WO2017176132A1

WO2017176132A1 - A method for modifying the structure of materials by means of a glow discharge and a device for modifying the structure of materials by means of a glow discharge

Info

Publication number: WO2017176132A1
Application number: PCT/PL2017/000034
Authority: WO
Inventors: Ihar YELLKIN
Original assignee: DECEWICZ, Sławomir; ADAMSKI, Sławomir; PASZKIEWICZ, Bartłomiej; BLUM, Rafał
Priority date: 2016-04-05
Filing date: 2017-04-03
Publication date: 2017-10-12
Also published as: PL416759A1

Abstract

The subject of the invention is a method for modifying the structure of materials by means of a glow discharge, and a device for modifying the structure of materials by means of a glow discharge occurring in a dilute gas environment, which is particularly suitable for the modification of solids and liquids. The method is based on placing the modified material in a vacuum chamber (1), in which pressure is kept at the level of 10^-1 Pa to 10^-7 Pa, which is followed by a glow discharge process initiated between the anode (5) and the cathode (6) by means of an electron potential difference of 30 V to 2,000 V, which is preceded by dosing humidified air by means of a humidified air dosing system (4) into the vacuum chamber (1), which is used to initiate the process of glow discharge. After the glow discharge has become stable, the inflow of humidified air is stopped, which results in the generation of an alternating electromagnetic field with carrier frequency (f_n) of 50 Hz to 150 Hz between the anode (5) and the cathode (6). The distance between the anode (5) and the cathode (6) is used to regulate the frequency of the alternating electromagnetic field until the initiation of molecule resonance in the modified material with a carrier resonance frequency (f_nr) of between 50 kHz and 200 kHz. The distance between the anode (5) and the cathode (6) is also used to regulate the alternating electromagnetic field until the initiation of molecule resonance in the modified material. The material modification process is performed at a temperature of under 50°C during a time period of between 1 minute and 4 hours. The device consists of an anode (5), which can be slid within the anode slide regulation system (10), which is mounted in the cylindrical casing of the vacuum chamber (2), which also comprises a humidified air dosing system (4), a resonance control system (9), a cathode temperature regulation block (11), and a pressure regulation block (12).

Description

A method for modifying the structure of materials by means of a glow discharge and a device for modifying the structure of materials by means of a glow discharge

The subject of the invention is a method for modifying the structure of materials by means of a glow discharge and a device for modifying the structure of materials by means of a glow discharge occurring in a dilute gas environment, which is particularly suitable for the modification of solids and liquids.

The device with a vacuum chamber for plasma processing of water, known from the Polish patent specification no. PL216025, consists of a vacuum chamber in the shape of a truncated cone with disk-shaped metal electrodes placed parallel to the base of the cone. The anode with a diameter of 40 mm to 50 mm and the cathode with adiameter of 350 mm to 450 mm are placed at a distance of 200 mm to 500 mm. At a distance of maximum 5 cm from the cathode, inside or outside the vacuum chamber, there is a container for flowing water. The vacuum chamber is connected to a vacuum pump, while the electrodes are connected to an electric power source, which is linked to an impulse generator and a measuring probe placed inside the vacuum chamber.

The device for modifying the structure of materials by means of a high- frequency electric discharge is known from the Russian patent specification no. RU2191113 and is used for the processing of polymer foil and synthetic fibers by means of physical modification of their structure and surface. The device comprises a power supply unit, a controllable high-frequency voltage generator connected to a converter, and a needle electrode for generating high-frequency electric voltage connected to them. The device also comprises a gasodynamic unit equipped with a reservoir for storing plasma-generated gas; a gas conduit and a nozzle which is mounted coaxially relative to the electrode and designed for supplying gas to the zone of hi h-frequency electric discharge and for directing stream of cold plasma onto the treated material. The generator is in the form of an active amplifying unit; a multi-pole electric network is connected to a self-excited oscillator. A converter is in the form of an electric five-pole network with its own resonance frequency. The converter includes a low-voltage section wound onto a hollow dielectric carcass, a high-voltage section wound onto the low- voltage one, and a core in the form of a hollow ferrite cylinder coaxially embracing the sections connected with the needle electrode. Terminals of the low-voltage section are connected with the multi-pole network.

