CN104661977A - Molten salt for use in toughening glass, production method of toughened glass, and life extension method of molten salt for use in toughening glass - Google Patents
Molten salt for use in toughening glass, production method of toughened glass, and life extension method of molten salt for use in toughening glass Download PDFInfo
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- CN104661977A CN104661977A CN201380048664.9A CN201380048664A CN104661977A CN 104661977 A CN104661977 A CN 104661977A CN 201380048664 A CN201380048664 A CN 201380048664A CN 104661977 A CN104661977 A CN 104661977A
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- Prior art keywords
- glass
- melting salt
- salt
- saltpetre
- ion
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
Abstract
Given a molten salt containing potassium nitrate used for chemically toughening glass, the purpose of the present invention is to provide a molten salt with a well-extended use life. This molten salt for use in toughening glass is used for forming a compressive stress layer on a glass surface by means of ion exchange, contains potassium nitrate and further contains carbonate anions and/or phosphate anions.
Description
Technical field
The present invention relates to glass reinforced melting salt, the manufacture method of chilled glass and the life method of glass reinforced melting salt.
Background technology
For digital camera, mobile telephone and PDA (personal digital assistant; Personal DigitalAssistants) protective glass of such display equipment etc. and the glass substrate of indicating meter; use the glass (hereinafter also referred to as chemically reinforced glass) after utilizing ion-exchange etc. to carry out chemical intensification treatment.Although glass theoretical strength is high, can intensity be caused significantly to reduce due to damage.With the glassy phase ratio do not strengthened, the physical strength of chemically reinforced glass is high, can prevent from bringing damage to glass surface, is therefore suitable for these purposes.
The chemical intensification treatment of ion-exchange is utilized to be make glass surface produce compressive stress layers by the metal ion (such as Na ion) of small ionic radii contained in displacement glass and the metal ion (such as K ion) of more heavy ion radius thus improve the process of the intensity of glass.
Containing Na in glass composition
2when O, by glass-impregnated in the melting salt (inorganic potassium salt) containing K ion, the Na ion in glass and the K ion in melting salt is made to carry out ion-exchange.Melting salt is in the inorganic potassium salt of molten state under being used in intensive treatment temperature, wherein mostly use saltpetre.
As one of the evaluation method of chemically reinforced glass, surface compression stress (Compressive Stress:CS) can be enumerated.Chemical enhanced melting salt using saltpetre as main component after chemical intensification treatment can to glass give the highest this result of CS value be only limitted to use melting salt (the new melting salt) that be not supplied to ion-exchange time, in fact correspond to accumulated glass processing area, the CS value obtained can slowly reduce.
The major cause that known CS value reduces be by because of ion-exchange from glass the Na ion of stripping saltpetre melting salt is caused by diluting, Na ionic concn reduces relevant with CS value.Therefore, if the CS value of more than certain certain value cannot be obtained, then the method all or part of of melting salt being exchanged for new melting salt can be considered.But in these methods, the exchange frequency of melting salt uprises, worrying be high cost, exchange time stop time cause processing efficiency to reduce.
Therefore, the method in the work-ing life (life-span) extending melting salt is studied.Such as disclose in non-patent literature 1 and in saltpetre melting salt, to add silicon-dioxide in advance to the method for the impact relaxing Na ion and bring.
Prior art document
Non-patent literature
Non-patent literature 1:Nagaoka Gijutsu Kagaku Daigaku KenkyuHokoku (1982), 4,1-4.
Summary of the invention
Invent problem to be solved
But, in the effect that interpolation silicon-dioxide described in non-patent literature 1 brings, for silicon-dioxide 0.1% adulterate only describe with SODIUMNITRATE relative to saltpetre be 0.2%, namely Na ion for extending the content in the life-span of melting salt when the indivisible like this mixing of 500ppm exists, do not mention the situation that Na ionic weight is many.
Therefore, the melting salt containing saltpetre that the object of the invention is to for the chemical enhanced middle use at glass provides a kind of melting salt fully extending work-ing life.
For the means of dealing with problems
Present inventor has performed further investigation found that, more than one adding in salt of wormwood and potassiumphosphate before chemical intensification treatment at glass in containing the melting salt of saltpetre in advance make containing at least one in carbonate anion and phosphate anion, the work-ing life of melting salt can be extended thus, thus complete the present invention.
That is, the present invention is as described below.
<1> glass reinforced melting salt, for forming compressive stress layers by ion-exchange at glass surface, wherein, this glass reinforced melting salt contains saltpetre, also containing at least one in carbonate anion and phosphate anion.
The glass reinforced melting salt of <2> as described in above-mentioned <1>, wherein, this glass reinforced melting salt contains saltpetre, carbonate anion and phosphate anion.
The glass reinforced melting salt of <3> as described in above-mentioned <1> or <2>, wherein, above-mentioned carbonate anion is the anionic species of salt of wormwood, and above-mentioned phosphate anion is the anionic species of at least one in potassium orthophosphate and potassium pyrophosphate.
The glass reinforced melting salt of <4> as described in above-mentioned <3>, wherein, the content of above-mentioned salt of wormwood is 3.5 ~ 24 % by mole relative to above-mentioned saltpetre.
The glass reinforced melting salt of <5> as described in above-mentioned <3> or <4>, wherein, the content of above-mentioned potassium orthophosphate is 0.8 ~ 13.5 % by mole relative to above-mentioned saltpetre.
The glass reinforced melting salt of <6> according to any one of above-mentioned <3> ~ <5>, wherein, the content of above-mentioned potassium pyrophosphate is 3.5 ~ 9.0 % by mole relative to above-mentioned saltpetre.
The manufacture method of a <7> chilled glass, it comprises the operation using the glass reinforced melting salt according to any one of above-mentioned <1> ~ <6> to form compressive stress layers at glass surface.
The life method of a <8> glass reinforced melting salt, the life being formed the glass reinforced melting salt of compressive stress layers by ion-exchange at glass surface will be used for, wherein, at least one in containing the melting salt before the intensive treatment of saltpetre in mixed carbonic acid potassium and potassiumphosphate, makes containing at least one in carbonate anion and phosphate anion.
Invention effect
According to melting salt of the present invention, can suppress or relax the reduction of the surface compression stress (CS) produced by the increase of the Na ionic concn from glass stripping, the work-ing life of melting salt can be extended.Consequently, the exchange frequency of melting salt can be reduced, the cost degradation of chemical intensification treatment can be realized and boost productivity.
Accompanying drawing explanation
Fig. 1 is the graphic representation that the relation of not add other inorganic potassium salt carries out chemical intensification treatment, in melting salt Na ionic concn and CS value in saltpetre melting salt is shown.
Fig. 2 illustrates in saltpetre melting salt, to add potassium orthophosphate carries out chemical intensification treatment, the addition of Na relative to saltpetre and the graphic representation of the relation of the CS value obtained.
