EA022538B1 - Coating for a device for shaping glass material - Google Patents

Abstract

The invention relates to a coating for a device for shaping glass materials, including a first quasicrystalline, approximate, or amorphous metal phase and a second phase consisting of a eutectic alloy having a fusion point of 950 to 1,150°C and a nominal hardness of 30 to 65 HRC; equipment for shaping glass into sheet glass or plate glass provided with said coating; a material consisting of said coating; a premixed or prealloyed powder, or a formed flexible cord or wire, making it possible to obtain said coating; and a thermal projection method for obtaining said coating.

Description

The present invention relates to the formation of glass products, according to which the molten glass is subjected to contact with a metal or similar surface for a certain time.

Such products are hollow glass products such as bottles, flasks, cans, etc., as well as glass products in the form of plates, sheets, etc.

Regardless of whether the molds used to make glass containers (bottles, flasks, jars, etc.) are made of cast iron or copper alloys (bronze), such molds require intensive lubrication to prevent glass from sticking to their cavities. Such lubrication involves the application of formulations containing solid lubricants such as graphite, and the lubricant must be applied to the hot mold very often during production (every 1-2 hours). This preparation has the following main disadvantages:

the occurrence of dangerous situations (evaporation of certain substances into the atmosphere of the plant, slippery floors as a result of substances entering the floor, manual application of lubricant to the device, etc.);

loss of productivity (after each application of the lubricant, the first bottles produced in the mold are discarded).

Therefore, the authors of the present invention drew attention to the development of a semi-permanent, non-sticky coating having a set of properties that have never been combined to date.

The coating should not be sticky to the glass draft form at high temperature without applying lubricants or applying their minimum amount.

Such a coating should be wear-resistant and have a service life that makes the additional costs economically viable. In particular, good mechanical resistance of the coating is required when exposed to high temperatures in contact with molten glass, as well as when closing the mold with cold glass, which can cause dents in some areas of the mold cavity (mainly sharp edges).

On the other hand, the coating must withstand strong thermal shocks (tension, thermomechanical stresses).

Particular attention was also paid to the compatibility of the coating with the repair operations of molds usually carried out at manufacturing plants: the accumulation by powder of brazing of a powder of the type No. CrgPre§1 (eutectic powder, melting point: from 1055 to 1090 ° C). Such repair operations are unavoidable and necessary due to the aforementioned minor irregularities when closing the mold with cold glass. The coating must withstand the accumulation of materials together with the materials contained in the re-melting at high temperature using a special blowtorch, and even better, have metallurgical compatibility with such accumulated materials so that the part being repaired is coherent with the rest of the cavity coating.

And finally, the coating should have sufficient thermal conductivity so as not to affect the heat removal from the glass too strongly by the forming device (shape, etc.).

The desired objectives were achieved as a result of the implementation of the present invention, one of the objects of which is a coating for a device intended for forming glass products, including the first quasicrystalline or close to it, or an amorphous metal phase and a second phase consisting of a eutectic alloy having a melting point from 950 to 1150 ° С and nominal hardness from 30 to 65 НКс.

In this context, the expression quasicrystalline phase means phases having rotational symmetries, usually incompatible with translational symmetry, i.e. symmetries with a 5-, 8-, 10- or 12-fold axis of rotation, detected by diffraction or radiation. As an example, the icosahedral phase of the I point group m 3 5 can be mentioned (cf. Ό. 8yesytap, I. В1есй, Ό. ОгаΙίαδ. IV. Saip, Ме1а1йс Ryakke , Ryukyu1 ReOe \ u Leyetk, Wo1. 53, Mar. 20, 1984, Radek 1951-1953) and the decagonal phase of the point group 10 / ttt (cf. L. Αχΐδ, Ryu8yu1 Be \ ae \ y Leyetk, Yo1. 55, No. 14, 1985, Radek 1461-1463). An X-ray diffraction diagram of the present decagonal phase was published in OyGtasyop Arrgoasy 1o 81e gis1ee oG Eesadopa 1 Oyakyuguk SHN TM. Niyo18, S. 1apo1, 1. Rappeyet, A. P1apey1, Ryukyuk Leyetk, A-117-8, 1986, 421427.

The expression close phases or close compounds in this description means real crystals as long as their crystallographic structure remains compatible with translational symmetry, but which in the electron diffraction photograph have diffraction patterns whose symmetry is close to 5-, 8-, 10- or 12x rotational axes.