The method for low-temperature processing of solid materials known from the Polish patent specification no. P.408953, in which stable non-equilibrium structures are created on the surface and inside the material, is based on subjecting the processed material to low-temperature plasma generated by a glow discharge with the electron density of 10⁹[cm^'3] do 10^!5[cm^"3], the temperature of electrically-neutral heavy particles in the range of 50[°C] to 1,500[°C], and electron energy in the range of 0.5[eV] do l,000[eV] in the time of between 1 [s] to 20 [hj.

The essence of the method according to the invention is based on the fact that the modified material is placed in a vacuum chamber, in which pressure is kept at the level of 10^" Pa to 10^"7 Pa, which is followed by a glow discharge between the anode and the cathode by means of an electron potential difference of 30 V to 2,000 V. The initiation of the process of material modification is preceded by dosing humidified air by means of a humidified air dosing system into the vacuum chamber, which is used to initiate the process of glow discharge. After the glow discharge has become stable, the inflow of humidified air is stopped, which results in the generation of alternating electromagnetic field with carrier frequency of 50 Hz to 150 Hz. The distance between anode 5 and cathode 6 regulates the frequency of the alternating electromagnetic field until the initiation of the molecule resonance in the modified material with a carrier resonance frequency of between 50 kHz and 200 kHz. The material modification process is performed at a temperature of under 50°C during a time period of between 1 minute and 4 hours.

Preferably, a cylindrical bowl is placed inside the cylindrical vacuum chamber, through which the modified material flows in a liquid form, wherein the liquid is modified at a pressure of 10^"1 Pa to 10^"3 Pa, during a time period of between 1 minute and 15 minutes.

Preferably, the liquid in the form of water or water solution is modified by means of changing the water cluster structure and eliminating free radicals, while liquid in the form of oil is modified by means of changing the length of its carbohydrate chains. Preferably, the electric permittivity of the liquid is measured after glow discharge processing; most preferably, the electric permittivity of the liquid is measured before and after glow discharge processing.

Preferably, the modified polymer material is placed on the cathode inside the vacuum chamber. This material is turned into powder at a pressure of 10^"1 Pa to 10^"2 Pa, during a time period of between 5 minutes and 30 minutes.

Preferably, the modified material in the form of a metal or metal alloy is placed inside the vacuum chamber and its surface layer is modified to the depth of 10 mm by ordering its crystal structure, at a pressure of 10^"' Pa to 10^"7 Pa, during a time period of between 5 minutes and 4 hours. The metal or metal alloy is placed on the cathode between the anode and the cathode; moreover, the anode and the cathode are made from the same materials as the modified material.

According to the invention, the essence of the device is based on the fact that the anode can be slid within the anode slide regulation system, which is mounted in the cylindrical casing of the vacuum chamber. The casing also comprises a humidified air dosing system, a resonance control system, a cathode temperature regulation block, and a pressure regulation block.

Preferably, the two-sided cylindrical bowl is mounted in the vacuum chamber, which is equipped with stub pipes for carrying inflowing and outflowing liquid; most preferably, the bowl adheres to the internal walls inside the cylindrical casing of the vacuum chamber.

Preferably, the stub pipe for carrying inflowing and, potentially, outflowing liquid is equipped with a system for measuring electric permittivity.

Preferably, the cathode-anode diameter ratio falls within the range of 5 to 10.

According to the invention, the method for modifying the structure of materials by means of a glow discharge is characterized by repeatability and stability. The method and the device make it possible to order the crystal structure of metals and metal alloys up to the depth of 10 mm. It is achieved by causing resonance vibrations in the processed material, which loosens Van der Waals bonds, which makes it possible for the atoms in the processed material to move and thus orders its crystal lo graphic structure. Metals and metal alloys subjected to glow discharge radiation significantly increase their mechanical durability, in polymer processing, the resonance breaks carbohydrate chains and consequently destroys the polymer. Water irradiated by glow discharge changes its cluster structure so that macro-cluster structure is replaced with micro- cluster structure. Micro-cluster water is characterized by decreased pH levels, varying between 3 and 5 depending on the length of processing and the voltage in the electrodes. Such water is also characterized by decreased electric conductivity, decreased solidification temperature, and increased boiling point. Moreover, the solubility of gases and other substances in thus processed water increases significantly, sometimes even eight-fold.