Fig. 3 is the graphic representation that the addition of potassium orthophosphate in melting salt and the relation of the life-span ratio of melting salt are shown.
Fig. 4 illustrates in saltpetre melting salt, to add salt of wormwood carries out chemical intensification treatment, the addition of Na relative to saltpetre and the graphic representation of the relation of the CS value obtained.
Fig. 5 is the graphic representation that the addition of salt of wormwood in melting salt and the relation of the life-span ratio of melting salt are shown.
Fig. 6 illustrates in saltpetre melting salt, to add potassium pyrophosphate carries out chemical intensification treatment, the addition of Na relative to saltpetre and the graphic representation of the relation of the CS value obtained.
Fig. 7 is the addition of potassium pyrophosphate in melting salt and the graphic representation of the relation of the life-span ratio of melting salt.
Fig. 8 is whole ion-exchange capacity of the anionic species that the potassium orthophosphate, potassium pyrophosphate and the salt of wormwood that add in melting salt are shown and the graphic representation of the relation of the life-span ratio of melting salt.
Fig. 9 illustrates in saltpetre melting salt, to add silicon-dioxide carries out chemical intensification treatment, the addition of Na relative to saltpetre and the graphic representation of the relation of the CS value obtained.
Figure 10 is the graphic representation that the addition of silicon-dioxide in melting salt and the relation of the life-span ratio of melting salt are shown.
Embodiment
Below, the present invention is described in detail.
It should be noted that, in this manual, " quality % " and " % by weight " is equivalent in meaning.
< melting salt >
Glass reinforced melting salt of the present invention (hereinafter also referred to melting salt of the present invention) is containing inorganic potassium salt.As inorganic potassium salt, be preferably and carrying out below the strain point (being generally 500 ~ 600 DEG C) of chemical enhanced glass and have the inorganic potassium salt of fusing point, in the present invention containing saltpetre (fusing point is 330 DEG C) as main component.If saltpetre is main component, be then molten state below the strain point of glass, and in use temperature region, manipulation is easy, is preferred from this respect.At this, main component refers to containing more than 50 quality %.
Melting salt of the present invention except as except the saltpetre of main component also containing at least one in carbonate anion and phosphate anion.Thus, and not compare with when phosphate anion containing carbonate anion, the work-ing life of melting salt can be extended.
When continuing to use same melt salt in chemical intensification treatment, carry out with utilizing the melting salt (hereinafter also referred to " melting salt of original state " or " new melting salt ") not being supplied to chemical intensification treatment compared with chemical enhanced situation, slowly reducing corresponding to accumulated glass processing area the CS value that glass can be given.
In the present invention, make containing at least one in carbonate anion and phosphate anion at more than one carrying out being pre-mixed in the melting salt before chemical intensification treatment in salt of wormwood and potassiumphosphate, carry out chemical intensification treatment, the carbonate anion be pre-existing in melting salt at sodium stripping initial stage sodium thus, phosphate anion caught, and the Na ion concentration near glass surface reduces.Further, the sodium salt of carbonate anion, phosphate anion exceeds saturation solubility amount and separates out, and thus suppresses the rising of the Na ion concentration in melting salt.Think the life-span that can be extended melting salt by this effect.
Consideration in quantitative comparison, evaluation is carried out as follows in the life ability brought added salt of wormwood, potassiumphosphate etc.Such as, when potassium orthophosphate, the negatively charged ion forming potassium orthophosphate is PO
4 3-, be the negatively charged ion of trivalent.The valence mumber of negatively charged ion is larger, attracts cationic power stronger, more easily keeps positively charged ion.
The positively charged ion K of monovalence in potassium orthophosphate
+there are three, but according to the acid ionization constant (pKa1=1.83, pka2=6.43, pka3=11.46) of phosphoric acid, think that to carry out with Na ion exchanging in melting salt is in three potassium one, the potential Na-K ion-exchange capacity of every 1 mole of potassium orthophosphate can be evaluated as:
Potential Na-K ion-exchange capacity=(valence mumber of anionic species) × (the K ionic weight that can exchange)=3 × 1=3
Thus, whole ion-exchange capacities of the potassium orthophosphate added in melting salt can be passed through to obtain as follows:
Whole ion-exchange capacity=(potassium orthophosphate addition) × (potential Na-K ion-exchange capacity)
Think that this whole ion-exchange capacity is higher, then carry out the probability that the Na ion in the melting salt after ion-exchange carries out ion-exchange with the K ion of added inorganic potassium salt further with glass higher, more can relax the ion-exchange obstruction that the sodium in melting salt causes, contribute to the life of melting salt.
In the present invention, following index is used in order to the work-ing life (life-span) to melting salt carries out quantitative evaluation.First, desired CS value is defined as: when the CS value obtained according to the melting salt that is made up of the saltpetre of original state being set as 100%, more than 90% CS value.Further, by when utilizing chemical intensification treatment cannot obtain desired CS value, CS value relative to desired CS value reduction by more than 10% time melting salt in Na ionic concn be defined as work-ing life of melting salt.
It should be noted that, the life-span of melting salt can be evaluated according to as described below.First, in order to simulate the state produced and repeatedly carry out after chemical intensification treatment, wittingly the SODIUMNITRATE of specified amount is added in melting salt as Na ion source.And utilize the melting salt after adding Na ion source to carry out chemical intensification treatment to glass, when the CS value of the glass after process is lower than desired CS value, calculates Na ionic concn by the addition of SODIUMNITRATE, the index in the life-span of melting salt can be it can be used as.
When melting salt of the present invention contains salt of wormwood, its content is preferably 3.5 % by mole ~ 24 % by mole (5.0 quality % ~ 30 quality %) relative to the saltpetre in melting salt, is more preferably 8.0 % by mole ~ 24 % by mole (10.9 quality % ~ 30 quality %), is particularly preferably 16.0 % by mole ~ 24 % by mole (21.5 quality % ~ 30 quality %).
If salt of wormwood is below 30 quality % relative to the addition of saltpetre, then do not worry that the solid phase amount in the melting salt that the salt of wormwood that fusing point is high causes increases, manipulation is good.In addition, in ion exchange treatment, do not worry producing temperature uneven, ion-exchange can be carried out to bulk glass equably.
As potassiumphosphate, potassium orthophosphate (K can be enumerated
3pO
4), potassium pyrophosphate (K
4p
2o
7), potassium metaphosphate, from the aspect of the life efficiency of the whole ion-exchange capacities relative to added anionic species, preferred potassium orthophosphate.
When adding potassium orthophosphate as potassiumphosphate, potassium orthophosphate both can be that hydrate also can carry out processed.In addition, the content of the potassium orthophosphate in melting salt is preferably 0.8 % by mole ~ 13.5 % by mole (1.5 quality % ~ 25 quality %) relative to saltpetre, is more preferably 1.5 % by mole ~ 13.5 % by mole (3.0 quality % ~ 25 quality %), more preferably 3.0 % by mole ~ 13.5 % by mole (6.0 quality % ~ 25 quality %), be particularly preferably 6.0 % by mole ~ 13.5 % by mole (11.5 quality % ~ 25 quality %).If lower limit is this scope, can by can obtain desired CS value melting salt life twice more than, thus preferably.