By amorphous alloy is meant an alloy containing only the amorphous phase, or an alloy in which some crystallites may be present among the dominant amorphous phase.

According to preferred features of the coating according to the present invention

- 1 022538 it includes a third solid lubricating phase;

said first, second and third phases are present in amounts of 30-75 vol.%, respectively 70-25 vol.% and respectively 0-30 vol.%, preferably 45-65 vol.%, respectively 4525 vol.% and respectively 0-20 vol.%; a content of less than 30 vol.% does not allow to obtain a sufficient effect to prevent adhesion; a content of less than 25 vol.% of said second phase reduces the compatibility of the coating with the above-mentioned mold repair operations below the required level and increases its fragility; the presence of said third phase may be particularly preferred when carrying out a process requiring good glide of glass on a glass forming device; and said first phase is a quasicrystalline and / or close phase and includes an aluminum-based alloy, and / or said first phase is an amorphous metal phase and includes a zirconium-based alloy and / or highly entropic alloy;

said first phase may include several of the above components as a mixture.

Numerous examples can be mentioned as aluminum-based alloys that can be included in the composition of said first quasicrystalline phase.

The document RK 2744839 describes quasicrystalline alloys having an atomic composition A1 _a X _a U _e 1 ₆ , in which X represents at least one element selected from B, C, P, 8, Oe and δί, Υ represents at least at least one element selected from V, Mo, Cr, Mn, Fe, Co, Νί, Ki, Ki and Ρά, I represents inevitable technological contaminants, 0 <q <2. 0 <ά <5, 18 <e <29, and a + b + e + d = 100%.

The document RK 2671808 describes quasicrystalline alloys having an atomic composition A1 _a Cu _b Co, _L (B, C) cMaHl, in which M represents one or more elements selected from Fe, Cr, Mn, Cu, Ki, Mo, Νί , Θδ, V, Md, Ζη and Ρά, N represents one or more elements selected from Τι, Cr, H £, Ky, ΝΒ, Ta, Υ, δί, Oe and rare earth elements, and I represents the unavoidable technological pollutants impurities, where a> 50, 0 <b <14, 0 <b '<22, 0 <b + b'<30, 0 <c <5, 8 <b <30, 0 <e <4, £ <2 , and a + b + b '+ c + ά + e + £ = 100%.

Alloys having the composition A1 _a Cu _{b L} Co _b ', (B, C) _with M ^ _e 1 _£ , in which 0 <b <5, 0 <b'<22, 0 <c <5, and M represents Mn + Fe + Cr or Fe + Cr are especially preferred.

The report Ζ. Msheuzku e1 a1. (8ushro8shsh MK8 PA11 2003 Ε1esΐ ^ ^ osoάero8 ΐeά OiazkgzyaShpe Soaypdz from £ Wn-8isk \ Ueag Ke8181ay Sookzuage mentioned alloy A1 ₆₅ Cu ₂₃ PE1 _2.

Also, within the context of the present invention, aluminum-based alloys described in document UO 2005/083139 containing more than 80 wt.% Of one or more quasicrystalline or similar phases having an atomic composition A1 _a (Fe1 _x X _x ) are also suitable _B (ίτι- _; Υ _{; /} ΤΖ _ζ Υ _{; /} , where

X represents one or more isoelectronic elements with Fe selected from Ki and Oz;

Υ represents one or more elements isoelectronic with Cr selected from Mo and;

Ζ is an element or a mixture of elements selected from Τί, Cr, H £, V, N6, Ta, Mn, Ke, Ky, Νί and Ρά;

I represents unavoidable contaminants other than Cu;

-a + b + c + ζ = 100;

- 5 <b <15; 10 <s <29; 0 <ζ <10;

- xb <2;

- whisker <2;

- 3 <1.

According to one specific embodiment, the quasicrystalline alloy has an atomic composition A1 _n Fe _L1 Cr _with 3 _| in which a + b + c + _) = 100;

<B <15; 10 <s <29; .) <1.

The following examples of aluminum-based alloys that can be incorporated into said first close phase may be mentioned.