The subject of the invention is explained by embodiments and depicted in the illustration, in which fig. 1 shows the device for modifying the structure of materials by means of a glow discharge; fig. 2 - the device for modifying the structure of liquids by means of a glow discharge, equipped with a system for measuring the electric permittivity of the liquid after the modification; fig. 3 - the device for modifying the structure of liquids by means of a glow discharge equipped with two systems for measuring electric permittivity; fig. 4 - the voltage characteristic of the process of metal processing; fig. 5 - the voltage characteristic of the process of polymer processing; and fig. 6 - the voltage characteristic of the process of liquid processing.

Example 1

The method for modifying the structure of materials by means of a glow discharge is based on modifying a material in the form of a metal, whose surface layer up to the depth of 10 mm is modified by ordering its crystal structure. The metal is placed in the vacuum chamber 1, in which pressure is kept at 10^"7 Pa, which is followed by initiating the glow discharge process between the anode 5 and the cathode 6 by means of electric potential difference of 2,000 V. Before the initiation of the metal modification process, humidified air is introduced into the vacuum chamber 1 through the humidified air dosing system 4, which is used to initiate the glow discharge process. The inflow of humidified air is stopped after the glow discharge process has become stable, so that alternating electromagnetic field with carrier frequency of f„ = 150 Hz is generated between the anode 5 and the cathode 6 ; moreover, the distance between the anode 5 and the cathode 6 is used to regulate the frequency of the alternating electromagnetic field until the moment of triggering the resonance of the molecules of the modified material by resonance carrier frequency of f„_r = 200 kHz. The metal is placed on the cathode 6 between the anode 5 and the cathode 6, while the anode 5 and the cathode 6 are made from the same material as the processed metal. Moreover, the cathode 6 is heated to the temperature of 400 °C by the cathode temperature regulation block 11, and the process takes 5 minutes. Voltage characteristic U of the metal modification process in frequency function f is presented in fig. 4, which shows the linear increase in the number of ions a, the ion saturation zone b, the zone of ionization by collision c, and the resonance zone d with period 30-1,800 ns.

Example 2

The method for modifying the structure of materials by means of a glow discharge proceeds identically to example 1 , with the only difference being that the modified material placed in the vacuum chamber 1 is a metal alloy whose surface up to the depth of 9 mm is modified by ordering its crystal structure at a pressure of 10^"4 Pa for four hours on the cathode 6 heated to the temperature of 100°C.

Example 3

The method for modifying the structure of materials by means of a glow discharge proceeds identically to example 1, with the only difference being that the modified material placed in the vacuum chamber 1 is a polymer, which is placed on the cathode 6 and turned into powder at a pressure of 10^"2 Pa in a time period of 30 minutes while the cathode 6 is cooled down to the temperature of -30°C. Voltage characteristic U of the polymer destruction process in frequency function f is presented in fig. 6, which shows the linear increase in the number of ions a, the ion saturation zone b, the zone of ionization by collision c, and the resonance zone d with period 30-1,800 ns. Moreover, an alternating electromagnetic field with carrier frequency f_n = 50 Hz is generated between the anode 5 and the cathode 6 ; the distance between the anode 5 and the cathode 6 is used to regulate the frequency of the alternating electromagnetic field until the moment of triggering the resonance of the molecules of the modified material by resonance carrier frequency of f_nr = 100 kHz.