In addition, the fusing point of potassium orthophosphate is high (>1000 DEG C), and in chemical enhanced middle used temperature province (<500 DEG C), the amount being dissolved in saltpetre is few.Piling up at the bottom settlings thing of container when therefore adding excessive causes the manipulation of melting salt to be deteriorated.Therefore, if be below 25 quality % relative to saltpetre, then can suppress the ratio of the solid phase of potassium orthophosphate, can guarantee to can be used for chemical enhanced liquid phase volume fully, potassium phosphate precipitation thing in melting salt and glass contact can not occurring and bring out the corrosion of glass surface, is preferred.
When adding potassium pyrophosphate as potassiumphosphate, be preferably 3.5 % by mole ~ 9.0 % by mole (10.5 quality % ~ 25 quality %) relative to the saltpetre in melting salt, be more preferably more than 7.5 % by mole (more than 21.0 quality %).If lower limit is this scope, can by can obtain desired CS value melting salt life twice more than, thus preferably.
In addition, potassium pyrophosphate also the same with potassium orthophosphate because of add excessive and cause powder and chemical enhanced glass contact time likely can etching glass surface, thus the upper limit of the content of potassium pyrophosphate is preferably set to 25 quality %.
It should be noted that, above-mentioned salt of wormwood and potassiumphosphate can be share.In this case, as long as salt of wormwood and potassiumphosphate addition separately meets above-mentioned scope respectively, then can be any combination.
Melting salt of the present invention except saltpetre, salt of wormwood and potassiumphosphate with except not hindering the scope of effect of the present invention to contain other chemical species, basic sulfatase, the alkaline chlorates etc. such as such as sodium sulfate, potassium sulfate, sodium-chlor, Repone K can be enumerated.It should be noted that, what can combinationally use in them is multiple.
The manufacture method > of < melting salt
Melting salt of the present invention can be manufactured by operation as follows.
Operation 1: the preparation of saltpetre melting salt
Operation 2: add other inorganic potassium salt in melting salt
(operation 1)
In operation 1, be fed into by saltpetre in container, the temperature being heated to more than fusing point carries out melting, prepares melting salt thus.The fusing point of saltpetre is 330 DEG C, boiling point is 500 DEG C, carries out melting at the temperature therefore within the scope of this.Especially from the surface compression stress can given glass and the balance of the stressor layers degree of depth and the aspect of enhanced time, more preferably melt temperature is set as 350 ~ 470 DEG C.
Container saltpetre being carried out to melting can use metal, quartz, pottery etc.Wherein, be preferably metal material from the viewpoint of weather resistance, be preferably stainless steel (SUS) material from the viewpoint of erosion resistance.
(operation 2)
In operation 2, add the inorganic potassium salt beyond the saltpetre such as salt of wormwood, potassiumphosphate in the saltpetre melting salt of preparation in operation 1, while making temperature be held in certain limit, be mixed to entirety by utilizing agitating vane etc. and become even.When share salt of wormwood and potassiumphosphate, order of addition does not limit, and first can add any one, also can add simultaneously.Temperature be preferably more than the fusing point of saltpetre, namely more than 330 DEG C, be more preferably 350 ~ 500 DEG C.In addition, churning time is preferably 1 minute ~ 10 hours, is more preferably 10 minutes ~ 2 hours.Then, leave standstill to precipitate and precipitate.The sodium salt of salt of wormwood, potassiumphosphate and carbonate anion, the sodium salt of phosphate anion that exceed saturation solubility is comprised in this precipitate.
So, melting salt of the present invention can be manufactured.
< chemical intensification treatment >
Then, to using the method for chemical strengthening treatment of melting salt of the present invention to be described.
Chemical intensification treatment passes through by glass-impregnated in melting salt, and the metal ion that the ionic radius be replaced in melting salt by the metal ion in glass is large carries out thus.Make by this ion-exchange the composition changing glass surface, produce stress under compression at surface layer of glass, thus can chilled glass.
Chemical intensification treatment in the present invention can be undertaken by the operation as follows after the manufacture method of above-mentioned melting salt (operation 1, operation 2).
Operation 3: the chemical intensification treatment of glass
Operation 4: discarding of melting salt
(operation 3)
In operation 3, preheating is carried out to glass, the melting salt of preparation in above-mentioned operation 1 and operation 2 is adjusted to and carries out chemical enhanced temperature.Then the glass after preheating is flooded the specified time in melting salt, then glass is mentioned from melting salt, carry out naturally cooling.It should be noted that, before chemical intensification treatment, preferably carry out processing according to the shape of purposes to glass, the mechanical workouts such as such as cut-out, end face processing and perforate processing.
The preheating temperature of glass depends on the temperature of flooding in melting salt, is usually preferably more than 100 DEG C.
Chemical enhanced temperature is preferably reinforced the strain point (being generally 500 ~ 600 DEG C) of glass below, is particularly preferably more than 350 DEG C to obtain higher stress under compression layer depth (Depth of Layer:DOL).
The dipping time of glass in melting salt be preferably 10 minutes ~ 12 hours, more preferably 30 minute ~ and 10 hours.If in this scope, then can obtain the chemically reinforced glass that the balance of the degree of depth of intensity and compressive stress layers is excellent.
(operation 4)
When repeatedly carrying out operation 3, the Na ionic concn in melting salt raises because of the ion-exchange between melting salt-glass, and therefore the ion-exchange capacity of melting salt increases along with glass treatment area and reduces, and cannot obtain desired CS value.Therefore, in operation 4, by measure Na ionic concn in melting salt or chemical enhanced after surface compression stress (CS) value, judge that can continue to use melting salt to carry out chemical intensification treatment still will discard melting salt.
< glass >
The glass used in the present invention contains sodium, if having can utilize shaping, chemical intensification treatment carries out the composition strengthened, then can use the glass of various composition.Specifically, such as soda-lime glass, alumina silicate glass, pyrex, lead glass, alkali barium glass, alumina borosilicate glass etc. can be enumerated.
The manufacture method of glass is not particularly limited, can by desired frit be fed into continuous fusion stove, after frit is carried out heating and melting, clarification at being preferably 1500 ~ 1600 DEG C, be supplied to building mortion, then melten glass is configured as tabular, carry out slow cooling, manufacture thus.
It should be noted that, for the shaping of glass, various method can be adopted.Such as can adopt glass tube down-drawing (such as, overflow downdraw, discharge orifice glass tube down-drawing and daraf(reciprocal of farad) etc. again), the various manufacturing process such as float glass process, roller laid process and pressing.
The thickness of glass is not particularly limited, and in order to effectively carry out chemical intensification treatment, being usually preferably below 5mm, being more preferably below 3mm.
