thickness within the range of 5-48 microns or within the range from exceeding 48 up to 50 microns. The method provides for the chemical conversion treatment realization on a surface of a steel material with utilization of a liquid containing zinc and phosphoric acid or manganese and phosphoric acid plus potassium. The invention allows to create a liquid, which due to addition of potassium forms a stable film of a phosphate type even on a steel,containing: chromium 0.5-13.0 %.

EFFECT: the invention ensures creation of a liquid, which forms a stable film of a phosphate type even on a steel, containing some % of chromium.

15 cl, 4 ex, 5 tbl, 1 dwg

 // 2246684

The invention relates to chemical surface treatment of metallic materials, and in particular to compositions for surface treatment of metals acidic aqueous solutions containing phosphates
The invention relates to the preparation of surfaces of metal parts to the operation of cold deformation (landing fasteners, extrusion, extrusion of pipes, wire drawing and other) with the use of phosphating and can be used in the metallurgical industry and mechanical engineering in the manufacture of wire, calibrated metal and machine parts

The invention relates to the field of corrosion of metals, and more specifically to protection from atmospheric and biological corrosion and can be used in mechanical engineering, instrumentation and other industries

The invention relates to the chemical, petrochemical, protection of metals from corrosion and can be used in mechanical engineering, instrumentation and other industries

The invention relates to the chemistry of protective coatings and can be applied to create a protective corrosion - and wear-resistant coatings

The invention relates to chemical treatment of metal surfaces by applying a phosphate coating
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