CA1310876C - Agent for preventing corrosion on ceramic surfaces - Google Patents
Agent for preventing corrosion on ceramic surfacesInfo
- Publication number
- CA1310876C CA1310876C CA000562702A CA562702A CA1310876C CA 1310876 C CA1310876 C CA 1310876C CA 000562702 A CA000562702 A CA 000562702A CA 562702 A CA562702 A CA 562702A CA 1310876 C CA1310876 C CA 1310876C
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- CA
- Canada
- Prior art keywords
- weight
- alkali metal
- agent
- ammonium
- fluorine compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/02—Apparatus characterised by their chemically-resistant properties
- B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/02—Apparatus characterised by their chemically-resistant properties
- B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
- B01J2219/0263—Ceramic
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Secondary Cells (AREA)
- Heat Treatment Of Sheet Steel (AREA)
- Television Signal Processing For Recording (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Paints Or Removers (AREA)
- Chemical Treatment Of Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
An agent for preventing corrosion on ceramic surfaces Abstract of the disclosure:
An agent is described for preventing corrosion on sur-faces produced from molten silicates, the agent contain-ing a fluorine compound which is at least sparingly soluble in aqueous media.
An agent is described for preventing corrosion on sur-faces produced from molten silicates, the agent contain-ing a fluorine compound which is at least sparingly soluble in aqueous media.
Description
~ 3 ~ 7 ~
AN A~ENr FOR PREVENTING CORROSI~N ON CERAMIC SURFACES
This invention relates to an agent for preventing corro-sion on surfaces produced from molten s;licates.
These surfaces include, for example, those of enamel, glazing on porcelain and, in particular, glass.
It ha~ been show~ that silicate surfaces of this type suffer from corrosion when, above all, they are repeat-edly brought into con~act with dish~`washing agents and detergents.
Such dish washing agents and detergents have hitherto been composed essentially of phosphates~
In attempting to limit the use of phosphates, the phosphates in these agents have increasingly been replaced by silicates, in some cases ;n combination with strong complex;rlg agents.
' this has the consequence that an increasing amount of corrosion is observed on glass surfaces when these new dis~h-washing agents and detergents are lused; this is even the case when the use of strong comp~exing agents, j such as, for example, alkylene diphosphon;c acids is ~` omitted.
Surpr;singly, it has now been found that this corrosion can be substantially avoided using an agent wh;ch con-tains a fluorine compound which is at least sparingly soluble in aqueous media. Fluorine compounds of this type are, for example~ a(kali metal monofluorides, am-monium monofluorides, alkali meta~ aluminum hexafluor-ides, ammonium aluminum hexafluorides or tin tetra-fluoride. However, alkali metal silicofluorides, ;
I
"` ~3~7~
AN A~ENr FOR PREVENTING CORROSI~N ON CERAMIC SURFACES
This invention relates to an agent for preventing corro-sion on surfaces produced from molten s;licates.
These surfaces include, for example, those of enamel, glazing on porcelain and, in particular, glass.
It ha~ been show~ that silicate surfaces of this type suffer from corrosion when, above all, they are repeat-edly brought into con~act with dish~`washing agents and detergents.
Such dish washing agents and detergents have hitherto been composed essentially of phosphates~
In attempting to limit the use of phosphates, the phosphates in these agents have increasingly been replaced by silicates, in some cases ;n combination with strong complex;rlg agents.
' this has the consequence that an increasing amount of corrosion is observed on glass surfaces when these new dis~h-washing agents and detergents are lused; this is even the case when the use of strong comp~exing agents, j such as, for example, alkylene diphosphon;c acids is ~` omitted.
Surpr;singly, it has now been found that this corrosion can be substantially avoided using an agent wh;ch con-tains a fluorine compound which is at least sparingly soluble in aqueous media. Fluorine compounds of this type are, for example~ a(kali metal monofluorides, am-monium monofluorides, alkali meta~ aluminum hexafluor-ides, ammonium aluminum hexafluorides or tin tetra-fluoride. However, alkali metal silicofluorides, ;
I
"` ~3~7~
a~moni.um silico~luorides, alkali metal fluoxophosphates and ammonium fluorophosphates, such as Na2P03F or NaP02F2 or NaPF5, are particularly suitable for this purpose.
Accordingly, the present invention provides a method for preventing corrosion on a surface produced ~rom a mol~en silicate comprising applying to the surface a fluorl.ne compound selected from the group consisting of alkali metal monofluorides, ammonium monofluorides, alkali metal aluminium hexafluorides, tin tetrafluoride, alkali metal fluorophosphates, ammonium fluorophosphates, alkali metal sllicohexa~luorides and ammonium silicofluorides.
