DE2430776C3 - Agent for cleaning and non-layer-forming phosphating of iron surfaces in one operation - Google Patents

Description

be generated.

The object of the invention is to provide a means for cleaning and non-layer-forming phosphating of

The invention relates to a means for cleaning and iron surfaces in one operation non-layer-forming phosphating of iron surfaces, which is operationally safe and economical surfaces in one operation, the phosphoric acid creates a firmly adhering phosphating layer and / or contains phosphate and oxidizing agents. 40 can be used.

According to the prior art, aqueous zinc This object is achieved by a means for

Phosphate or iron phosphate solutions as surface cleaning and non-layer-forming phosphating surface treatment agents for the formation of a chemical iron surface in one operation that uses a conversion layer on metal surfaces. Despite phosphoric acid and / or phosphate as well as oxidation the low cost of the iron phosphate solution and containing medium, characterized by a content of the good machinability of the layer formed in a cleaning effect showing culture bulbs, an iron phosphate treatment solution sion of lithotrophic strains of iron bacteria was hardly used, since the resulting chemical conversion (Ferrobacillus) and / or the Thiobacillus ferrooxidans Settlement layer not good on the to be applied and a pH of 1.5 to 5.
The top layer adheres when the microorganisms used with a zinc 50 The reaction layer formed for the treatment agent according to the invention phosphate solution are the so-called identical. Therefore, efforts have been made in the industry to eliminate the lithotrophic bacteria, the disadvantage mentioned above as a carbon source. In addition, carbon dioxide and inorganic nitrogen sources were used in the conventional processes for the formation of nitrogen compounds and the energy necessary for their chemical reaction layer with the above-mentioned assimilation was required from the oxidation surface treatment agents, which remove inorganic substances that can be oxidized to energy, the metal surface to be treated before formation of the Before, in particular, the conversion layer used according to the invention, by degreasing, cleaning the oxidized microorganisms from rusting and the like, so that the treatment iron (II) salts are used as assimilation energy. Examples of the procedure involved at least two stages. In addition, 60 are Ferrobazillus ferrooxidans (American Type, these steps were generally carried out at a relatively high Culture Collection: ATCC Deposition No. 13,661), temperature, e.g. B. at 80 ° C or above, Ferrobazillus sulfooxidans (ATCC Deposition so that the system and operations complicated No. 14119) and Thiobazillus ferrooxidans WU-66B and led to economic disadvantages. (Governmental Fermentation Research Institute in Finally, the removal of the iron ions dissolved in the waste 65 Japan, Deposition No. 1191 = ATCC Deposition solution after the treatment No. 21 834). The systematic characteristic values above are not easy. Microorganisms are shown in Table 1 below

From the Auslegeschrift 12 81 774 a means is given.

Table 1 properties

Name of the microorganisms Ferrobacilius ferrobacillus

ferrooxidans sulfooxidans

A.T.C.C. A.T.C.C.

Deposition Deposition

No. 13 661 No. 14119

ThiobazUius ferrooxidans Ferm. Research Inst. Deposition No. 1191

shape

Size (μ)

agility

scourge

Grief staining

Optimal growth temperature

Optimal growth pH

Oxygen demand

Carbon source (COg requirement)

Nitrogen source

(Ammonia nitrogen)

(Nitrate nitrogen)

Energy source liquid medium
(Iron (lf))

Energy source liquid medium
(Sulfur)

Energy source liquid medium
(Sodium thiosulfate)

Agar medium (iron (II))

Agar-Medhim (sodium thiosulfate)

Silica gel medium (iron (II))

Chopsticks chopsticks

0.6-1.0-1.0-1.6 0.5 x 1.0-1.5

single-chiseled

up to 35 ° C
2.5 to 5.0

single-chiseled

25 to 35 ° C
2.0 to 5.0

rod
0.3-0.5-1.0-1.5

single-chiseled

25 to 35 ° C
1.5 to 4.0

The present invention usable phosphates may be those which are soluble in water from 10 to 50 ⁰ C. For example, sodium phosphate, potassium phosphate, ammonium phosphate, sodium metaphosphate, potassium metaphosphate, ammonium metaphosphate, sodium pyrophosphate, potassium pyrophosphate, ammonium pyrophosphate or mixtures thereof can be used. Further, phosphates, phosphoric acid, metaphosphoric acid and pyrophosphoric acid other than the above can be used. The amount of phosphoric acid or phosphate added is in the range of 0.001 to 2 percent by weight, preferably 0.1 to 1 percent by weight, to the surface treatment solution.

