DE102009039586A1 - Cleaning surface of metal, particularly weapons, involves utilizing oil component by performing sonication at elevated temperature - Google Patents

Abstract

Metal surface cleaning involves utilizing an oil component by performing sonication at elevated temperature.

Description

Field of the invention

The invention is in the field of metal treatment and relates to a method for the cleaning of metallic surfaces with the interaction of ultrasound, oil bodies, optionally surface-active agents and / or elevated temperatures.

State of the art

For cleaning hard surfaces of stains of all kinds, surface-active agents are usually used, which initially detach the dirt and solubilize it in the cleaning liquor. If the surfaces are metals, then there is a special case, because many cleaning agents which are excellently suitable for plastics, for example, are out of the question here because they attack the surfaces. In particular, when the surfaces are drawn and have been processed, for example, by burnishing or Ziselierungen, the range of cleaning agents is further limited, since only those can be used that are sufficiently mild; Conversely, these substances are not necessarily characterized by the highest cleaning power.

A particular problem arises when cleaning weapons. Here are all conceivable problems together: the run is drawn and therefore particularly sensitive. The surface of the weapons often decorated and the shaft is usually made of a very different material, preferably wood, which does not tolerate any detergent. Conversely, particularly stubborn deposits of powder, smut, lead, copper, nickel and especially Tombak, an alloy of zinc and tin, are found in the barrel, which are particularly difficult to remove. Thus, the problem with the weapon cleaning is on the one hand particularly mild and on the other to use particularly effective cleaning agents, which almost excludes.

The prior art also discloses alternative methods for cleaning metallic surfaces, especially handguns, in which these are introduced into an ultrasonic bath. However, this has a number of disadvantages: firstly, conventional ultrasonic baths are far too small to clean more than one weapon at the same time, let alone long guns for which they have not been considered at all. Furthermore, the cleaning results are unsatisfactory, since especially caking of Tombak are hardly completely removed even after prolonged or repeated use. Finally, the weapons must then be dried consuming and back-greased to avoid any kind of corrosion.

In practice, therefore, the cleaning of weapons does not take place in an aqueous environment, but with the aid of special gun oils, which are preferably aliphatic hydrocarbons, for example paraffin oil. However, this method is not free of disadvantages: on the one hand it is time consuming, since only one weapon at a time can be cleaned. To clean the barrel, the oil-soaked cotton wool must be pulled through with the help of a chain; This can easily lead to damage to the inner surface and thus by the change in the spin of the fired projectile to an impairment of accuracy. Finally, the cleaning success depends heavily on the care of the one who cleans the weapon: here, in particular, powder and Tombakanschmutzungen can only be reliably removed if the procedure is repeated several times.

The present invention has set itself the complex task of overcoming the described disadvantages of the prior art. Therefore, a method should be provided for cleaning metallic surfaces, preferably drawn metal surfaces and especially weapons, by means of which, on the one hand, stubborn soiling of powder and tombac can be reliably removed in a short time with little effort, without damaging it the surfaces, be it for example the drawn barrel or the burnishing of external parts comes. At the same time, the process should allow several weapons, especially long guns, to be cleaned, fattened and maintained at the same time, preferably without having to remove non-metallic components (such as the stem) beforehand.

Description of the invention

The invention relates to a cleaning method in which one brings metallic surfaces in contact with an oil component and at the same time exposes, optionally at elevated temperatures, an ultrasound.

In a special embodiment of the invention, the metal parts, preferably firearms, are introduced into an ultrasonic bath, which is filled with the oil component and exposed there to ultrasound for about 1 to 10 minutes. Surprisingly, it was found that in this way the complex requirement profile is solved in an ideal manner: The method is technically simple and allows in a short time several weapons, especially long guns to clean at the same time. It is extremely efficient, due to the interaction of oils and the cavitation generated by the sonication. H. Even the most stubborn powder deposits and Tombak deposits are reliably removed without the risk of damaging the barrel due to excessive or awkward mechanical force. At the same time, the oil behaves completely inert towards sensitive burnishings, nourishes and lubricates the weapon in one work step. It is not even necessary, for example, to remove wood parts from the weapon.

