Surface treatment method and application of glazed tile

文档序号:148708 发布日期:2021-10-26 浏览:38次 中文

阅读说明:本技术 一种釉面砖的表面处理方法及应用 (Surface treatment method and application of glazed tile ) 是由 柯善军 周营 马超 田维 朱志超 孙飞野 张缇 于 2021-07-01 设计创作,主要内容包括:本发明涉及陶瓷工艺技术领域,具体公开了一种釉面砖的表面处理方法及应用。釉面砖的表面处理方法,包括以下步骤:取钾盐、吸附剂和活化剂混合,并加热至熔融状态,得熔盐混合物;将釉面砖浸没于所述熔盐混合液中进行表面处理后取出,得表面处理的釉面砖。本发明将釉面砖浸没于低温熔盐混合物中,使釉层中的碱金属离子与熔盐混合物中的碱金属离子因互相扩散而发生离子交换,并使釉层表面产生压应力,从而实现釉面耐磨性能的增强。吸附剂可吸附釉层中的杂质离子,活化剂用于消除钾盐在离子交换过程中的钝化,从而进一步提高离子交换速率,钾盐、吸附剂和活化剂的协同增效作用,共同增强釉面砖的耐磨性能,适用于有釉陶瓷的表面处理。(The invention relates to the technical field of ceramic processes, and particularly discloses a surface treatment method and application of a glazed tile. The surface treatment method of the glazed tile comprises the following steps: mixing potassium salt, adsorbent and activating agent, and heating to a molten state to obtain a molten salt mixture; and immersing the glazed tile in the molten salt mixed solution for surface treatment, and taking out the glazed tile to obtain the surface-treated glazed tile. The glazed tile is immersed in the low-temperature molten salt mixture, so that the alkali metal ions in the glaze layer and the alkali metal ions in the molten salt mixture are subjected to ion exchange due to mutual diffusion, and the surface of the glaze layer generates compressive stress, thereby enhancing the wear resistance of the glaze. The adsorbent can adsorb impurity ions in the glaze layer, and the activator is used for eliminating the passivation of potassium salt in the ion exchange process, so that the ion exchange rate is further improved, the synergistic effect of the potassium salt, the adsorbent and the activator is realized, the wear resistance of the glazed tile is enhanced together, and the glaze ceramic surface treatment agent is suitable for the glazed ceramic surface treatment.)

1. A surface treatment method of a glazed tile is characterized by comprising the following steps:

s1, mixing potassium salt, an adsorbent and an activating agent, and heating to a molten state to obtain a molten salt mixture;

and S2, immersing the glazed tile into the molten salt mixed solution for surface treatment, and taking out the glazed tile to obtain the surface-treated glazed tile.

2. The method for surface treatment of glazed tile according to claim 1, wherein the potassium salt comprises KNO3、KCl、K2SO4At least one of (1).

3. The method for surface treatment of a glazed tile according to claim 2, wherein the method comprises the step of subjecting the glazed tile to a heat treatmentCharacterized in that the potassium salt accounts for 90 to 97 percent of the molten salt mixture in percentage by mass, and the KNO3、KCl、K2SO4The mass ratio of (55-65): (15-25): (10-20).

4. The method of claim 1, wherein the adsorbent comprises Al2O3

5. A surface treatment method for glazed tiles according to claim 1 or 4, characterised in that the adsorbent represents 0.2-3% by mass of the molten salt mixture.

6. The method of claim 1, wherein the activator comprises Sb2O3

7. A method of surface treatment of glazed tiles according to claim 1 or 6 characterised in that the activator is present in a mass percentage of 0.5-5% of the molten salt mixture.

8. The method as claimed in claim 1, wherein the temperature of the surface treatment in step S2 is 440-460 ℃.

9. The method for surface treatment of glazed tile according to claim 1, wherein the time of the surface treatment in step S2 is 7-9 hours.

10. Use of a method of surface treatment of a glazed tile as claimed in any one of claims 1 to 9 in glazed ceramics.

Technical Field

The invention relates to the technical field of ceramic processes, in particular to a surface treatment method and application of a glazed tile.