The present invention also provides a use of a fluorine compound selected from the group consisting of alkali metal monofluorides, ammonium monofluorides, alkali metal alumlnium hexafluoridest tin tetrafluoride, alkali metal fluorophosphates, : ammonium fluorophosphates, alkali metal silicohexafluorides and ammonium silicofluorides to prevent corrosion on a surface produced from a molten silicate.
Preferably, the fluorine compound ls added as a component of an agent that con~ains 3.1 to 5.0% by weight of the fluorine compound and, in addition, other components which are used in dish-washing agents and detergents.
Components of this type are, in general, builders, such as, for example, alkali metal triphosphates, zeolites, hentonites, :
:~ polycarboxylatasr phyllosilicates, nitrilotriacetic acid (NTA), ethylene-diamine-te~raace~ic acid, phosphonocarboxylic acids, ~`l3~7~
-2a- 23343-832 amido-phosphonic acid etc., alkali carriers such as, for example Na2SiO3, Na2Si2O5, NaOH and Na2CO3~ surfactants such as, for example, moderately foaming hlock polymers containing ethylene and propylene groups, activated chlorine carriers, such as NaOCl, di-and trichlorisocyanurates, chloramin T, chlorosulfonic acids, chlorinated orthophosphates etc., fillers such as water, Na2SO4, SiO2 etc., per~umes and dyes.
In the agents according to the inven~ion, these components ~ay be present individually or in ~ixtures in additlon to the fluorine compounds.
The mix~ures produced therefrom advantageously contain 30 to 95% by weight of bullders and alkali carriers together, and 0.1 to 5.0~ by weight, preferably 0.5 to 2.0% by weigh~, of the fluorine compound, the amount of the latter being selected so that the content of fluorine in ~he mixtuxe mentioned is a~ least 0.05 by weight.
Since it is generally known that fluorine attacks surfaces produced from molten silicates - such as, in particulax, glass - it could not have been predicted by '~ ~
:; :
~: :
;~ ~ B
.~ ...
, .
... .
1 3 ~
those skilled in the art and was entirely surpr;sing that fl~orine compounds have a corrosion-inhibiting action on sur-faces of this type, in particular in an aqueous med;um at a pH greater than 7. I~ the agents according to the invention are employed, for example, as dish-washing agents or detergents, a welcome s;de effect occurs.
It has namely been shown that, when dish-~ashing agents are used wh;ch are dist~;nguishë"ct'~y a`h;lh content of s;licates and strong complexing agents, deposits of varying thickness can be seen on metall;c machine wall or cutlery surfaces and appear init;a(ly in blue-violet tarnish colors and later in bluish-whi~e, cloudy, adherent coatings. It is only possible to remove these coatings by means of strong ac;ds - such as, for example, concen-trated hydrochloric acid - with mechanical abrasion.
It has now been shown that the deposits of the type described and the corrosion on metallic sur~aces can both be prevented by the agents according to the invention, in part;cular by those which contain fluoro-phosphates or silicofluorides as fluorine compound.
References to the corros;on-inh;biting act;on of certain fluorine compounds in water-carrying pipel;nes made from metal have already bee~n given ;n US-A-4~613, 45û.
~.
The action of the agents accordiny to the ;nvention is intended to be descr;bed in greater detail by the examples which follow.
Example 1 ~Comparison example) ~ standard commercial dishwasher was loaded w;th 12 standard sett;ngs o~ wh;te porcelain as the basic load.
~ 11 3~76 At the same t;me, 12 each of stainless steel knives, forks and spoons were added to the load. In addition, six glasses each of different ~anufacture were placed in the upper basket. These were the following types of glass:
a) "ROMA" tumblers, Messrs. Schott-Zwiesel-Glaswerke AG
b) Kolsch glasses, Messrs. YE~A-GLAS
c~ "Alexandra" wine glasses, Messrs. Nachtmann The glasses had glass materials of different composi-tions, with unknown analyses, and very di~ferent surfacedesigns due to their ma~ufacturing processes. The d;sh-washer contents without food residues were washed 1000 times using softened water of Z to a maximum of 5 (German hardness) and using 30 g of detergent per wash-ing cycle and 3 ml o~ clear r;nsing agent per washingcycle7 The clean1ng cycle was carried out using 6.5 l of water at 65C. The contents were dried for 30 min-utes ~ith the door open bet~een each washing cycle.