Metallic surfaces

The inventive method is basically suitable for virtually any type of soiled metallic surfaces. Examples of this are parts of motor vehicles or printing presses, which can be made of conventional steel with the typical admixtures of other elements such as chromium, titanium, nickel, copper, lead, tin, tin and the like. Preferably, the method is suitable for cleaning firearms, i. H. Both handguns such as pistols, revolvers and the like, as well as long guns, such as those used by hunters.

oil components

Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear or branched C ₆ -C ₂₂ fatty alcohols or esters of branched C ₆ -C are used as oil components ₁₃ carboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, such as. B. myristyl myristate, myristyl palmitate, myristyl stearate, Myristylisostearat, myristyl, Myristylbehenat, Myristylerucat, cetyl myristate, cetyl palmitate, cetyl stearate, Cetylisostearat, cetyl oleate, cetyl behenate, Cetylerucat, Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostearat, stearyl oleate, stearyl behenate, Stearylerucat, isostearyl, isostearyl palmitate, Isostearylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearyloleat, oleyl, oleyl palmitate, oleyl stearate, oleyl isostearate, oleate, Oleylbehenat, oleyl, behenyl myristate, behenyl, behenyl, Behenylisostearat, behenyl oleate, behenyl, erucyl, erucyl, erucyl, erucyl, erucyl, erucyl, erucyl behenate and erucyl. Also suitable are esters of linear C ₆ -C ₂₂ -fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C ₁₈ -C ₃₈ -alkylhydroxycarboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, in particular dioctyl malates, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimerdiol or trimer triol) and / or Guerbet alcohols, triglycerides based on C ₆ -C ₁₀ fatty acids, liquid mono- / di- / triglyceride mixtures based on C ₆ - C ₁₈ fatty acids, esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C ₂ -C ₁₂ dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 Carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C ₆ -C ₂₂ fatty alcohol carbonates, such as. B. Dicaprylyl carbonates (Cetiol ^® CC) Guerbetcarbonate based on fatty alcohols having 6 to 18, preferably 8 to 10 C atoms, esters of benzoic acid with linear and / or branched C ₆ -C ₂₂ alcohols (eg Finsolv ^® TN), linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as. B. dicaprylyl ethers (Cetiol ^® OE), ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (Cyclomethicone, silicon methicone types, etc.) and / or aliphatic or naphthenic hydrocarbons, such as. As paraffins, isoparaffins, white oils, squalane, squalene or dialkylcyclohexanes into consideration.

With regard to the selection of the oil components, those which have no double bonds, ie do not polymerize and thus lead to resin formation over time, have proven to be particularly advantageous. For this reason, especially white oils, paraffins and isoparaffins and mixtures thereof are particularly preferred oil components in the context of the invention.

Surfactants

In a further preferred embodiment of the present invention, the cleaning action of oil components and ultrasound is assisted by the addition of surfactants. In this way, in particular, the cleaning time can be further shortened. Since it makes sense for the cleaning process to work with a homogeneous cleaning liquor, the surface-active compounds themselves should be either oil-soluble or at least sufficiently oil-dispersible. Preference is given to substances which have an HLB value below 12, preferably below half of 10 and in particular in the range from 7 to 9.

As surface-active substances it is possible to use anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants whose use amount, based on the oil components, is usually about 1 to 50, preferably 5 to 20 and in particular 10 to 15,% by weight. Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, alkyl ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates , Mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially wheat-based vegetable products) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, optionally partially oxidized alk (en) yloligoglycosides or glucuronic acid derivatives, fatty acid N-alkylglucamides, protein hydrolysates (in particular vegetable products based on wheat), Polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds such as dimethyl distearyl ammonium chloride, and ester quats, especially quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds. Typical examples of particularly suitable mild, d. H. particularly skin-compatible surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, α-olefinsulfonates, ether carboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines, amphoacetals and / or protein fatty acid condensates, the latter preferably based on wheat proteins.

Moreover, suitable cleansing surfactants should be low-foaming and should be made slightly alkaline or slightly acidic, for which reason, for example, low-ethoxylated fatty alcohols or mixed ethers are particularly preferred. A product of the market that meets the requirements, for example Curatech ^® TN 237, which is marketed by Arnsperger.

sonication

The operating principle of ultrasonic cleaning is cavitation, ie the formation and dissolution of cavities in liquids due to pressure fluctuations. Corresponding methods are used especially for cleaning optical devices [ DE 10 2007 057 026 A1 , Carl Zeiss].

Soft cavitation is undesirable in ultrasonic cleaning, therefore, the cleaning liquid, so here the oil component is usually degassed before the start of the program. The ultrasonic field present in the fluid generates waves with overpressure and underpressure. If such a vacuum wave hits the metal surface to be cleaned, cavities filled with steam form on small air bubbles which act as germs. When the subsequent high-pressure wave impinges on the cavity, the static pressure in the cavity rises again via the saturation vapor pressure due to its compression. As a result, the vapor bubbles condense abruptly at the speed of sound, with pressure peaks of up to 100,000 bar. These cyclical and vanishing cavities virtually process the surface and clean it with it. Dirt and other attachments are thereby mechanically solved. As a result of cavitation there is a heating of the liquid. However, it may also be useful to additionally heat the bath and sonicate at temperatures in the range of about 20 to about 60 ° C, as long as it is ensured that the flash point of the oil component used is safely and clearly undercut in any case.