First of all, we should mention the orthorhombic phase Οι, characteristic of an alloy having an atomic composition A1 ₆₅ Cu ₂₀ Fe1 ₀ Cr ₅ , the parameters of individual elements of which in nanometers are: a ₀ ⁽¹⁾ = 2,366, b0 ⁽¹⁾ = 1,267, с0 ^{( 1)} = 3.252. Such an orthorhombic phase Οι is called close to the decagonal phase. Moreover, such a phase is so close to it that it is impossible to distinguish its X-ray diffraction pattern from the decagonal phase.

It may also be referred to rhombohedral phase having the following parameters: a _z = 3.208 nm, α = 36 °, present in the alloys having a composition close to Cu A1 _{64 24 2} PE1, from the standpoint of the number of atoms (AM AzYueg Abl Ρ Oiuoy. Mutosguzyi Shpe A1ReSi Ryase o £ RzeUo 1co5a1vMga1 8utte1gu sh OshMsguyay, e8. M.M Tts ay δ.

This phase is close to the icosahedral phase.

Orthorhombic phases Ο2 and Ο3 may also be mentioned, having the corresponding parameters a ₀ ⁽²⁾ = 3.83, b0 ⁽²⁾ = 0.41, c0 ⁽²⁾ = 5.26 and a0 ⁽³⁾ = 3.25, B0 ⁽³⁾ = 0.41, c ₀ ⁽³⁾ = 9.8 in nanometers present in an alloy having the composition A ^ Cn ^ Cn ^ C, from the standpoint of the number of atoms, or also orthorhombic

- 022538 phase O ₄ having parameters ao ⁽⁴⁾ = 1.46, b0 ⁽⁴⁾ = 1.23, c0 ⁽⁴⁾ = 1.24 in nanometers, formed in an alloy having the composition Λ1 ₆₃ ίτι _χ Ρθι ₂ ίτι ₂ . from the position of the number of atoms. Orthorhombic phases with similar composition are described, for example, in S. Eopd, GM. Enok 1. Ma1epak 8s1epse, 26 (1991), 1647.

Phase C having a cubic structure, very often observed together with quasicrystalline or close phases, may also be mentioned. This phase, which is formed in some A1-Si-Fe and A1-Si-Re-Cr alloys, consists of a superstructure due to the chemical order of the alloy elements relative to aluminum sites having a structure phase of the C8-C1 type and also having a lattice parameter a! = 0.297 nm. A diffraction pattern of such a cubic phase was published (S. Eopd, 1.M. Enbok M. Be Vo1881ei, S. 1po1; No, and no EShtasbop 81 у £ Не (Not RegNesNs Cgo \ y (у £ Не (Not A1 ₆₅ Cu ₂₀ Re ₁ 5 1§aNebga1 Oshsbgsgu ^ ak 1. RNu 8. Sopbeppseb Mayeg, 2 (1990), 6339-6360) of a sample having a pure cubic phase and composition A1 ₆₅ Cu ₂₀ Fe ₁₅ , from the standpoint of the number of atoms.

Mention may also be made of phase H having a hexagonal structure formed, as shown by the epitaxial bonds observed using electron microscopy, directly from phase C, between the crystals of phases C and H and simple bonds connecting the lattice parameters, namely, _n = 3 ^ 2 a ₁ / ^ 3 (up to 4.5%), and with _n = 3 ^ 3 a ₁ / ^ 2 (up to 2.5%). This phase is isotypic with a hexagonal phase, designated as FA1Mp, found in A1-Mp alloys containing 40 wt.% Mp [M.A. Tau1og, 1n1gsh1a1Ns RNakek sh (Not AShshshsh-Mapapeke V1pagu 8u81esh, Asta Me1a11igdua 8 (1960) 256].

The cubic phase, its superstructures and the phases formed from it constitute a class of close phases of quasicrystalline phases having similar compositions.

On the other hand, said first phase may be an amorphous metal phase.

Firstly, a type 1 alloy may be mentioned. This alloy is an amorphous alloy, the atomic composition of which contains at least 50% of elements such as Τι and Ζγ; while the dominant and necessarily present element is Ζγ, while the quantity Τι may be equal to zero. The elements constituting the rest are preferably selected from the group consisting of A1, Co, Cr, Cu, Fe, Νί, 8ί, Mn, Mo and V. Of particular interest are such compositions as ^{Ζ ^} 48.5 ^Τ ^ 5.5 ^Α1 Π ^Cu 22 ^N ^! 3 ^{, Ζ ^} 55 ^{C from} 0 ^Α1 ! 0 ^N ^ 5 ^{, Ζ} ^ 55 ^Τ ^ 5 ^N ^ | 0 ^Ά1 | 0 ^{С and} 20. ^Ζ ^ 65 ^Ά1 -.5 ^C and 2-.5 ^N ^ | 0. ^Ζ ^ 65 ^Ά1 -.5 ^N ^ | 0 ^C and | -.5. ^{Ζ ^} 48.5 ^Τ ^ 5.5 ^Cu 22 ^N ^! 3 ^Α1 7 ^, ^ 60 ^A 115 ^Co 2.5 ^Ν 17.5 ^ 15, ^ 55 ^ 20 ^ 10 ^ ½ ^{in particular} . ^ 556.4.130 ^ 10 ^ 5.