Serve as components of the culture medium for the microorganisms used according to the invention Nitrogen sources, such as ammonium sulfate, iron (II) salt, such as iron (II) sulfate, calcium salt, such as calcium nitrate, Magnesium salt, e.g. B. magnesium sulfate, and the above-mentioned phosphoric acid or phosphates. These compounds are preferably used in admixture with each other, but they can also be used Phosphoric acid and phosphate can also be used alone.

The metal surface treatment agent of the invention is prepared by adding phosphoric acid and / or phosphate of a culture suspension containing dense microorganisms or a culture medium adds, which is inoculated with the said microorganism. The pH of the treatment agent must be in the range of about 1.5 to 5.0 and the concentration of the microorganism in the treating agent can be 0.1 or more in the absorption of a light radiation of 470 μ.

In the metal surface treatment with the treatment agent according to the invention, the metal objects to be treated are immersed in the treatment agent, or the agent is applied to the Sprayed on metal surface. Then the metal objects with water or hot water rinsed, whereby the phosphate conversion layer is formed on the surfaces of the metal object will. The treatment agent according to the invention must be used in the temperature range from 20 to 45.degree because the activity of the microorganisms decreases when the temperature is lower than 20 ° C is what results in insufficient formation of the phosphate conversion layer. When the temperature is higher than 45 ° C, the microorganisms die. The contact time between the treated Metal surface and the treatment agent varies according to the state of the metal surface and the concentration of the microorganisms. However, it can range from about 5 minutes to Lie for 2 hours.

5 6

The microorganisms used according to the invention with regard to operational safety and economy

find aerobic bacteria so that it is necessary to improve the condition.

agent by ventilation, shaking or to better understand the invention

Stirring during the carbon surface treatment - preferred examples below and additional ones

supplying dioxide and oxygen to the 5 characteristics described, maintain medium in an aerobic state.

Furthermore, the surface treatment must be carried out as in Example 1, so that the treatment agent is protected from contamination by other more vigorous bacteria or a solution of 0.5 g of potassium phosphate (KH ₂ PO ₄ ), other adverse factors. io 3.0 g ammonium sulfate, 0.5 g magnesium sulfate, 0.1 g

Several unknown aspects remain with the potassium chloride, 0.01 g calcium nitrate, 1 ml 10 nH ₂ SO ₄ for the surface treatment according to the invention and 1000 ml water were sterilized, and 140 g medium-used microorganisms with regard to iron (II) sulfate (FeSO) ₄ -TH ₁ O) were systematizing the solution. The biochemical properties are also added, so that a phosphate-containing culture medium and functions of the microorganisms were created. This culture medium was replicated with 20 ml, so that some details of a rinsing suspension of Ferrobacillus sulfooxidans are still unknown. The mechanism of inoculating the present invention (ATCC Deposition No. 14119) and metal surface treatment with the microorganisms, a cotton plug was placed on the container, but the phenomenon is obvious. Then, when the medium in aerobic state under the treatment agent with the treated metal 20 shaking was grown for 72 hours at 30 ⁰ C, thereby tailfläche comes into contact, the oxidase of a culture suspension acts (surface treating agent) microorganisms on the metallic surface with a cell concentration of 0.24 arose (Abein, with the rust and dyes from the metal sorption of the light beam of 470 μ). In the next area removed and the surface activated. Step was a plate made of carbon steel then the reaction between the phosphor 25 (300 χ 100 X 0.5 mm) immersed for 30 minutes in the above acid and / or phosphate in the treatment agent mentioned culture suspension, with sterile and the activated surface mentioned in acted air through the cotton plug to the hand-held device, with the detergent being supplied to the metal surface. After this treatment iron phosphate protective coating is formed. The plate has been rinsed and its surface has become possible with the means of simultaneously searching for both the fluorescent X-ray method with cleaning of the metallic surface and the search. As a result, the formation of iron formation of the phosphate conversion layer by the phosphate layer was confirmed.

to lead. Surprisingly, the reactivity is the Zeil concentration of the above-mentioned