The detergent used was formulated as follows tInter-ZO national Electrochemical Commission standard) 50.00 % by weight of sodium tripolyphosphate, partiallyhydrated containing about 7% by weight of water of crystallization 40.00X by we;ght of sodium metasilicate, anhydrous 2.25% by weight of sodium dichloroisocyanurate.2 H20 tNaDCC) 2.00 % by weight of surfactant and 5~75X by weight of sod;um sulphate, anhydrous ~The surfactant used was a block polymer from Messrs 8ASF
Wyandotte Corp. w1th the trade name ~ lurafac Ra 43).
The damage was determined by visual assessment of the glasses and metal parts after 50, 125, 250, 375~ 500, 750 and 1000 washing cycles. the amount of damage was evaluated w;th referenc0 to an evaluation table, ~hose ~.
` ~3~87~
grad;ng ;n 0.5 Point steps permits good d;fferent;a-tion. 0 po;nts ;n this table denote no damage~ whereas 3.5 po;nts denote complete corrosion or destruction.
The mean corros;on data are collated in Table I.
Table I
. _ ~ash,~n~ Glass Cutlery Cycles Roma Alexandra Kolsch ~eives Spoons Forks _ _ 0,5 0 0 0 0 0 125 0,5 0 0,5 0 0 3 250 1,0 0,5 1,0 0 0 0 375 l,S 1,0 1.0 0 0 0 500 1,5 1,5 1,0 0 0 5,5 750 2,0 1,~ 1~5 0,5 0 0,5 1000 2,5 1,5 2~0 1~0 0 î,S
_ ._ Example 2 : 1% by weight ~f Na2P03F (in place of 1~ by ~eight ; of Na2S04) ~as added to the d;sh-washing agent described in Example 1. The course of damage during the 1000 washing cycles is illustrated in Table II.
Table II
Wash,in~ Glass Cutlery Cycles ~ama Alexandra Kalsch ~;ves Spoons Forks . __ __ . T ~
0 0 0 0 ~ 0 ~: 375 0 Q 0 0 0 0 n ~ n o o O
:~~750 0 0 0,5 0,5 0 0 lG00 0,5 D 0,5 0,5 0 0 . I I
~ 3 ~
Co~pared to Example 1, the corros;on inhibition can be seen clearly.
Example 3 1X by we;ght of Na2SiF6 was added as formulation (~), ;n place of 1% of Na2S04~ to a low-phosphate dish-washing agent of the following composition tA) 15% by weight of sodium tripolyphosphate, partially hydrated, containing 2X by ~e;ght of water of crystal-lization 60% by weight of sodium metasilicate, anhydrous 2~ by weight of NaDCC
2% by weight of surfactant and 21% by weight o~ Na2504, anhydrous The corrosion data for these two formulations are com-pared in Table lll. Using formulation A, the staihlesssteel hous;ng of the dishwasher and the cutlery had tarnished in a blue-violet colour after about 50 ~ash-ing cycles. The coating beca~e cloudy ~hite after 1Z5 washing cycles, and the coating was so considerable after 750 washing cycles that evaluation of the cutlery could no longer b~ carried out.
Table IIl .
Washing Glass Cutlery Cycles ~o~a Alex~ndra Kalsch ~ive~ Spoons Foaks A B A 8 A ~ A 9 ~ B` A 3 _ ~ .
0 0 0 0 0,5 0 1,G 0 1,0 0 ;,0 0 lZ5 0.5 0 0 0 0,5 0 1, 5 0 1 b5 0 1 ~5 0 2$0 1~5 0 0~5 0 1~0 0 1~S 0 1.5 0 1~5 0 ;~ 375 1,5 0 1~0 0 1,5 0 2,0 0 1,5 a 2Ao o 500 Z,0 0 1,0 0 2,0 0 2.5 0 2~5 0 2,5 0 750 2~5 0 2,5 Oi5 2,0 0 n.e.lO n.e. 0 n.e. 01 1000 2,5 0,5 2,5 0,5 2,0 0 n.e 0 n.e. 0 n e 0,5 n.e. = evaluation not possible ' ,` :' '. ~ ' ' `. ' ' ~3~7~
Example 4 2% by we;ght of NaF (D) ~ere added to a for~ulat;on w;thout triphosphate, but containing hydroxyethylene d;phosphonic acid (HEDP) as complexing agent (C). The corrosion data are shown in Table IV.