Secondly, a highly entropic alloy may be mentioned. High entropy alloy is an alloy that does not contain one dominant element, but consisting of 5-13 elements present in an equimolar amount, which can be from 5 to 13%. The advantage is that in such an alloy the formation of disordered solid solutions is favorable relative to the synthesis of brittle intermetallic crystalline phases. In addition, it consists of nanocrystallites dispersed in an amorphous or crystalline matrix. Typically, a high-entropy alloy contains at least 5 elements selected from the group consisting of A1, Co, Cr, Cu, Pe, Νί, 8ί, Mn, Mo, V, Ζγ and Τι.

The alloy compositions of particular interest are highly entropic alloys containing from 5 to 13 basic elements in equimolar quantities, the atomic composition of each of which is less than 35%, such as FeCoCrCiA1Mn, ReCoCrCiAl _{0> 5} , CuCoN ^ C ^ Α1PeMoΤ ^ VΖ ^, CuΤ ^ ReN ^ Ζ ^ Сο, Α1Τ ^ VРеN ^ Ζ ^, МοΤ ^ VРеN ^ Ζ ^, ^ Έ ^ ΝίΖ ^, А1ТГТРе№2гСо, МοΤ ^ VРеN ^ Ζ ^ Сο, CuΈ ^ ΝίΖ ^ α-, Α1Τ ^ VРеN ^ Ζ ^ СοС ^, МοΤ ^ VРеN ^ Ζ ^ СοС ^, А18ШСгРеСо№Мо ₀ , ₅ , А18ГПСгРе№Мо _{0> 5} .

According to the present invention, said second phase preferably mainly consists of a nickel-based alloy comprising the following elements in the following amounts in wt.%:

Sg: 0-20

C: 0.01-1 0-30

Re: 0-6

8ί: 0.4-6

B: 0.5-5

Co: 0-10

MP: 0-2

Mo: 0-4

Cu: 0-4 or from an alloy based on cobalt, comprising the following elements in the following amounts in wt.%:

Νί: 10-20

Sg: 0-25

C: 0.05-1.5 0-15

Re: 0-5

8ί: 0.4-6

- 3 022538

B: 0.5-5

Μη: 0-2

Mo: 0-4

Cu: 0-4 or from a mixture of two such alloys.

According to one preferred embodiment, said third phase, the presence of which is optional, mainly consists of at least one of the following compounds or a mixture of several of them:

- XP ₂ , in which X is selected from Ca, Md, 8g, Ba, in particular CaP ₂ , MdR ₂ and BaP ₂ ,

- XP ₃ , in which X is selected from 8c, Υ, ba or any other rare earth elements,

- ΒΝ with hexagonal structure,

- Mo3 ₂ , (molybdenite), \ U82 (tungsten), StZ,

- X ₂ MoO8 ₃ , where X represents C§ or Νί,

- M _a 31 _b , where M = Mo, Νί or Cr, for example Μοδί ₂ ,

- X _and B _b, wherein X represents Mo, Cr, Co, Νί, Fe, Mn, V, Τί or Ζτ, in particular ΤίΒ _2, ΖτΒ ₂

- X _and Υ Β _{L c,} where X and Υ selected from Mo, Cr, Co, Νί, Fe, Mn, V, Τί and Ζτ, in particular MOFs or Mo ₂ №V ₂

- Xδ ^ Β. where X is Mo, Cr, Co, Νί, Pe, Mn, V, Τί or Ζτ.

According to the present invention, the thickness of the coating, preferably in decreasing order, is at least 5, 10, 20 microns, on the other hand; maximum 500, 350, 200 microns, on the other hand.