Example 4

The method for modifying the structure of materials by means of a glow discharge proceeds identically to example 1, with the only difference being that the cylindrical bowl 8 is placed inside the cylindrical vacuum chamber 1, through which the modified material flows in a liquid form, wherein the liquid is modified at a pressure of 10^"! Pa, during a time period of 15 minutes. The liquid in the form of water is modified by changing the cluster structure of water and eliminating free radicals. An alternating electromagnetic field with carrier frequency f„ = 100 Hz is generated between the anode 5 and the cathode 6 ; the distance between the anode 5 and the cathode 6 is used to regulate the frequency of the alternating electromagnetic field until the moment of triggering the resonance of the molecules of the modified material by resonance carrier frequency of f_nr ~ 100 kHz. Moreover, electric permittivity of the water is measured after glow discharge processing.

Example 5

The method for modifying the structure of materials by means of a glow discharge proceeds identically to examples 1 and 4, with the only difference being that a liquid in the form of oil is modified by changing the length of its carbohydrate chains; moreover, electric permittivity of the oil is measured before and after glow discharge processing. The oil is modified at a pressure of 10^"4 Pa during a time period of 45 minutes.

Example 6

The device for modifying the structure of materials by means of a glow discharge consists of the vacuum chamber 1 enclosed within the vacuum chamber cylindrical casing 2. The vacuum chamber 1 is connected with the vacuum pumping system 3 ; inside the vacuum chamber 1 , the anode 5 and the cathode 6 are connected to the power supply unit 7, which is a unipolar source of electric current with voltage regulated in the range of 50-2,000 V and current regulated in the range of 3-100 mA. The anode slide regulation system 10, in which the sliding anode 5 is mounted, is placed in the vacuum chamber casing 2. Moreover, the vacuum chamber casing 2 comprises the humidified air dosing system 4, the resonance control system 9, the cathode temperature regulation block 11, and the pressure regulation block 12. In this solution, the diameter of the cathode 6 is five times greater than the diameter of the anode 5.

Example 7

The device for modifying the structure of materials by means of a glow discharge is prepared identically to example 5, with the only difference being that the two-wall cylindrical bowl 8 equipped with stub pipes for carrying inflowing and outflowing liquid is mounted in the vacuum chamber 1. The stub pipe for carrying inflowing liquid is equipped with the electric permittivity measuring system 13. The bowl 8 adheres to the internal walls of the vacuum chamber's cylindrical casing 2. In this solution, the diameter of the cathode 6 is ten times greater than the diameter of the anode 5.

Example 8

The device for modifying the structure of materials by means of a glow discharge is prepared identically to example 6, with the only difference being that the stub pipes for carrying inflowing and outflowing liquid are equipped with two systems for measuring electric permittivity 13, at the inlet and at the outlet.

The method for modifying the structure of materials by means of a glow discharge uses the electrodynamic influence of the glow discharge on the modified material, in which the glow discharge triggers a space charge of heavy ions that acts as aperiodic transmitters of transverse automatic oscillations as a result of rapid production of energy from the source of unipolar electric current initiating the glow discharge. The transmitters of transverse automatic oscillations in the form of a space charge of heavy ions are produced cyclically as a result of a very rapid increase in the ionization level of the residual gases in the vacuum chamber 1, and after the dispersion of the ion stream energy on the cathode 6, they gather the energy necessary to produce another impulse from the power supply. Voltage characteristic U of the metal modification process in frequency function f is presented in fig. 4, which shows the linear increase in the number of ions a, the ion saturation zone b, the zone of ionization by collision c, and the resonance zone d with period 30-1,800 ns, which is read by the resonance control system 9. Modification of solids occurs as a result of cyclical impulses of ions directed at the surface of the processed material, which produces dynamic tensions generating resonance in the modified material. The maximum depth of influence on a material in the solid state of aggregation is directly proportional to the speed at which the transverse ultrasound wave travels in a given material, and inversely proportional to the squared average value of the frequency of automatic oscillations transmitters. Simultaneously with the influence of the impulses of aperiodic transmitters of transverse automatic oscillations of the space charge of ions, the modified material is heated or cooled down. List of designations used in the illustration:

1. Vacuum chamber,

2. Vacuum chamber casing,

3. Vacuum pumping system,

4. Humidified air dosing system,

5. Anode,

6. Cathode,

7. Power supply unit,

8. Bowl,

9. Resonance control system,

10. Anode slide regulation system,

11. Cathode temperature regulation block,

12. Pressure regulation block,

13. Electric permittivity measuring system, a - Linear increase in the number of ions, b - ion saturation zone,

c - Zone of ionization by collision, d - Resonance zone,

e - Initial resonance zone,

f - Proper resonance zone.