After about 50 washing cycles using formulation C~
the dishwasher housing and also some oflthe cutlery handles increasingly exhibited the discoloration and deposits described in Example 3, but not quite to the same extent. These phenomena do not appear using for-mulation D. However, white, rough str;pes which could not be removed appeared on the dishwasher housing ~rom about 1Z5 washing cycles.
Formulation composition C D
2Z~ by weight of HEDP 2X by weight of HEDP
60% by weight of Na2SiO3 60% by weight of Na2SiO3 34% by we;ght of NazC03 32% by weight of Na7C03 Z% by weight of NaDCC 2% by we;ght of NaDCC 0 2~ by weight of surfactants 2~ by weight of surfactants 2X by weight of NaF
Table IV
__ __ .
. ~ash~ng Glass Cutlery Cycles Ra~a Alexandra Kolsch ~nives Spoons Fnrks _ _ .
O O O O O, 5 0 1 ,0 0 1 ,0 0 1 ,0 0 125 0,5 0 O~S 0 0,5 0 2,0 0 1,0 0 1,~ 0 ;; 250 1,0 0 0,5 0 1.0 0 1.0 0 1,0 0 1,0 0 375 1,5 0 1,0 0 1,0 0 1,5 0 l,S 0 1,~ ~
500 1,5 0 1,0 0 l,S 0 1,5 0 1,5 0 l,S 0 750 2,0 0 1,5 0 Z~0 0 2.0 0 Z,0 0 1,5 0 1000 2, 5 0, 5 2, 0 ~ 2 ,, 5 0 2 G O O ~ 5 2, 0 0 ;' . O O
__ 1 ~ 7 ~
The corros;on result in these two exper;ments after 1000 wash;ng cycles was investigated us;ng a scanning elec-tron microscope for the example of "ROMA" tumbler~ Even at a magnification of about 10,000 times, hardly any damage was visible when fluorine ions were present.
Example 5 As for E~ample 4, but Na2P03F was used in formula-tion D in place of NaF. The course of damage on the washed pieces was virtually comparable to that for formulation D. However, no white str;pes were v;sible on the metalLic housing of the dishwasher even after 1000 washing cycles.
Example 6 On the one hand, a d;shwashing agent of composition E:
; 15 40% by weight of crystalline alkali ~etal phy~losilicate 25% by weight of sodium carbonate, anhydrous.
28.85X by weight of sodium sulphater anhydrous 1.9% by weight of the methylene-vinyl qster of maleic anhydride, powder (92% of active substance) 20 2.25~ by weight of sodium dichloroisocyanurate.2H20 2% by weight of surfactant and on the other hand a dishwashing agent of composition F which essentially corresponded to that of E but in which the 2% by weight of sodium carbonate were replaced by ZZ by weight of Na2P03F, were used.
The results of this comparison are collated in Table V.
, ~
- - ~ 3 ~
'rable V
_ Washing Glass ¦ Cutlery Cycles ~o~a Alexandra Kolsch ¦ ~nives Spoons Forks E F E r E ~ ! E F E ~ E
____ ~ _ _ 125 3 ~ 5 0 0 0 5 0 0 0 5 375 0,5 0 0 0 0,5 0 0,5 a 0 0 0,5 0 500 0,5 0 0 0 0,5 0 0.5 0 0 0 0,5 0 750 0,5 0 0,5 3 0,5 0 1,0 0 0 o 0,5 0 1000 1,5 C ~ 0,5 0,5 1,~ ol 0 C 0.5 It is clear that even the only sl;ghtl~ corrosive formulation E based on a phyllosilicate can still be positively affected as regards total corros;on by the simultaneous use of a fluorine compound contain;ng hydrolyzable fluor;de ;ons.
Accordingly, the present invention provides a method for preventing corrosion on a surface produced ~rom a mol~en silicate comprising applying to the surface a fluorl.ne compound selected from the group consisting of alkali metal monofluorides, ammonium monofluorides, alkali metal aluminium hexafluorides, tin tetrafluoride, alkali metal fluorophosphates, ammonium fluorophosphates, alkali metal sllicohexa~luorides and ammonium silicofluorides.
The present invention also provides a use of a fluorine compound selected from the group consisting of alkali metal monofluorides, ammonium monofluorides, alkali metal alumlnium hexafluoridest tin tetrafluoride, alkali metal fluorophosphates, : ammonium fluorophosphates, alkali metal silicohexafluorides and ammonium silicofluorides to prevent corrosion on a surface produced from a molten silicate.