Other objects of the invention include a mold for the manufacture of hollow glass products, in particular a draft mold comprising a bottom wall, at least one part of the cavity of which has the above-described coating or loading chute, i.e. a device for receiving a glass preform and transporting it towards a shape, at least one part of the surface (contact with the preform) of which has the coating described above;

equipment for forming glass in the form of sheets or plates, at least one part of the surface of which, in contact with the glass, has the coating described above;

the material constituting such a coating;

pre-mixed or pre-alloyed powder, providing the possibility of obtaining such a coating;

flexible bead or flux-cored electrode wire, providing the possibility of obtaining such a coating; and a thermal spraying process to produce a coating, in particular plasma spraying or ΗνΟΡ spraying (high-speed flame spraying).

The present invention is illustrated by the following illustrative embodiment.

Example.

a) Surface preparation with an abrasive jet

After covering the non-treated areas, the surface is prepared by spraying abrasive grains of alumina-zirconia of 80 mesh size onto it (i.e., their average size is 180 microns). This material is preferable because of its high adhesion force, which limits the destruction of grains and, therefore, the inclusion of fractions of grains in the surface, inclusions that are detrimental to the adhesion of the coating.

b) Obtaining a filler material for coating

The first phase A is formed from a quasicrystalline powder having the following composition, wt.%: Aluminum 54.1; copper 17.8; iron 13; chrome 14.9.

The granulometric composition of the phase A powder is from 25 to 60 μm (only about 10% of the particles are less than 25 μm, and only about 10% of the particles are more than 60 μm).

The second phase A is formed from a powder of an alloy based on nickel having the following composition, wt.%: Chromium 7.8; iron 2.45; boron 1.6; silicon 3.6; carbon 0.26; nickel - the rest.

The particle size distribution of the phase B powder is from 15 to 45 microns (only about 10% of the particles are less than 15 microns, and only about 10% of the particles are larger than 45 microns).

Phases A and B are combined in a proportion of 40 vol.% Of product B to 60 vol.% Of product A.

Two powders A and B are mixed in such a way as to obtain a homogeneous distribution in the entire mass of the obtained powder.

Such a composite mixture is used to obtain a coating.

c) Obtaining coating by spraying

The coating is obtained by thermal spraying a previously prepared mixture. The spraying process is a ΗνΟΡ (high speed flame spraying) process. To carry out such a spraying process, the following components are required:

- 4 022538 model K2 spray gun manufactured by OTU OshVN (Ό); raw material chamber and powder dispersant.

In the described example, the K2 gun works on the principle of burning oxygen and kerosene Εχχδοί® Ό60 (trademark Εχχοη MoЫ1) with a high feed rate and a nozzle that emits a flame at a very high speed. The gun is cooled by chilled water circulation. The sprayed composite powder is injected into the combustion chamber, and then sprayed at high speed, feeding it to the center of the flame, so the powder partially or completely melts during the journey before it collides with the surface of the coated part (a principle known from thermal spraying).

The spray gun is attached to a maintenance robot that is programmed to clean the entire surface to be coated and at the same time maintain such an orientation that the angle of impact of particles on the surface is close to 90 °, and provides an adjustable cleaning speed, selected in such a way as to obtain the desired thickness.

In the described example, the following spraying parameters are used:

Options Units Control value Oxygen flow rate [l / min.] 800 Kerosene Flow Rate [l / hour] twenty λ (stoichiometric ratio flame) 1.15 Combustion chamber pressure [bar] 7.2 Nozzle design [mm] 150/12 Powder carrier gas [l / min.] 7.2 Powder Speed [g / min] 2 * 40 Cleaning speed [m / s] 1,6 Spray gun / distance to the sprayed surface [mm] 400

The cleaning cycle carried out by the robot is controlled so that the thickness of the resulting coating is from 50 to 100 microns.

It should be noted that the loss of phase A during the implementation of this process is greater than the loss of phase B, so the resulting coating contains only 55 vol.% Phase A by 45 vol.% Phase B.

g) Coating finish

After thermal spraying, the final operation is carried out to polish the surface of the coating.

Such an operation involves removing possible excess coating from the mold line;

reducing the surface roughness of the form in order to reduce it to a value of approximately 2 to 3 μm (Ra). This operation is preferably carried out using grinding washers from the abrasives used and the corresponding mechanism that rotates these grinding washers and exerts pressure on the surface of the mold.