Composition as chemical enhanced glass of the present invention is not particularly limited, such as, can enumerate the composition of following glass.
(i) with in % by mole composition represented, containing the SiO of 50 ~ 80%
2, 2 ~ 25% Al
2o
3, 0 ~ 10% Li
2o, 0 ~ 18% Na
2o, 0 ~ 10% K
2the ZrO of O, the MgO of 0 ~ 15%, the CaO of 0 ~ 5% and 0 ~ 5%
2glass
(ii) SiO of 50 ~ 74% is contained with % by mole composition represented
2, 1 ~ 10% Al
2o
3, 6 ~ 14% Na
2o, 3 ~ 11% K
2the ZrO of O, the MgO of 2 ~ 15%, the CaO of 0 ~ 6% and 0 ~ 5%
2, SiO
2and Al
2o
3content add up to less than 75%, Na
2o and K
2the content of O add up to 12 ~ 25%, the content of MgO and CaO add up to 7 ~ 15% glass
(iii) SiO of 68 ~ 80% is contained with % by mole composition represented
2, 4 ~ 10% Al
2o
3, 5 ~ 15% Na
2o, 0 ~ 1% K
2o, the MgO of 4 ~ 15% and the ZrO of 0 ~ 1%
2glass
(iv) SiO of 67 ~ 75% is contained with % by mole composition represented
2, 0 ~ 4% Al
2o
3, 7 ~ 15% Na
2o, 1 ~ 9% K
2o, the MgO of 6 ~ 14% and the ZrO of 0 ~ 1.5%
2, SiO
2and Al
2o
3content add up to 71 ~ 75%, Na
2o and K
2the content of O add up to 12 ~ 20%, containing the glass that its content when CaO is less than 1%
Glass can grind as required before chemical intensification treatment.As Ginding process, can enumerate such as supplying ground slurry and utilize grinding pad to carry out the method for grinding, for ground slurry, the ground slurry comprising abrasive substance and water can be used.As abrasive substance, be preferably cerium oxide (cerium dioxide) and silicon-dioxide.
When grinding glass, scavenging solution is utilized to clean the glass after grinding.As scavenging solution, be preferably neutral cleaners and water, clean with water again after more preferably utilizing neutral cleaners to clean.Commercially available neutral cleaners can be used as neutral cleaners.
Scavenging solution is utilized finally to clean the glass substrate after above-mentioned matting cleaning.As scavenging solution, such as water, ethanol and Virahol etc. can be enumerated.Wherein be preferably water.
After above-mentioned final cleaning, make glass dry.Drying conditions can consider that the characteristic etc. of scavenging solution and the glass used in matting selects top condition.
Embodiment
Below embodiments of the invention are described particularly, but the present invention is not defined in these embodiments.
(glass composition)
Soda-lime glass and alumina silicate glass two kinds of glass are used for carrying out chemical enhanced glass.
Soda-lime glass (with % by mole composition represented): SiO
272.0%, Al
2o
31.1%, Na
2o
312.6%, K
2o 0.2%, MgO 5.5%, CaO 8.6%
Alumina silicate glass (with % by mole composition represented): SiO
264.4%, Al
2o
38.0%, Na
2o
312.5%, K
2o 4.0%, MgO 10.5%, CaO 0.1%, SrO 0.1%, BaO 0.1%, ZrO
22.5%
(evaluation of glass)
The evaluation of glass is by measuring surperficial stress under compression (CS) and stress under compression layer depth (DOL) is carried out.CS and DOL obtains by using surface stress meter (rolling over the made FSM-6000LE of former making) to measure the refringence of glass surface and inside.
[embodiment 1: the interpolation of potassium orthophosphate]
(embodiment 1A-1 ~ 1A-6)
(embodiment 1A-1)
In the cup of SUS, add saltpetre 250g, utilize mantle heater be heated to 430 DEG C thus prepare melting salt.30.4g potassium orthophosphate trihydrate (K is added in the melting salt prepared thus
3pO
4content relative to saltpetre: 4.4 % by mole), use stirring motor, four propeller blades stir two hours, leave standstill two hours.Then soda-lime glass is preheated to 100 DEG C, in the melting salt of 430 DEG C, dipping carries out chemical intensification treatment in 4 hours.Then the ion exchanged water of 100 DEG C is utilized to clean glass, 60 DEG C of dryings two hours.Measure CS, the DOL of this glass after chemical intensification treatment respectively.
(embodiment 1A-2)
In the melting salt after carry out chemical intensification treatment in embodiment 1A-1, add 0.93g SODIUMNITRATE, use stirring motor, four propeller blades stir two hours, leave standstill two hours.Then soda-lime glass is preheated to 100 DEG C, in the melting salt of 430 DEG C, dipping carries out chemical intensification treatment in 4 hours.The ion exchanged water of 100 DEG C is utilized to clean glass, 60 DEG C of dryings two hours.Then CS, DOL is measured respectively.
(embodiment 1A-3)
In the melting salt after carry out chemical intensification treatment in embodiment 1A-2, add 0.92g SODIUMNITRATE (addition of SODIUMNITRATE adds up to 1.85g) further, use stirring motor, four propeller blades stir two hours, leave standstill two hours.Then soda-lime glass is preheated to 100 DEG C, in the melting salt of 430 DEG C, dipping carries out chemical intensification treatment in 4 hours.The ion exchanged water of 100 DEG C is utilized to clean glass, 60 DEG C of dryings two hours.Then CS, DOL is measured respectively.
(embodiment 1A-4)
In the melting salt after carry out chemical intensification treatment in embodiment 1A-3, add 0.94g SODIUMNITRATE (addition of SODIUMNITRATE adds up to 2.79g) further, use stirring motor, four propeller blades stir two hours, leave standstill two hours.Soda-lime glass is preheated to 100 DEG C, in the melting salt of 430 DEG C, dipping carries out chemical intensification treatment in 4 hours.The ion exchanged water of 100 DEG C is utilized to clean glass, 60 DEG C of dryings two hours.Then CS, DOL is measured respectively.
(embodiment 1A-5)
In the melting salt after carry out chemical intensification treatment in embodiment 1A-4, add 1.93g SODIUMNITRATE (addition of SODIUMNITRATE adds up to 4.72g) further, use stirring motor, four propeller blades stir two hours, leave standstill two hours.Soda-lime glass is preheated to 100 DEG C, in the melting salt of 430 DEG C, dipping carries out chemical intensification treatment in 4 hours.The ion exchanged water of 100 DEG C is utilized to clean glass, 60 DEG C of dryings two hours.Then CS, DOL is measured respectively.