Preferably, the fluorine compound ls added as a component of an agent that con~ains 3.1 to 5.0% by weight of the fluorine compound and, in addition, other components which are used in dish-washing agents and detergents.
Components of this type are, in general, builders, such as, for example, alkali metal triphosphates, zeolites, hentonites, :
:~ polycarboxylatasr phyllosilicates, nitrilotriacetic acid (NTA), ethylene-diamine-te~raace~ic acid, phosphonocarboxylic acids, ~`l3~7~
-2a- 23343-832 amido-phosphonic acid etc., alkali carriers such as, for example Na2SiO3, Na2Si2O5, NaOH and Na2CO3~ surfactants such as, for example, moderately foaming hlock polymers containing ethylene and propylene groups, activated chlorine carriers, such as NaOCl, di-and trichlorisocyanurates, chloramin T, chlorosulfonic acids, chlorinated orthophosphates etc., fillers such as water, Na2SO4, SiO2 etc., per~umes and dyes.
In the agents according to the inven~ion, these components ~ay be present individually or in ~ixtures in additlon to the fluorine compounds.
The mix~ures produced therefrom advantageously contain 30 to 95% by weight of bullders and alkali carriers together, and 0.1 to 5.0~ by weight, preferably 0.5 to 2.0% by weigh~, of the fluorine compound, the amount of the latter being selected so that the content of fluorine in ~he mixtuxe mentioned is a~ least 0.05 by weight.
Since it is generally known that fluorine attacks surfaces produced from molten silicates - such as, in particulax, glass - it could not have been predicted by '~ ~
:; :
~: :
;~ ~ B
.~ ...
, .
... .
1 3 ~
those skilled in the art and was entirely surpr;sing that fl~orine compounds have a corrosion-inhibiting action on sur-faces of this type, in particular in an aqueous med;um at a pH greater than 7. I~ the agents according to the invention are employed, for example, as dish-washing agents or detergents, a welcome s;de effect occurs.
It has namely been shown that, when dish-~ashing agents are used wh;ch are dist~;nguishë"ct'~y a`h;lh content of s;licates and strong complexing agents, deposits of varying thickness can be seen on metall;c machine wall or cutlery surfaces and appear init;a(ly in blue-violet tarnish colors and later in bluish-whi~e, cloudy, adherent coatings. It is only possible to remove these coatings by means of strong ac;ds - such as, for example, concen-trated hydrochloric acid - with mechanical abrasion.
It has now been shown that the deposits of the type described and the corrosion on metallic sur~aces can both be prevented by the agents according to the invention, in part;cular by those which contain fluoro-phosphates or silicofluorides as fluorine compound.
References to the corros;on-inh;biting act;on of certain fluorine compounds in water-carrying pipel;nes made from metal have already bee~n given ;n US-A-4~613, 45û.
~.
The action of the agents accordiny to the ;nvention is intended to be descr;bed in greater detail by the examples which follow.
Example 1 ~Comparison example) ~ standard commercial dishwasher was loaded w;th 12 standard sett;ngs o~ wh;te porcelain as the basic load.
~ 11 3~76 At the same t;me, 12 each of stainless steel knives, forks and spoons were added to the load. In addition, six glasses each of different ~anufacture were placed in the upper basket. These were the following types of glass:
a) "ROMA" tumblers, Messrs. Schott-Zwiesel-Glaswerke AG
b) Kolsch glasses, Messrs. YE~A-GLAS
c~ "Alexandra" wine glasses, Messrs. Nachtmann The glasses had glass materials of different composi-tions, with unknown analyses, and very di~ferent surfacedesigns due to their ma~ufacturing processes. The d;sh-washer contents without food residues were washed 1000 times using softened water of Z to a maximum of 5 (German hardness) and using 30 g of detergent per wash-ing cycle and 3 ml o~ clear r;nsing agent per washingcycle7 The clean1ng cycle was carried out using 6.5 l of water at 65C. The contents were dried for 30 min-utes ~ith the door open bet~een each washing cycle.
The detergent used was formulated as follows tInter-ZO national Electrochemical Commission standard) 50.00 % by weight of sodium tripolyphosphate, partiallyhydrated containing about 7% by weight of water of crystallization 40.00X by we;ght of sodium metasilicate, anhydrous 2.25% by weight of sodium dichloroisocyanurate.2 H20 tNaDCC) 2.00 % by weight of surfactant and 5~75X by weight of sod;um sulphate, anhydrous ~The surfactant used was a block polymer from Messrs 8ASF
Wyandotte Corp. w1th the trade name ~ lurafac Ra 43).