The final coating thickness is checked (zone by zone) before using the mold. f) Evaluation, test coverage

Coated molds are finished according to the rules in force in this technique by applying a protective varnish or Regtar1a1e® glaze in the same way as on uncoated molds (application and then curing of the glaze in an oven).

The draft molds are then set in a bottle forming machine (type 18) and used without lubricant. Typically, jets of grease (graphite, ΒΝ or another type of grease) are regularly sprayed over the molds (with a frequency of several hours) in order to facilitate the placement of the glass blank in the mold and prevent its adhesion.

With the coating of the present invention, no lubrication is required during operation.

The methodology used includes the simultaneous testing of 4 to 8 forms having the same coating option, as well as evaluating the life of the coating based on the following 2 criteria:

when the mold stops working correctly (the workpiece in the mold is placed incorrectly, begins to stick), it is removed from the machine and inspected. Record the number of bottles received;

in the event that a malfunction occurs that is not related to the coating, use the same methodology: local repair, for example, with a dent on the material. The mold is then reinstalled in the machine.

The local repair procedure is carried out in accordance with the rules in force in this type of technology, using brazing material and then re-coating.

ί) Benefits from coating

Due to the fact that during operation no lubrication is required, there are no drawbacks associated with such lubrication due to the coating that is the subject of the present invention:

unspent lubricants are saved;

elimination of risks associated with the safety of the workstation - inhalation of vapors of chemicals during the hot-form lubrication operation, slippery surrounding area due to repeated deposition of partially evaporated lubricant around the machine, risk of injury, including the hands of the operator performing the lubrication;

reduction of waste - when lubricating molds, bottles obtained from freshly lubricated molds are discarded.

The above example has quantified the following benefits:

Waste at bottle production Coated as per the present invention Uncoated and greased Amount of waste after car 2% 3, 5% Amount of waste after the end inspection 0, 35% 0, 8%

During the 2-week production cycle, a total of 32 molds are determined, which were coated according to the above example, and compared with a 32 mold without coating. The number of bottles thrown into waste from coated molds decreased by 37,000 compared to production using uncoated molds (and lubricated).

d) the quality of the coating according to the present invention

The thermal conductivity of the coating is comparable to the thermal conductivity of the process and does not radically change the heat exchange between the mold and the glass preform, which means that it does not significantly change the operating parameters of the bottle making machine.

The service life of the coating according to the present invention is at least about 20,000 hours or from about 160,000 to 320,000 products. In other embodiments, the service life may be 1,000 hours or 800,000 articles.

The coating according to the present invention is compatible with standard mold repair operations traditionally carried out in accordance with the following procedure:

preparation of the area to be repaired by optional grinding to smooth the defect;

pre-heating the mold and then local heating in order to reach the melting point of the nickel-based powder used for local replenishment (melting point: from 950 to 1150 ° C);

feeding material through a blowtorch for powder; local reprocessing to restore geometry.

Most coatings cannot withstand such an operation; local heating of the mold usually causes the coating to loosen, and, on the other hand, metallurgical adhesion does not occur between the repair filler and the brazing alloy. According to the present invention, the component, known as the second phase B, is fully metallurgically compatible with the filler material used to repair the molds, in other words, in the field the two materials undergo mutual diffusion or even form an alloy, providing good continuity between the repair area and the original coating.

In addition, the coating according to the present invention, unlike many other coatings, can be etched, for example, by sandblasting, after losing their functionality, which again allows you to get a new coating described in this application, as long as the equipment for glass forming will not fail.

Claims (31)