Claims

Patent claims

1. A method for modifying the structure of materials by means of a glow discharge, wherein the modified material is placed in a vacuum chamber (1), in which pressure is kept at between 10-1 Pa to 10-7 Pa, after which a glow discharge process is initiated between the anode (5) and the cathode (6) by means of a difference in electric potentials of between 30 V to 2,000 V, said material modification process is preceded by introducing humidified air into the vacuum chamber (1) by means of a humidified air dosing system (4), which initiates the process of glow discharge, and once said process of glow discharge has become stable, the inflow of humidified air is stopped, so that an alternating electromagnetic field with carrier frequency (fn) of between 50 Hz and 150 Hz is generated between the anode (5) and the cathode (6); moreover, the distance between the anode (5) and the cathode (6) is used to regulate the frequency of the alternating electromagnetic field until the moment of triggering the resonance of the molecules of the modified material with carrier resonance frequency (fnr) of between 50 kHz and 200 kHz; moreover, the distance between the anode (5) and the cathode (6) is used to regulate the alternating electromagnetic field until the moment of triggering the resonance of the molecules of the modified material; moreover, the process of material modification is performed at a temperature lower than 50°C during a time period of between 1 minute and 4 hours.

2. A method as set forth in claim 1 wherein a cylindrical bowl (8) is placed inside a cylindrical vacuum chamber (1), through which the modified material flows in a liquid form, wherein the liquid is modified at a pressure of 10-1 Pa to 10-3 Pa, during a time period of between 1 minute and 15 minutes.

3. A method as set forth in claim 2 wherein a liquid in the form of water or water solution is modified by changing the cluster structure of water and eliminating free radicals.

4. A method as set forth in claim 2 wherein a liquid in the form of oil is modified by changing the length of its carbohydrate chains.

5. A method as set forth in claim 2 wherein electric permittivity of the liquid is measured after glow discharge processing; preferably, electric permittivity of the liquid is measured before and after glow discharge processing.

6. A method as set forth in claim 1 wherein the modified polymer material is placed in the vacuum chamber (1) on the cathode (6), which said material is turned into powder at a pressure of 10-1 Pa to 10-2 Pa, during a time period of between 5 minutes and 30 minutes.

7. A method as set forth in claim 1 wherein the modified material in the form of a metal or metal alloy is placed inside the vacuum chamber (1), whose surface layer is modified to the depth of 10 mm by ordering its crystal structure, at a pressure of 10-1 Pa to 10-7 Pa, during a time period of between 5 minutes and 4 hours, wherein the metal or metal alloy is placed on the cathode (6) between the anode (5) and the cathode (6), wherein the anode (5) and the cathode (6) are made from a material identical to the modified material.

8. A device for modifying the structure of materials by means of a glow discharge, consisting of a system for pumping vacuum connected with a vacuum chamber, in which an anode and a cathode are connected to a power supply unit, wherein the anode (5) can be slid within the anode slide regulation system (10), which is mounted in the cylindrical casing of the vacuum chamber (2), which also comprises a humidified air dosing system (4), a resonance control system (9), a cathode temperature regulation block (11), and a pressure regulation block (12).

9. A device as set forth in claim 8 wherein a two-sided cylindrical bowl (8) is mounted in the vacuum chamber (1), which is equipped with stub pipes for carrying inflowing and outflowing liquid, preferably with the bowl adhering to the internal walls inside the cylindrical casing of the vacuum chamber (2),

10. A device as set forth in claim 9 wherein the stub pipe for carrying inflowing and, potentially, outflowing liquid is equipped with a system for measuring electric permittivity (13).

11. A device as set forth in claim 8 wherein the ratio of the diameter of the cathode (6) to the diameter of the anode (5) falls within 5 to 10.