The damage was determined by visual assessment of the glasses and metal parts after 50, 125, 250, 375~ 500, 750 and 1000 washing cycles. the amount of damage was evaluated w;th referenc0 to an evaluation table, ~hose ~.
` ~3~87~
grad;ng ;n 0.5 Point steps permits good d;fferent;a-tion. 0 po;nts ;n this table denote no damage~ whereas 3.5 po;nts denote complete corrosion or destruction.
The mean corros;on data are collated in Table I.
Table I
. _ ~ash,~n~ Glass Cutlery Cycles Roma Alexandra Kolsch ~eives Spoons Forks _ _ 0,5 0 0 0 0 0 125 0,5 0 0,5 0 0 3 250 1,0 0,5 1,0 0 0 0 375 l,S 1,0 1.0 0 0 0 500 1,5 1,5 1,0 0 0 5,5 750 2,0 1,~ 1~5 0,5 0 0,5 1000 2,5 1,5 2~0 1~0 0 î,S
_ ._ Example 2 : 1% by weight ~f Na2P03F (in place of 1~ by ~eight ; of Na2S04) ~as added to the d;sh-washing agent described in Example 1. The course of damage during the 1000 washing cycles is illustrated in Table II.
Table II
Wash,in~ Glass Cutlery Cycles ~ama Alexandra Kalsch ~;ves Spoons Forks . __ __ . T ~
0 0 0 0 ~ 0 ~: 375 0 Q 0 0 0 0 n ~ n o o O
:~~750 0 0 0,5 0,5 0 0 lG00 0,5 D 0,5 0,5 0 0 . I I
~ 3 ~
Co~pared to Example 1, the corros;on inhibition can be seen clearly.
Example 3 1X by we;ght of Na2SiF6 was added as formulation (~), ;n place of 1% of Na2S04~ to a low-phosphate dish-washing agent of the following composition tA) 15% by weight of sodium tripolyphosphate, partially hydrated, containing 2X by ~e;ght of water of crystal-lization 60% by weight of sodium metasilicate, anhydrous 2~ by weight of NaDCC
2% by weight of surfactant and 21% by weight o~ Na2504, anhydrous The corrosion data for these two formulations are com-pared in Table lll. Using formulation A, the staihlesssteel hous;ng of the dishwasher and the cutlery had tarnished in a blue-violet colour after about 50 ~ash-ing cycles. The coating beca~e cloudy ~hite after 1Z5 washing cycles, and the coating was so considerable after 750 washing cycles that evaluation of the cutlery could no longer b~ carried out.
Table IIl .
Washing Glass Cutlery Cycles ~o~a Alex~ndra Kalsch ~ive~ Spoons Foaks A B A 8 A ~ A 9 ~ B` A 3 _ ~ .
0 0 0 0 0,5 0 1,G 0 1,0 0 ;,0 0 lZ5 0.5 0 0 0 0,5 0 1, 5 0 1 b5 0 1 ~5 0 2$0 1~5 0 0~5 0 1~0 0 1~S 0 1.5 0 1~5 0 ;~ 375 1,5 0 1~0 0 1,5 0 2,0 0 1,5 a 2Ao o 500 Z,0 0 1,0 0 2,0 0 2.5 0 2~5 0 2,5 0 750 2~5 0 2,5 Oi5 2,0 0 n.e.lO n.e. 0 n.e. 01 1000 2,5 0,5 2,5 0,5 2,0 0 n.e 0 n.e. 0 n e 0,5 n.e. = evaluation not possible ' ,` :' '. ~ ' ' `. ' ' ~3~7~
Example 4 2% by we;ght of NaF (D) ~ere added to a for~ulat;on w;thout triphosphate, but containing hydroxyethylene d;phosphonic acid (HEDP) as complexing agent (C). The corrosion data are shown in Table IV.
After about 50 washing cycles using formulation C~
the dishwasher housing and also some oflthe cutlery handles increasingly exhibited the discoloration and deposits described in Example 3, but not quite to the same extent. These phenomena do not appear using for-mulation D. However, white, rough str;pes which could not be removed appeared on the dishwasher housing ~rom about 1Z5 washing cycles.
Formulation composition C D
2Z~ by weight of HEDP 2X by weight of HEDP
60% by weight of Na2SiO3 60% by weight of Na2SiO3 34% by we;ght of NazC03 32% by weight of Na7C03 Z% by weight of NaDCC 2% by we;ght of NaDCC 0 2~ by weight of surfactants 2~ by weight of surfactants 2X by weight of NaF
Table IV
__ __ .
. ~ash~ng Glass Cutlery Cycles Ra~a Alexandra Kolsch ~nives Spoons Fnrks _ _ .