CLAIM 1. Powder mixture to obtain a coating for a device intended for forming glass products, containing the first quasicrystalline or close to it or amorphous metal phase and the second phase, including a eutectic alloy having a melting point from 950 to - 6 022538 1150 ° С and nominal hardness from 30 to 65 NKs. 2. The mixture according to claim 1, characterized in that it includes a third solid lubricating phase. 3. The mixture according to claim 1, characterized in that said first and second phases are present in amounts constituting 30-75 and 70-25% by volume, respectively, optionally up to 30% by volume of the third solid lubricating phase. 4. The mixture according to claim 1, characterized in that said first phase is a quasicrystalline or close to it phase and includes an aluminum-based alloy and / or said first phase is an amorphous metal phase and includes a zirconium-based alloy and / or high-entropy alloy. 5. The mixture according to claim 1, characterized in that said second phase comprises a nickel-based alloy comprising the following elements in the following amounts, wt.%: Cr: 0-20; C: 0.01-1; V: 0-30; Re: 0-6; δΐ: 0.4-6; B: 0.5-5; Co: 0-10; MP: 0-2; Mo: 0-4; C: 0-4, or an alloy based on cobalt, comprising the following elements in the following amounts, wt.%: Νί: 10-20; Cr: 0-25; C: 0.05-1.5; V: 0-15; Re: 0-5; δΐ: 0.4-6; B: 0.5-5; MP: 0-2; Mo: 0-4; C: 0-4, or a mixture of two such alloys. 6. The mixture according to claim 2, characterized in that said third phase comprises at least one of the following compounds or a mixture of two or more of them: XP ₂ in which X is selected from the group consisting of at least Ca, Md, δτ and Ba, XP ₃ , in which X is selected from the group consisting of at least rare earth elements, Г with a hexagonal structure, at least one selected from the group consisting of Μοδ ₂ , νδ ₂ and ίτδ. Χ ₂ ΜοΟδ ₃ , where X is Νί, and Χ δίΒ, where X is Mo, Cr, Co, Νί, D, Mn, V, Τι or Ζτ. 7. The mixture according to claim 2, characterized in that said first, second and third phases are present in amounts of 45-65% by volume, 45-25% by volume and up to 20% by volume, respectively. 8. The mixture according to claim 6, characterized in that said third phase comprises XP ₃ , in which X is selected from the group consisting of at least δ ^ and b. 9. The mixture according to claim 6, characterized in that said third phase comprises XP ₂ , in which X is selected from the group consisting of at least Ca, Md, δτ and Ba. 10. The mixture according to claim 6, characterized in that said third phase comprises XP ₃ , in which X is selected from the group consisting of at least rare earth elements. 11. The mixture according to claim 6, characterized in that said third phase comprises ΒΝ with a hexagonal structure. 12. The mixture according to claim 6, characterized in that said third phase includes at least one selected from the group consisting of Μοδ ₂ , νδ ₂ and ίτδ. 13. The mixture according to claim 6, characterized in that said third phase comprises X ₂ ΜοΟδ ₃ , where X is Νί. 14. The mixture according to claim 2, characterized in that said third phase includes Μδ ^ ₂ , where M = Mo, V, Νί, or Cr. 15. The mixture according to claim 2, characterized in that said third phase comprises a boron compound containing boron and at least one metal selected from the group consisting of Mo, Cr, Co, Νί, Pe, Mn, V, Τι or Ζτ. 16. The mixture according to claim 2, characterized in that said third phase comprises a boron compound containing boron and at least two metals selected from the group consisting of Mo, Cr, Co, Νί, Fe, Mn, - 7 022538 V, Τι or Ζγ. 17. The mixture according to claim 6, characterized in that said third phase includes ΧδίΒ, where X is Mo, Cr, Co, Νΐ, Pe, Μη, V, ι or Ζτ. 18. The mixture according to claim 9, characterized in that said third phase comprises XP ₂ selected from the group consisting of CaP ₂ , MDR ₂ and BaP ₂ . 19. The mixture according to claim. 14, characterized in that said third phase includes Μοδι ₂ . 20. The mixture according to claim 15, characterized in that said third phase comprises ΤίΒ ₂ and / or ΖτΒ ₂ . 21. The mixture according to claim. 16, characterized in that said third phase includes MoCoV and / or Μο _{2 2} . 22. The form for the manufacture of hollow glass products, including the bottom wall containing a cavity in which at least part of the cavity wall is covered with a mixture according to claim 1. 23. The form according to p. 22, characterized in that the coating thickness is at least equal to 5 microns. 24. The form according to p. 22, characterized in that the coating thickness is maximally 500 microns. 25. The form according to p. 22, characterized in that the coating thickness is at least equal to 20 microns. 26. The form according to p. 22, characterized in that the coating thickness is maximally 200 microns. 27. A device for forming glass in the form of sheets or plates, at least one part of the surface of which, being in contact with glass, is coated with a mixture according to claim 1. 28. The device according to p. 27, characterized in that the coating thickness is at least equal to 5 microns. 29. The device according to p. 27, characterized in that the coating thickness is maximally equal to 500 microns. 30. The device according to p. 27, characterized in that the coating thickness is at least equal to 20 microns. 31. The device according to p. 27, characterized in that the coating thickness is maximally 200 microns.