(embodiment 1A-6)
In the melting salt after carry out chemical intensification treatment in embodiment 1A-5, add 4.87g SODIUMNITRATE (addition of SODIUMNITRATE adds up to 9.59g) further, use stirring motor, four propeller blades stir two hours, leave standstill two hours.Soda-lime glass is preheated to 100 DEG C, in the melting salt of 430 DEG C, dipping carries out chemical intensification treatment in 4 hours.The ion exchanged water of 100 DEG C is utilized to clean glass, 60 DEG C of dryings two hours.Then CS, DOL is measured respectively.
(embodiment 1B-1 ~ 1B-6)
Glass is changed to alumina silicate glass, prepares melting salt in addition in the same manner as embodiment 1A-1 ~ 1A-6, carry out chemical intensification treatment, measure CS, DOL respectively.
[comparative example 1: only have saltpetre]
(comparative example 1A-1 ~ 1A-6)
Do not add potassium orthophosphate trihydrate and use the melting salt only having saltpetre, carrying out chemical intensification treatment in addition in the same manner as embodiment 1A-1 ~ 1A-6, measure CS, DOL respectively.
(comparative example 1B-1 ~ 1B-6)
Do not add potassium orthophosphate trihydrate and use the melting salt only having saltpetre, carrying out chemical intensification treatment in addition in the same manner as embodiment 1B-1 ~ 1B-6, measure CS, DOL respectively.
[embodiment 2: add potassium orthophosphate]
(embodiment 2A-1 ~ 2A-6)
The addition of potassium orthophosphate trihydrate is made to be 6.7g (K
3pO
4content relative to saltpetre: 1 % by mole), carry out chemical intensification treatment in addition in the same manner as embodiment 1A-1 ~ 1A-6, measure CS, DOL respectively.
(embodiment 2B-1 ~ 2B-6)
The addition of potassium orthophosphate trihydrate is made to be 6.7g (K
3pO
4content relative to saltpetre: 1 % by mole), carry out chemical intensification treatment in addition in the same manner as embodiment 1B-1 ~ 1B-6, measure CS, DOL respectively.
[embodiment 3: add potassium orthophosphate]
(embodiment 3A-1 ~ 3A-6)
The addition of potassium orthophosphate trihydrate is made to be 43.2g (K
3pO
4content relative to saltpetre: 6 % by mole), carry out chemical intensification treatment in addition in the same manner as embodiment 1A-1 ~ 1A-6, measure CS, DOL respectively.
(embodiment 3B-1 ~ 3B-6)
The addition of potassium orthophosphate trihydrate is made to be 43.2g (K
3pO
4content relative to saltpetre: 6 % by mole), carry out chemical intensification treatment in addition in the same manner as embodiment 1B-1 ~ 1B-6, measure CS, DOL respectively.
The measurement result of embodiment 1 ~ 3 is shown in Table 1, the measurement result of comparative example 1 is shown in Table 2.
[table 1]
[table 2]
[embodiment 4: add salt of wormwood]
(embodiment 4A-1)
In the cup of SUS, add saltpetre 250g, utilize mantle heater be heated to 430 DEG C thus prepare melting salt.29.7g salt of wormwood (K is added in the melting salt prepared thus
2cO
3content relative to saltpetre: 8 % by mole), use stirring motor, four propeller blades stir 10 hours, leave standstill two hours.Then soda-lime glass is preheated to 100 DEG C, in the melting salt of 430 DEG C, dipping carries out chemical intensification treatment in 4 hours.Then the ion exchanged water of 100 DEG C is utilized to clean glass, 60 DEG C of dryings two hours.Measure CS, the DOL of this glass after chemical intensification treatment respectively.
(embodiment 4A-2 ~ 4A-6)
In the same manner as embodiment 1A-2 ~ 1A-6, in the melting salt carrying out chemical intensification treatment, add SODIUMNITRATE successively, carry out chemical intensification treatment, measure CS, DOL respectively.
(embodiment 4B-1 ~ 4B-6)
Glass is changed to alumina silicate glass, prepares melting salt in addition in the same manner as embodiment 4A-1 ~ 4A-6, carry out chemical intensification treatment, measure CS, DOL respectively.
[embodiment 5: add salt of wormwood]
(embodiment 5A-1 ~ 5A-6)
The addition of salt of wormwood is made to be 18.0g (K
2cO
3content relative to saltpetre: 5 % by mole), carry out chemical intensification treatment in addition in the same manner as embodiment 4A-1 ~ 4A-6, measure CS, DOL respectively.
(embodiment 5B-1 ~ 5B-6)
The addition of salt of wormwood is made to be 18.0g (K
2cO
3content relative to saltpetre: 5 % by mole), carry out chemical intensification treatment in addition in the same manner as embodiment 4B-1 ~ 4B-6, measure CS, DOL respectively.
[embodiment 6: add salt of wormwood]
(embodiment 6A-1 ~ 6A-6)
The addition of salt of wormwood is made to be 55.6g (K
2cO
3content relative to saltpetre: 14 % by mole), carry out chemical intensification treatment in addition in the same manner as embodiment 4A-1 ~ 4A-6, measure CS, DOL respectively.
(embodiment 6B-1 ~ 6B-6)
The addition of salt of wormwood is made to be 55.6g (K
2cO
3content relative to saltpetre: 14 % by mole), carry out chemical intensification treatment in addition in the same manner as embodiment 4B-1 ~ 4B-6, measure CS, DOL respectively.
The measurement result of embodiment 4 ~ 6 is shown in Table 3.
[table 3]
[embodiment 7: add potassium pyrophosphate]
(embodiment 7A-1 ~ 7A-6)
(embodiment 7A-1)
In the cup of SUS, add saltpetre 250g, utilize mantle heater be heated to 430 DEG C thus prepare melting salt.30.4g potassium pyrophosphate trihydrate (K is added in the melting salt prepared thus
4p
2o
7content relative to saltpetre: 4.4 % by mole), use stirring motor, four propeller blades stir two hours, leave standstill two hours.Then soda-lime glass is preheated to 100 DEG C, in the melting salt of 430 DEG C, dipping carries out chemical intensification treatment in 4 hours.Then the ion exchanged water of 100 DEG C is utilized to clean glass, 60 DEG C of dryings two hours.Measure CS, the DOL of this glass after chemical intensification treatment respectively.
(embodiment 7A-2 ~ 7A-6)
In the melting salt after carrying out chemical intensification treatment, add SODIUMNITRATE successively in the same manner as embodiment 1A-2 ~ 1A-6, carry out chemical intensification treatment, measure CS, DOL respectively.
(embodiment 7B-1 ~ 7B-6)
Glass is changed to alumina silicate glass, prepares melting salt in addition in the same manner as embodiment 7A-1 ~ 7A-6, carry out chemical intensification treatment, measure CS, DOL respectively.
[embodiment 8: add potassium pyrophosphate]
(embodiment 8A-1 ~ 8A-6)
The addition of potassium pyrophosphate trihydrate is made to be 6.7g (K
4p
2o
7content relative to saltpetre: 1 % by mole), carry out chemical intensification treatment in addition in the same manner as embodiment 7A-1 ~ 7A-6, measure CS, DOL respectively.