O O O O O, 5 0 1 ,0 0 1 ,0 0 1 ,0 0 125 0,5 0 O~S 0 0,5 0 2,0 0 1,0 0 1,~ 0 ;; 250 1,0 0 0,5 0 1.0 0 1.0 0 1,0 0 1,0 0 375 1,5 0 1,0 0 1,0 0 1,5 0 l,S 0 1,~ ~
500 1,5 0 1,0 0 l,S 0 1,5 0 1,5 0 l,S 0 750 2,0 0 1,5 0 Z~0 0 2.0 0 Z,0 0 1,5 0 1000 2, 5 0, 5 2, 0 ~ 2 ,, 5 0 2 G O O ~ 5 2, 0 0 ;' . O O
__ 1 ~ 7 ~
The corros;on result in these two exper;ments after 1000 wash;ng cycles was investigated us;ng a scanning elec-tron microscope for the example of "ROMA" tumbler~ Even at a magnification of about 10,000 times, hardly any damage was visible when fluorine ions were present.
Example 5 As for E~ample 4, but Na2P03F was used in formula-tion D in place of NaF. The course of damage on the washed pieces was virtually comparable to that for formulation D. However, no white str;pes were v;sible on the metalLic housing of the dishwasher even after 1000 washing cycles.
Example 6 On the one hand, a d;shwashing agent of composition E:
; 15 40% by weight of crystalline alkali ~etal phy~losilicate 25% by weight of sodium carbonate, anhydrous.
28.85X by weight of sodium sulphater anhydrous 1.9% by weight of the methylene-vinyl qster of maleic anhydride, powder (92% of active substance) 20 2.25~ by weight of sodium dichloroisocyanurate.2H20 2% by weight of surfactant and on the other hand a dishwashing agent of composition F which essentially corresponded to that of E but in which the 2% by weight of sodium carbonate were replaced by ZZ by weight of Na2P03F, were used.
The results of this comparison are collated in Table V.
, ~
- - ~ 3 ~
'rable V
_ Washing Glass ¦ Cutlery Cycles ~o~a Alexandra Kolsch ¦ ~nives Spoons Forks E F E r E ~ ! E F E ~ E
____ ~ _ _ 125 3 ~ 5 0 0 0 5 0 0 0 5 375 0,5 0 0 0 0,5 0 0,5 a 0 0 0,5 0 500 0,5 0 0 0 0,5 0 0.5 0 0 0 0,5 0 750 0,5 0 0,5 3 0,5 0 1,0 0 0 o 0,5 0 1000 1,5 C ~ 0,5 0,5 1,~ ol 0 C 0.5 It is clear that even the only sl;ghtl~ corrosive formulation E based on a phyllosilicate can still be positively affected as regards total corros;on by the simultaneous use of a fluorine compound contain;ng hydrolyzable fluor;de ;ons.
Claims (7)
1. A method for preventing corrosion on a surface produced from a molten silicate comprising applying to the surface a fluorine compound selected from the group consisting of alkali metal monofluorides, ammonium monofluorides, alkali metal aluminium hexafluorides, tin tetrafluoride, alkali metal fluorophosphates, ammonium fluorophosphates, alkali metal silicohexafluorides and ammonium silicofluorides.
2. The method according to claim 1, wherein the fluorine compound is added as a component of an agent that contains 0.1 to 5.0% by weight of the fluorine compound.
3. The method according to claim 2, wherein said agent is a dish-washing agent or detergent that further contains one or more builders, alkali carriers, surfactants, activated chlorine carriers/ fillers, perfumes or dyes, individually or mixed with one another.
4. The method according to claim 3, wherein said agent contains 30 to 95% by weight of builders and alkali carriers combined, and 0.1 to 5.0% by weight of the fluorine compound.