The speed between phosphoric acid and / or phosphate and surface treatment agent was measured as follows:

the metallic surface is very strong because it is in the 35 20 ml of the treatment agent (Kultursusper.sion)

cleaned state is very active. The property was filtered through a filter paper, and that in the

the formation of the iron phosphate layer will not have been contaminated with any microorganisms contained in the filtrate

worse, even if the concentration of the phos centrifuge separated at 0 ° C and with 8000 g. the

phosphoric acid decreases. Therefore the phosphate needs the precipitate obtained in this way was dissolved with 1 nH ₂ SO _4.

and / or the phosphoric acid replenished less frequently 40 rinsed and rinsed again through a centrifuge under the

to become, which for the practical operation very pre-separated conditions as before. the

is partaking. Precipitation of the microorganisms was then in

The iron phosphate formed according to the invention is suspended in 10 ml of distilled water. By measuring

In comparison to the known solution, the settlement layer shows the transmittance of light at 470 μ on this

Excellent adhesion to the upper suspension resulted from the determined absorption

layer. In addition, the treatment temperature a measure of the concentration of microorganisms, temperature (20 to 45 ⁰ C) lower than comparable

The procedure is such that the plant and procedure are Example 2 what can be simplified from economic

Advantage is. Finally, the remaining metal test plates are the same as in Example 1 with the same treatment agent and the ions in the treatment agent after the treatment that they were tested by neutralization treatment activity. Each test panel was easily separated as a precipitate. The 10 minute treatment in the surface treatment agent is therefore immersed in terms of avoidance. 50 plates per day alternating between environmental pollution were also beneficial. submerged. Such a treatment was continued for 3 days. In addition, the waste solution from this handler can be continued in order to eliminate the change in the surface treatment by only finding it out as a treatment effect. As Vergleichsveretwa heated 50 ⁰ C or above, because the used was examined, the same treatment solution for EntMikroorganismen at such a temperature filtered their fernung 60 of the microorganisms and einhüßen with the so efficacy. If enough mycological sterile filtrate has arisen, the same care is produced, the treatment itself being carried out. The pore diameter of the filter and its waste matter had no harmful effect on it was 10 μ. The changes in the effectiveness of the. human health, so that an operationally safe two treatment agents can be carried out in the following operation. 65 Table 2, in which the iron phosphate concentration with the surface treatment solution of the eruption on the surface of the fiftieth, with the invention, the surface treatment of the metal treatment agent according to the invention can be simplified, and it can also be set test plate equal to 100.

Table 2

tahldcr treatment solution

Treatments culture suspension culture medium

according to the invention after filtration

50 100 80 100 100 40 150 100 20th

As is clear from Table 2 above, the surface treatment effect can be used to form the Iron phosphate layer can be maintained by the microorganisms present.

Example 3

A solution of 0.6 g of potassium pyrophosphate, 3.0 g of ammonium sulfate, 0.5 g of magnesium sulfate, 0.01 g of calcium nitrate, 0.1 g of potassium chloride, 1 ml of 10 nH ₂ SO ₄ and 1000 ml of water was sterilized, and 140 g of iron (II) sulfate (FeSO ₁ -7 H _? O) were added to produce a culture medium. This culture medium was inoculated with 20 ml of a rinse suspension of Thiobazillus ferrooxidans (Ferm. Res. Inst. Deposition No. 1191), and a cotton plug was placed on the container. The medium was then grown under aerobic conditions with shaking at 30 ^° C. for 72 hours. As a result, a cultured suspension having a cell concentration (absorption of light rays of 470 μ) of 0.26 was obtained. The cultured suspension thus obtained was sprayed on the surface of a rusty mild steel plate. The plate was allowed to stand for 60 minutes, then it was rinsed. As a result of this treatment, it was found that the rust had been removed and a clean treated surface was formed.

Example 4

A solution of 0.3 g of sodium metaphosphate, 3.0 g of ammonium sulfate, 0.5 g of magnesium sulfate, 0.01 g of calcium nitrate, 0.1 g of potassium chloride, 1 ml of 10 ^ H ₁ SO ₄ and 1000 ml of water was sterilized, and it 140 g of iron (II) sulfate (FeSO, -7H ₂ O) were added, whereby a culture medium was formed. This culture medium was inoculated with 20 ml of Ferrobazillus ferrooxidans rinsing suspension (ATCC Deposition No. 13,661), and a cotton plug was placed on the container. The medium was then kept for 72 hours at 30 ⁰ C in aerobic condition with shaking. The result obtained was a culture suspension with a cell concentration of 0.26 (absorption with light beams of 470 μ). A rusty mild steel plate was immersed in this culture suspension (treatment agent) for 2 levels at 30 ^° C. After this, the rust on the plate was removed and on

a light-colored phosphate layer had formed on her. Then an alkyd resin coating material was applied applied to the surface of the treated panel. In the meantime, the coating material became also applied to the surface of another test panel that was treated with an iron phosphate treating agent had been treated according to the state of the art. The latter preparation is regarded as a comparative example.