(embodiment 8B-1 ~ 8B-6)
The addition of potassium pyrophosphate trihydrate is made to be 6.7g (K
4p
2o
7content relative to saltpetre: 1 % by mole), carry out chemical intensification treatment in addition in the same manner as embodiment 7B-1 ~ 7B-6, measure CS, DOL respectively.
[embodiment 9: add potassium pyrophosphate]
(embodiment 9A-1 ~ 9A-6)
The addition of potassium pyrophosphate trihydrate is made to be 43.2g (K
4p
2o
7content relative to saltpetre: 6 % by mole), carry out chemical intensification treatment in addition in the same manner as embodiment 7A-1 ~ 7A-6, measure CS, DOL respectively.
(embodiment 9B-1 ~ 9B-6)
The addition of potassium pyrophosphate trihydrate is made to be 43.2g (K
4p
2o
7content relative to saltpetre: 6 % by mole), carry out chemical intensification treatment in addition in the same manner as embodiment 7B-1 ~ 7B-6, measure CS, DOL respectively.
The measurement result of embodiment 7 ~ 9 is shown in Table 4.
[table 4]
(evaluation in the life-span of melting salt)
The result of example 1 based on the comparison, when having carried out chemical intensification treatment by not adding other inorganic potassium salt in saltpetre melting salt, in melting salt Na ionic concn is (by NaNO
3be set as A (mole), by KNO
3the value of the A/ (A+B) when being set as B (mole)) be summarized in Fig. 1 with the relation of CS.According to the result of Fig. 1, for the CS of chemically reinforced glass, compared to soda-lime glass (comparative example 1A), alumina silicate glass (comparative example 1B) as one man obtains high value.Therefore, below, in order to confirm the effect of adding inorganic potassium salt in melting salt, use utilize the result of alumina silicate glass carry out after investigation.
Further, in comparative example 1B, the CS value utilizing the melting salt of original state (comparative example 1B-1) to give is 864MPa, therefore the CS value (800MPa) reducing about 10% than this value is set as the benchmark of deterioration state.That is, using CS value for the Na ion content (addition (% by mole) relative to SODIUMNITRATE) in melting salt during 800MPa is as the index in the life-span of melting salt, evaluate afterwards.
(in melting salt, adding the effect of potassium orthophosphate)
Based on the result of embodiment 1B, embodiment 2B and embodiment 3B, when having carried out chemical intensification treatment by adding potassium orthophosphate in saltpetre melting salt, Na is relative to saltpetre (KNO
3) addition (quality ppm) be summarized in Fig. 2 with the relation of CS obtained.In order to contrast, the relation for only having saltpetre, when namely not adding inorganic potassium salt also illustrates (comparative example 1B) together.
Further, by each relation of Fig. 2, be similar to by straight line, calculate the Na ion content (addition (% by mole) relative to SODIUMNITRATE) in melting salt when CS value reaches 800MPa respectively.And then, according to this Na ion content, will not add the benchmark (1.00 times) of situation (comparative example 1B-1) as the melting salt life-span of the inorganic potassium salt beyond saltpetre in melting salt, calculate life-span ratio.
In addition, by aforesaid method, calculate the whole ion-exchange capacities corresponding with potassium orthophosphate addition.Potassium orthophosphate due to the valence mumber of negatively charged ion be 3, when tradable potassium ion number is set as 1, potential Na-K ion-exchange capacity is 3.
Whole ion-exchange capacity=(potassium orthophosphate addition) × (potential Na-K ion-exchange capacity)
Above result is shown in Table 5.
Further, potassium orthophosphate is shown in Figure 3 with the relation of the life-span ratio (ratio when being 1.00 times by only having the lifetime settings of the melting salt of saltpetre) of melting salt relative to the addition (% by mole) of saltpetre.
[table 5]
According to Fig. 2; when not adding potassium orthophosphate in melting salt; along with the increase of the Na amount in melting salt; the reduction of the CS of chilled glass obviously (comparative example 1B); on the other hand; by adding potassium orthophosphate in advance in melting salt, the reduction of CS slowly (embodiment 1B, 2B and 3B).In addition, according to Fig. 3, along with the increase of the addition of potassium orthophosphate, the life effect of melting salt raises.
According to known above, add the long lifetime performance unusual effect of potassium orthophosphate for melting salt.
(in melting salt, adding the effect of salt of wormwood)
Based on the result of embodiment 4B, embodiment 5B and embodiment 6B, when having carried out chemical intensification treatment by adding salt of wormwood in saltpetre melting salt, Na is relative to saltpetre (KNO
3) addition (quality ppm) be summarized in Fig. 4 with the relation of CS obtained.In order to contrast, the relation by only having saltpetre, when namely not adding inorganic potassium salt also illustrates (comparative example 1B) together.
According to each relation of Fig. 4, as described above, be similar to by straight line, calculate the Na ion content in melting salt when CS value reaches 800MPa, and then calculate life-span ratio according to Na ion content.
In addition, according to aforesaid method, calculate the whole ion-exchange capacities corresponding with salt of wormwood addition.Salt of wormwood due to the valence mumber of negatively charged ion be 2, when thus tradable potassium ion number being set as 1, potential Na-K ion-exchange capacity is 2.
Whole ion-exchange capacity=(salt of wormwood addition) × (potential Na-K ion-exchange capacity)
Above result is shown in Table 6.
Further, by salt of wormwood relative to saltpetre (KNO
3) addition (% by mole) shown in Figure 5 with the relation of the life-span ratio (ratio when being 1.00 times by only having the lifetime settings of the melting salt of saltpetre) of melting salt.
[table 6]
According to Fig. 4, when not adding salt of wormwood in melting salt, along with the Na amount in melting salt increases, the reduction of the CS of chilled glass obviously (comparative example 1B), on the other hand, by adding salt of wormwood in advance in melting salt, the reduction of CS becomes slowly (embodiment 4B, 5B and 6B).In addition, according to Fig. 5, along with the increase of the addition of salt of wormwood, the life effect of melting salt raises.
According to known above, add the long lifetime performance unusual effect of salt of wormwood for melting salt.
(in melting salt, adding the effect of potassium pyrophosphate)
Based on the result of embodiment 4B, embodiment 5B and embodiment 6B, when having carried out chemical intensification treatment by adding potassium pyrophosphate in saltpetre melting salt, Na is relative to saltpetre (KNO
3) addition (quality ppm) be summarized in Fig. 6 with the relation of CS obtained.In order to contrast, the relation by only having saltpetre, when namely not adding inorganic potassium salt also illustrates (comparative example 1B) together.
According to each relation of Fig. 6, as described above, be similar to by straight line, calculate the Na ion content in melting salt when CS value reaches 800MPa, and then calculate life-span ratio according to Na ion content.