5. The method according to claim 4, wherein said agent contains 0.5 to 2.0% by weight of the fluorine compound.
6. The method according to claim 4, wherein the content of fluorine in the total mixture is at least 0.05% by weight.
7. A use of a fluorine compound selected from the group consisting of alkali metal monofluorides, ammonium monofluorides, alkali metal aluminium hexafluorides, tin tetrafluoride, alkali metal fluorophosphates, ammonium fluorophosphates, alkali metal silicohexafluorides and ammonium silicofluorides to prevent corrosion on a surface produced from a molten silicate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3714451.0 | 1987-04-30 | ||
| DE19873714451 DE3714451A1 (en) | 1987-04-30 | 1987-04-30 | AGENT FOR PREVENTING CORROSION ON CERAMIC SURFACES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1310876C true CA1310876C (en) | 1992-12-01 |
Family
ID=6326604
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000562702A Expired - Fee Related CA1310876C (en) | 1987-04-30 | 1988-03-28 | Agent for preventing corrosion on ceramic surfaces |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0288812B1 (en) |
| JP (1) | JPS63284297A (en) |
| AT (1) | ATE66018T1 (en) |
| CA (1) | CA1310876C (en) |
| DE (2) | DE3714451A1 (en) |
| DK (1) | DK232588A (en) |
| FI (1) | FI882000A (en) |
| NO (1) | NO881901L (en) |
| PT (1) | PT87373B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO303457B1 (en) * | 1987-12-17 | 1998-07-13 | Domtar Inc | Procedure for inhibiting corrosion and composition for deicing of reinforced concrete |
| US5071579A (en) * | 1988-08-29 | 1991-12-10 | Domtar Inc. | Corrosion inhibiting systems, products containing residual amounts of such systems, and methods therefor |
| ATE130025T1 (en) * | 1991-02-14 | 1995-11-15 | Domtar Inc | METHOD FOR REDUCING CONCRETE SHALLING CAUSED BY FREEZE AND THAW. |
| US5624892A (en) * | 1995-05-19 | 1997-04-29 | Lever Brothers Company, Division Of Conopco, Inc. | Process for incorporating aluminum salts into an automatic dishwashing composition |
| DE19540087A1 (en) * | 1995-10-27 | 1997-04-30 | Henkel Kgaa | Dishwashing liquid |
| JP2008531829A (en) | 2005-03-04 | 2008-08-14 | ザ プロクター アンド ギャンブル カンパニー | Automatic dishwashing composition having a corrosion inhibitor |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2750257A1 (en) * | 1977-11-10 | 1979-05-17 | Collo Gmbh | Compsn. for cleaning heat resistant articles - esp. glass ceramic oven-ware, contains acidic fluoride cpd. in non-aqueous medium esp. paraffin |
| GB2023165B (en) * | 1978-06-15 | 1982-10-13 | Allied Chem | Organic stripping composition and method with improved metal corrosion inhibitor system |
| FR2527643B1 (en) * | 1982-05-28 | 1985-09-27 | Ouest Union Chimique Indle | NOVEL CORROSION INHIBITOR AND COMPOSITION CONTAINING THE SAME |
| DE3444068A1 (en) * | 1984-12-03 | 1986-06-05 | Henkel KGaA, 4000 Düsseldorf | AGENT AND METHOD FOR TREATING WASHED LAUNDRY |
-
1987
- 1987-04-30 DE DE19873714451 patent/DE3714451A1/en not_active Withdrawn
-
1988
- 1988-03-28 CA CA000562702A patent/CA1310876C/en not_active Expired - Fee Related
- 1988-04-12 DE DE8888105761T patent/DE3864063D1/en not_active Expired - Fee Related
- 1988-04-12 EP EP88105761A patent/EP0288812B1/en not_active Expired - Lifetime
- 1988-04-12 AT AT88105761T patent/ATE66018T1/en not_active IP Right Cessation
- 1988-04-25 JP JP63100444A patent/JPS63284297A/en active Pending
- 1988-04-28 DK DK232588A patent/DK232588A/en not_active Application Discontinuation
- 1988-04-28 FI FI882000A patent/FI882000A/en not_active Application Discontinuation
- 1988-04-29 PT PT87373A patent/PT87373B/en not_active IP Right Cessation
- 1988-04-29 NO NO881901A patent/NO881901L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3864063D1 (en) | 1991-09-12 |
| NO881901D0 (en) | 1988-04-29 |
| NO881901L (en) | 1988-10-31 |
| EP0288812A1 (en) | 1988-11-02 |
| JPS63284297A (en) | 1988-11-21 |
| DK232588D0 (en) | 1988-04-28 |
| FI882000A (en) | 1988-10-31 |
| PT87373A (en) | 1988-05-01 |
| PT87373B (en) | 1992-08-31 |
| DK232588A (en) | 1988-10-31 |
| FI882000A0 (en) | 1988-04-28 |
| DE3714451A1 (en) | 1988-11-10 |
| EP0288812B1 (en) | 1991-08-07 |
| ATE66018T1 (en) | 1991-08-15 |
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