ίο The adhesion of these two test plates was through determined the cross-cut test, the results of which are given in Table 3 below. The cross cut test was carried out as follows: With a knife were in the layer of the coating material Make 100 cuts to form 1 mm squares in a checkered arrangement. A Self-adhesive tape was placed on the cut area; then the tape was peeled off and counted the number of cut squares that remained on the surface.

Table 3

Implementation layer
according to the known mitdemerfin method

treated means treated

Remaining cross-cut area (%)

spat

100

A solution of 4.0 g of ammonium phosphate, 0.5 g of magnesium sulfate, 0.01 g of calcium nitrate, 0.1 g of potassium chloride, 1 ml of 10 nH _t SO ₄ and 1000 ml of water was sterilized, and 140 g of ferrous sulfate (FeSO ₁ -7 H ₂ O) was added and a culture medium was prepared in this way. This culture medium was inoculated with 20 ml of Ferrobazillus ferrooxidans rinse suspension (ATCC Deposition No. 13 661), and a cotton plug was placed on the container. Then, the Kultunnedium was kept for 72 hours at 30 ⁰ C in aerobic condition unier shaking to grow the microorganisms. After this cultivation, a culture suspension with a cell concentration of 0.20 was formed (absorption with a light of 470 μ). A mild steel plate was then immersed in the culture suspension obtained at 40 ° C. for 10 minutes. The surface of the plate thus treated was examined by IR absorption spectra. It was found that an iron phosphate settlement layer had formed on the surface of the test plate.

As can be seen from the above, it is a metal surface treatment agent of the invention is very advantageous compared to the known treatment agents

Claims (6)

for cleaning and degreasing as well as paint stripping and claims: phosphating of iron surfaces, consisting of essentially of phosphoric acid and / or alkali ) 1. Agents for cleaning and non-film-forming phosphates or salts of heavy metals as well the phosphating of iron surfaces in an accelerator and phenol or its homo process, the phosphoric acid and / or phosphate were lying, dissolved in methylene chloride and / or ethylene as well as Oxidizing agent contains, labeled chloride, designated for treatment in one operation by a salary of one knows. This agent requires a relatively high concentration cleaning effect The culture suspension showing trations of phosphoric acid in order to achieve the desired depletion and phosphatization of lithotrophic strains of iron bacteria. Besides that (Ferrobacillus) and / or the Thiobacillus ferro- is the adhesion of the applied phosphating oxidant and a pH of 1.5 to 5th layer is insufficient. 2. Means according to claim 1, characterized in US-PS 36 79 397 is a method for draws that the culture suspension Ferrobacillus extraction of metallic components from metallurferrooxidans and / or Ferrobazillus sulfooxidans 15 gischen substances known in which an iron sulfate contains. and leachate containing bacteria with the 3. Means according to claim 1 or 2, characterized in that metallurgical material is brought into contact, indicates that the culture suspension is ferro- This is about certain metals bazillus ferrooxidans with the A.T.C.C.-Low-grade ore and then as laying no. 13 661 contains. ao to knock down metal from it. With the well-known 4. Means according to claim 1 or 2, thereby processes are iron-oxidizing bacteria with indicates that the culture suspension contains a small amount of carbamide phosphoric acid and ferro-ferrous bazillus sulfooxidans with the A.T.C.C.-Nieder- possibly with another source of phosphorus, such as laying no. 14 119 contains. water-soluble phosphates of alkali metals, 5. Means according to claim 1 or 2, characterized as set to the extraction of metal from the ore indicates that the culture susceptibility to thio reinforce. Apart from the relatively complibacillus ferrooxidans WU-66B (Governmental adorned composition of the well-known leach fermentation Research Institute Deposition Nr. Solutions it is not possible with these Phosphatie-1 191 in Japan). generating layers. 6. Agent according to one of claims 1 to 5, 30 Finally, it is known from DT-OS 22 55 640, characterized in that the absorption of the cleaning treatment of metallic surfaces Use culture suspension with a light of 470 μ 0.1 microorganisms. Through this or more. However, no phosphating layer can drive