The method according to the invention is usually carried out in a heatable bath of non-rusting material filled with the oil component, one or more ultrasonic transducers or ultrasonic transducers and a generator which supplies the transducer (s) with high-frequency electrical energy. Sound vibrators can be flange-mounted both directly on the outside of the walls and under the bottom of the tub, but only if the wall thickness of the wall or floor is not too strong. In this construction, the ultrasound is then released directly through walls and / or floor in the liquid. Another variant are so-called immersion transducers, which are suspended in the fluid or attached to racks in the pelvis. Finally, there are plate vibrators, which are flanged to a corresponding opening in the pelvic wall. The arrangement and distribution of the sound vibrator must be such that a uniformly strong, non-static sound field is created. Some manufacturers therefore modulate the frequency to prevent standing waves. Also, a function for "degassing" the cleaning liquid is typical. Here, the power output of the device is pulsed to allow any gas bubbles to rise to the surface. The background is the poor formation of cavitation bubbles in the presence of gas bubbles, as these would "swallow" the power. A good starting point for the sound power is about 10 W per liter of cleaning fluid. The sound generators need a minimum distance to form a homogeneous sound field. The housings of the machine must be insulated against escaping sound vibrations. Touching of vibrating parts must be prevented. Frequencies of 20 kHz to 2 MHz are usually used. Low frequencies around 20 kHz produce larger diameter bubbles with powerful pressure surges, whereas higher frequencies around 35 kHz are better for intensive and gentle cleaning of surfaces. The current frequency is approximately 200 kHz (US) for particles larger than 1 μm in diameter. The frequency range above 400 kHz to 1-2 MHz is referred to in the literature as Megasonic (MS). Here, particles with a diameter smaller than 1 μm are optimally cleaned. The required frequency is determined by the smallest opening or structure that can be cleaned by the sound. The wavelength in the oil component should be less than half of the structure.

Industrial Applicability

cleaning concentrate

• (a) naphthenische Kohlenwasserstoffe und
• (b) oberflächenaktive Stoffe mit einem HLB-Wert unterhalb von 12.

Another object of the invention relates to cleaning concentrates, especially for the cleaning of metallic surfaces, containing

• (a) naphthenic hydrocarbons and
• (b) surfactants with an HLB value below 12.

The concentrates may contain components (a) and (b) in a weight ratio of 99: 1 to 50:50, preferably 95: 5 to 60:40 and especially 90:10 to 80:20. The concentrates may be anhydrous, but they may also have a water phase up to a proportion of 50% by weight of the concentrate. It is furthermore preferred to adjust the cleaning agents alkaline, ie to a pH in the range from 8 to 10. In sum, preferred is a mixture of (iso) paraffin oil and Curatech ^® TN 237, preferably in a weight ratio of 99: 1 to 80:20.

• (a) naphthenische Kohlenwasserstoffe und
• (b) oberflächenaktive Stoffe mit einem HLB-Wert unterhalb von 12

zur Reinigung metallischer Oberflächen, speziell von Waffen.A final object of the invention relates to the use of mixtures containing

• (a) naphthenic hydrocarbons and
• (b) surfactants with an HLB value below 12

for cleaning metallic surfaces, especially of weapons.

Examples

Comparative Examples V1 and V2, Example 1

• – Die erste Waffe wurde konventionell mit Waffenöl des Typs „BRUNOX” der gleichnamigen Firma behandelt. Dabei wurde das Öl auf einen an einer Kette befestigten Putzkörper aufgebracht und dieser 10mal durch den Lauf der Waffe gezogen (Vergleichsbeispiel V1).
• – Die zweite Waffe wurde ebenfalls zerlegt und in einem wässrigen Ultraschallbad 15 Minuten behandelt, wobei die Temperatur bis auf 55°C anstieg. Anschließend wurde die Waffe getrocknet und der Lauf mit Waffenöl rückgefettet (Vergleichsbeispiel V2).
• – Die dritte Waffe wurde im Ganzen in ein Ultraschallbad eingebracht, welches mit Paraffinöl gefüllt war und dort 4 Minuten der Ultrabeschallung ausgesetzt, wobei die Temperatur bis auf 40°C anstieg. Anschließend wurde die Waffe äußerlich trocken gewischt und der Lauf mit Hilfe eines trockenen Putzkörpers von anhaftendem Öl befreit (Beispiel 1).