In addition, by aforesaid method, calculate the whole ion-exchange capacities corresponding with potassium pyrophosphate addition.Potassium pyrophosphate due to the valence mumber of negatively charged ion be 4, when therefore tradable potassium ion number being set as 1, potential Na-K ion-exchange capacity is 4.
Whole ion-exchange capacity=(potassium pyrophosphate addition) × (potential Na-K ion-exchange capacity)
Above result is shown in Table 7.
Further, by potassium pyrophosphate relative to saltpetre (KNO
3) addition (% by mole) shown in Figure 7 with the relation of the life-span ratio (ratio when being 1.00 times by only having the lifetime settings of the melting salt of saltpetre) of melting salt.
[table 7]
According to Fig. 6, when not adding potassium pyrophosphate in melting salt, along with the Na amount in melting salt increases, the reduction of the CS of chilled glass obviously (comparative example 1B), on the other hand, by adding potassium pyrophosphate in advance in melting salt, the reduction of CS becomes slowly (embodiment 7B, 8B and 9B).In addition, according to Fig. 7, along with the increase of the addition of potassium pyrophosphate, the life effect of melting salt raises.
According to known above, add the long lifetime performance unusual effect of potassium pyrophosphate for melting salt.
Gather above-mentioned, by shown in Figure 8 with the relation of the life-span ratio (ratio when being 1.00 times by only having the lifetime settings of the melting salt of saltpetre) of melting salt for whole ion-exchange capacities (valence mumber × addition (% by mole) of the anionic species added) of each inorganic potassium salt (anionic species) of the potassiumphosphate added in melting salt or salt of wormwood.
According to Fig. 8, these inorganic potassium salts are added in advance to the glass reinforced melting salt taking saltpetre as main component, the long life in life-span can be realized thus.Wherein, the life successful that brings of known potassium orthophosphate.
[comparative example 2: add SiO 2 powder]
(comparative example 2A-1 ~ 2A-4)
(comparative example 2A-1)
In the cup of SUS, add saltpetre 250g, utilize mantle heater be heated to 430 DEG C thus prepare melting salt.0.2g SiO 2 powder (SiO is added in the melting salt prepared thus
2content relative to saltpetre: 0.1 quality %), use stirring motor, four propeller blades stir two hours, leave standstill two hours.Then soda-lime glass is preheated to 100 DEG C, in the melting salt of 430 DEG C, dipping carries out chemical intensification treatment in 4 hours.Then the ion exchanged water of 100 DEG C is utilized to clean glass, 60 DEG C of dryings two hours.Measure CS, the DOL of this glass after chemical intensification treatment respectively.
(comparative example 2A-2 ~ 2A-4)
In the same manner as embodiment 7A-2 ~ 7A-4, in the melting salt after carrying out chemical intensification treatment, add SODIUMNITRATE successively, carry out chemical intensification treatment, measure CS, DOL respectively.
(comparative example 2B-1 ~ 2B-4)
Glass is changed to alumina silicate glass, prepares melting salt in addition in the same manner as comparative example 2A-1 ~ 2A-4, carry out chemical intensification treatment, measure CS, DOL respectively.
[comparative example 3: add SiO 2 powder]
(comparative example 3A-1 ~ 3A-4)
The addition of SiO 2 powder is made to be 25.1g (SiO
2content relative to saltpetre: 10 quality %), carry out chemical intensification treatment in addition in the same manner as comparative example 2A-1 ~ 2A-4, measure CS, DOL respectively.
(comparative example 3B-1 ~ 3B-4)
The addition of SiO 2 powder is made to be 25.1g (SiO
2content relative to saltpetre: 10 quality %), carry out chemical intensification treatment in addition in the same manner as comparative example 2B-1 ~ 2B-4, measure CS, DOL respectively.
The measurement result of comparative example 2A, 2B, 3A and 3B is shown in Table 8.
[table 8]
(in melting salt, adding the effect of silicon-dioxide)
The result of routine 2B, 3B based on the comparison, when having carried out chemical intensification treatment by adding silicon-dioxide in saltpetre melting salt, Na is relative to saltpetre (KNO
3) addition (quality ppm) shown in Figure 9 with the relation of CS obtained.In order to contrast, the relation by only having saltpetre, when namely not adding inorganic potassium salt also illustrates (comparative example 1B) together.
Further, according to each relation of Fig. 9, be similar to by straight line, calculate the Na ion content (addition (% by mole) relative to SODIUMNITRATE) in melting salt when CS value reaches 800MPa respectively.And then, according to this Na ion content, the situation (comparative example 1B-1) of not adding the inorganic potassium salt beyond saltpetre in melting salt is set as the benchmark (1.00 times) in melting salt life-span, calculates life-span ratio.
The above results are shown in table 9.
Further, by addition (the silicon-dioxide SiO of silicon-dioxide
2relative to saltpetre KNO
3addition (quality %)) shown in Figure 10 with the relation of the life-span ratio (ratio when being 1.00 times by only having the lifetime settings of the melting salt of saltpetre) of melting salt.
[table 9]
According to Fig. 9, when not adding inorganic salt in melting salt, along with the Na amount in melting salt increases, the reduction of the CS of chilled glass obviously (comparative example 1B), even if add silicon-dioxide in advance in melting salt, the reduction of CS also obviously (comparative example 2B, 3B).In addition, according to Figure 10, even if the addition of silicon-dioxide increases, the life effect of melting salt also almost can not be confirmed.
According to known above, add silicon-dioxide inoperative for the long lifetime of melting salt.
In detail and describe the present invention with reference to specific embodiment, but under the condition not departing from the spirit and scope of the present invention can various change in addition, amendment, this it will be apparent to those skilled in the art that.The Japanese patent application (Japanese Patent Application 2012-205039) that the application proposed based on September 18th, 2012, is incorporated in this by its content in the mode of reference.
Utilizability in industry
According to melting salt of the present invention, the CS value of giving glass can be made to remain the exchange frequency of the situation decline low melt salt of degree as in the past, repeatedly can be applied to the chemical intensification treatment of glass.Consequently can realize the raising of the cost degradation in the chemical intensification treatment of glass, productivity.
Claims (8)
1. a glass reinforced melting salt, for forming compressive stress layers by ion-exchange at glass surface, wherein,
This glass reinforced melting salt contains saltpetre, also containing at least one in carbonate anion and phosphate anion.
2. glass reinforced melting salt as claimed in claim 1, wherein, containing saltpetre, carbonate anion and phosphate anion.
3. glass reinforced melting salt as claimed in claim 1 or 2, wherein, described carbonate anion is the anionic species of salt of wormwood, and described phosphate anion is the anionic species of at least one in potassium orthophosphate and potassium pyrophosphate.
4. glass reinforced melting salt as claimed in claim 3, wherein, the content of described salt of wormwood is 3.5 ~ 24 % by mole relative to described saltpetre.
5. the glass reinforced melting salt as described in claim 3 or 4, wherein, the content of described potassium orthophosphate is 0.8 ~ 13.5 % by mole relative to described saltpetre.
6. the glass reinforced melting salt according to any one of claim 3 ~ 5, wherein, the content of described potassium pyrophosphate is 3.5 ~ 9.0 % by mole relative to described saltpetre.
7. a manufacture method for chilled glass, it comprises the glass reinforced melting salt used according to any one of claim 1 ~ 6 forms compressive stress layers operation at glass surface.
8. a life method for glass reinforced melting salt, will be used for the life being formed the glass reinforced melting salt of compressive stress layers by ion-exchange at glass surface, wherein,
At least one in containing the melting salt before the intensive treatment of saltpetre in mixed carbonic acid potassium and potassiumphosphate, makes containing at least one in carbonate anion and phosphate anion.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012205039 | 2012-09-18 | ||
| JP2012-205039 | 2012-09-18 | ||
| PCT/JP2013/074583 WO2014045978A1 (en) | 2012-09-18 | 2013-09-11 | Molten salt for use in toughening glass, production method of toughened glass, and life extension method of molten salt for use in toughening glass |
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|---|---|
| CN104661977A true CN104661977A (en) | 2015-05-27 |
| CN104661977B CN104661977B (en) | 2016-10-12 |
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|---|---|---|---|
| CN201380048664.9A Active CN104661977B (en) | 2012-09-18 | 2013-09-11 | Glass reinforced fuse salt, the manufacture method of strengthening glass and the life method of glass reinforced fuse salt |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JP5692463B2 (en) |
| KR (1) | KR20150058224A (en) |
| CN (1) | CN104661977B (en) |
| TW (1) | TW201414683A (en) |
| WO (1) | WO2014045978A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017147853A1 (en) * | 2016-03-03 | 2017-09-08 | 深圳市力沣实业有限公司 | High-strength chemically strengthened glass and glass strengthening method |
| CN111099840A (en) * | 2019-12-24 | 2020-05-05 | 维达力实业(深圳)有限公司 | Molten salt impurity removal method suitable for chemical tempering production and method for improving glass strength |
| WO2021115441A1 (en) * | 2019-12-11 | 2021-06-17 | 深圳市东丽华科技有限公司 | Salt bath impurity ion purification method |
| CN113727953A (en) * | 2019-04-26 | 2021-11-30 | Ａｇｃ株式会社 | Method for extending life of molten salt composition, method for producing chemically strengthened glass, glass auxiliary agent, and raw material for glass |
| US11242282B2 (en) | 2017-12-29 | 2022-02-08 | Guangdong Oppo Mobile Telecommunications Corp., Ltd. | Method for producing reinforced glass, reinforced glass and electronic device |
| CN114787095A (en) * | 2019-12-02 | 2022-07-22 | 康宁股份有限公司 | Method for reducing haze caused during ion exchange using carbonate salts |
| CN116002992A (en) * | 2022-12-29 | 2023-04-25 | 东莞市晶博光电股份有限公司 | Glass strengthening process capable of prolonging service life of furnace salt |
| CN116639889A (en) * | 2019-12-26 | 2023-08-25 | Ａｇｃ株式会社 | Method for producing chemically strengthened glass and lithium ion adsorbent |
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|---|---|---|---|---|
| TWI510443B (en) * | 2014-06-30 | 2015-12-01 | G Tech Optoelectronics Corp | Method for increasing strengthening behavior of glass |
| WO2016129729A1 (en) * | 2015-02-13 | 2016-08-18 | 엘지전자 주식회사 | Composition for preparing aluminosilicate tempered glass and method for tempering glass by using same |
| WO2018043361A1 (en) * | 2016-09-02 | 2018-03-08 | 旭硝子株式会社 | Method for producing chemically toughened glass |
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| JPH07330382A (en) * | 1994-06-03 | 1995-12-19 | Asahi Glass Co Ltd | Production of scuff-resistant glass molding |
| JP2013067555A (en) * | 2011-09-09 | 2013-04-18 | Hoya Corp | Method for producing cover glass for potable appliance |
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- 2013-09-11 WO PCT/JP2013/074583 patent/WO2014045978A1/en active Application Filing
- 2013-09-11 JP JP2014512208A patent/JP5692463B2/en active Active
- 2013-09-11 CN CN201380048664.9A patent/CN104661977B/en active Active
- 2013-09-11 KR KR1020157006828A patent/KR20150058224A/en not_active Application Discontinuation
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| US3791809A (en) * | 1973-01-12 | 1974-02-12 | Owens Illinois Inc | Method of strengthening glass articles using powdered salts for ion exchange |
| DD155766A3 (en) * | 1980-01-22 | 1982-07-07 | Olga V Sceglova | MELTING BELT FOR FASTENING GLASS PRODUCTS |
| JPS6110025A (en) * | 1984-06-23 | 1986-01-17 | Toagosei Chem Ind Co Ltd | Purification of aqueous solution |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017147853A1 (en) * | 2016-03-03 | 2017-09-08 | 深圳市力沣实业有限公司 | High-strength chemically strengthened glass and glass strengthening method |
| US11242282B2 (en) | 2017-12-29 | 2022-02-08 | Guangdong Oppo Mobile Telecommunications Corp., Ltd. | Method for producing reinforced glass, reinforced glass and electronic device |
| CN113727953A (en) * | 2019-04-26 | 2021-11-30 | Ａｇｃ株式会社 | Method for extending life of molten salt composition, method for producing chemically strengthened glass, glass auxiliary agent, and raw material for glass |
| CN113727953B (en) * | 2019-04-26 | 2023-06-27 | Ａｇｃ株式会社 | Method for prolonging life of molten salt composition, method for producing chemically strengthened glass, glass aid, and glass raw material |
| CN114787095A (en) * | 2019-12-02 | 2022-07-22 | 康宁股份有限公司 | Method for reducing haze caused during ion exchange using carbonate salts |
| WO2021115441A1 (en) * | 2019-12-11 | 2021-06-17 | 深圳市东丽华科技有限公司 | Salt bath impurity ion purification method |
| CN111099840A (en) * | 2019-12-24 | 2020-05-05 | 维达力实业(深圳)有限公司 | Molten salt impurity removal method suitable for chemical tempering production and method for improving glass strength |
| CN116639889A (en) * | 2019-12-26 | 2023-08-25 | Ａｇｃ株式会社 | Method for producing chemically strengthened glass and lithium ion adsorbent |
| CN116002992A (en) * | 2022-12-29 | 2023-04-25 | 东莞市晶博光电股份有限公司 | Glass strengthening process capable of prolonging service life of furnace salt |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2014045978A1 (en) | 2016-08-18 |
| CN104661977B (en) | 2016-10-12 |
| TW201414683A (en) | 2014-04-16 |
| JP5692463B2 (en) | 2015-04-01 |
| WO2014045978A1 (en) | 2014-03-27 |
| JP2014208591A (en) | 2014-11-06 |
| KR20150058224A (en) | 2015-05-28 |
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