Three new assault rifles of type G36K, 5.56 mm caliber Heckler & Koch were cleaned after firing on the shooting range, in which from each weapon about 300 rounds of ammunition (corresponding to 10 magazines) were fired.

• - The first weapon was conventionally treated with "BRUNOX" gun oil from the company of the same name. The oil was applied to a plaster body attached to a chain and this ten times pulled by the barrel of the weapon (Comparative Example V1).
• - The second weapon was also disassembled and treated in an aqueous ultrasonic bath for 15 minutes, with the temperature rising to 55 ° C. The gun was then dried and the barrel refilled with gun oil (Comparative Example V2).
• - The third weapon was placed in a whole in an ultrasonic bath, which was filled with paraffin oil and exposed there for 4 minutes of the sonication, the temperature rose to 40 ° C. Subsequently, the weapon was wiped dry on the outside and the barrel was freed from adhering oil with the aid of a dry brush (Example 1).

The cleaning result was assessed visually: on the one hand, a clean, soaked with gun oil cleaning body was once pulled through the barrel and then checked whether other dirt particles adhered. On the other hand, the runs were optically examined for recognizable deposits. The results are summarized in Table 1: TABLE 1 Cleaning of long arms example cleaning performance Dirt in the barrel V1 Slight dirt on the plaster body A few encrustations in the barrel recognizable V2 Significant dirt on the plaster body Significant encrustations in the barrel to recognize 1 Cleaning body shows no dirt residues No encrustations visible

The results show that only the cleaning method according to the invention leads to an optimal cleaning of the weapons.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 102007057026 A1 [0015]

Claims (10)

Cleaning process in which one brings metallic surfaces in contact with an oil component while at the same time exposing it, optionally at elevated temperatures, to an ultrasound treatment. A method according to claim 1, characterized in that the metallic surfaces are weapons. Process according to claims 1 and / or 2, characterized in that one uses oil components selected from the group formed by oil bodies selected from the group consisting of fatty alcohols having 6 to 18, carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear or branched C ₆ -C ₂₂ fatty alcohols or esters of branched C ₆ -C ₁₃ carboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, esters of linear C ₆ -C ₂₂ fatty acids with branched alcohols, esters of C ₁₈ -C ₃₈ -alkylhydroxycarboxylic acids with linear or branched C ₆ -C ₂₂ -fatty alcohols, esters of linear and / or branched fatty acids with polyhydric alcohols and / or Guerbet alcohols, triglycerides based on C ₆ - C ₁₀ fatty acids, liquid mono- / di- / Triglyceridmisungen based on C ₆ -C ₁₈ fatty acids, esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, esters of C ₂ -C ₁₂ -Di carboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C ₆ -C ₂₂ fatty alcohol carbonates, Guerbet carbonates based on fatty alcohols with 6 to 18 carbon atoms, esters of benzoic acid with linear and / or branched C ₆ -C ₂₂ -alcohols, linear or branched, symmetrical or unsymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, ring-opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons. A method according to any one of claims 1 to 4, characterized in that one uses as oil components paraffins or isoparaffins. Process according to at least one of Claims 1 to 4, characterized in that the oil components are used together with oil-soluble or at least oil-dispersible surface-active substances. A method according to any one of claims 1 to 5, characterized in that the surface-active substances are selected from the group consisting of soaps, alkylbenzenesulfonates, alkanesulfonates, Olefinsulfonaten, Alkylethersulfonaten, Glycerinethersulfonaten, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, alkyl ether sulfates, Glycerinethersulfaten , Fatty acid ether sulfates, hydroxymethylene ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids, protein fatty acid condensates, alkyl ( ether) phosphates, fatty alcohol polyglycol ethers, alkylphenolpolyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, if appropriate s partially oxidized alk (en) yloligoglycosides or glucuronic acid derivatives, fatty acid N-alkylglucamides, protein hydrolysates, polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates, amine oxides, quaternary ammonium compounds, esterquats, alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines, sulfobetaines and mixtures thereof. Method according to at least one of claims 1 to 6, characterized in that the ultrasonic treatment is carried out at temperatures in the range of 20 to 60 ° C. Cleaning concentrates containing (a) naphthenic hydrocarbons and (b) surfactants with an HLB value below 12. Concentrates according to claim 8, characterized in that they contain the components (a) and (b) in a weight ratio of 99: 1 to 50:50. Use of mixtures containing (a) naphthenic hydrocarbons and (b) surfactants having an HLB value below 12. for cleaning hard surfaces.