Background

The glazed tile is a ceramic tile which is formed by glazing the surface of a tile and firing at high temperature and high pressure, and the ceramic tile consists of a green body layer and a glazed layer. The glazed tile is suitable for various decoration means, is richer in color and pattern than polished tiles, and has the main defect of poor wear resistance. Because of the existence of the glazed layer on the surface of the glazed tile, the hardness is low, the wear resistance is poor, the use of the glazed tile is limited, and particularly when the glazed tile is used as a floor tile, scratches are easy to appear, and the glazed tile is not suitable for public places with large pedestrian volume.

At present, the methods for enhancing the surface wear resistance of glazed tiles in the prior art mainly comprise the following steps: the first method is to add superfine alumina or aluminum hydroxide wear-resistant medium into glaze to improve the wear resistance of the glaze, but the preparation process of the method is quite complex: firstly, the particle size of alumina or aluminum hydroxide is controlled, the alumina or aluminum hydroxide is dissolved in a glass phase when the particle size is too small, and a bulge is formed on a glaze surface when the particle size is too large; secondly, the cooling system is controlled, and the cooling system can influence crystallization; thirdly, taking the proportion of each component in the glaze into consideration, and precipitating a required wear-resistant crystalline phase in the cooling process; the second method is to add the frit into the transparent glaze to improve the wear resistance of the glaze, and the method has high requirements on the quality of the frit, and the quality of the frit has great influence on the melting temperature range of the glaze and the glossiness and whiteness of the glaze, so that the method is not easy to control.

Therefore, it is desirable to provide a new method for surface treatment of a glazed tile, so as to improve the wear resistance of the glazed tile and facilitate the application of the glazed tile.

Disclosure of Invention

The invention provides a surface treatment method and application of a glazed tile, which aim to solve one or more technical problems in the prior art and at least provide a beneficial choice or creation condition.

In order to overcome the technical problems, the technical scheme adopted by the invention is as follows:

a surface treatment method of a glazed tile comprises the following steps:

s1, mixing potassium salt, an adsorbent and an activating agent, and heating to a molten state to obtain a molten salt mixture;

and S2, immersing the glazed tile into the molten salt mixed solution for treatment, and taking out the glazed tile to obtain the glazed tile with the treated surface.

The invention discloses a glazed tile surface treatment method, which comprises the following steps: the glaze layer of the glazed tile contains alkali metal ions, the glazed tile is immersed in the molten salt mixture for treatment, in the treatment process, the alkali metal ions in the glaze layer and the alkali metal ions in the molten salt mixture are subjected to ion exchange due to mutual diffusion, the alkali metal ions are relatively active, in the heated molten salt mixture, the activation energy of the alkali metal ions is increased, and Na in the glaze layer+K in molten salt mixture is separated out from the inside of glaze layer+Entering into a three-dimensional network structure of glaze layer glass, and obtaining the K with larger radius in a molten salt mixture+Replacing Na with smaller radius in the glaze layer+And large ions are 'plugged' into the original small ions, so that the density of the glaze surface is increased, and compressive stress is generated, thereby enhancing the wear resistance of the glaze surface. Meanwhile, the molten salt mixture is formed by heating and melting sylvite, an adsorbent and an activator, wherein: the potassium salt being K in said ion exchange+The adsorbent can adsorb impurity ions in the glaze layer, and the activator has the function of eliminating the passivation of potassium salt in the ion exchange process, so that the ion exchange rate is improved, the synergistic effect of the potassium salt, the adsorbent and the activator is realized, and the wear resistance of the glaze surface is enhanced together.

As a further improvement of the above, the potassium salt comprises KNO3、KCl、K2SO4At least one of (1).

In particular, different potassium salts have different effects on enhancing the wear resistance of the glaze, wherein KNO3、KCl、K2SO4The strengthening effect of the mixed salt of the three is optimal and is better than that of a single potassium salt or the combination of any two salts, so that the potassium salt is preferably KNO3、KCl、K2SO4The mixed salt of (1). The reason for thisThe method comprises the following steps: KNO3Impurity pair K in+-Na+Exchange generating blocking and inhibiting effects, Cl-、SO4 2-Can react with impurities to generate precipitates, thereby eliminating the obstruction of the impurities to ion exchange. At the same time, KNO3Has a melting temperature of 400 ℃ and a melting temperature of KCl of 770 ℃ and K2SO4The melting temperature of the three is 1069 ℃, the eutectic mixed salt is formed after the three are mixed, and the melting temperature is lower than 400 ℃. Therefore, the melting temperature can be effectively reduced by mixing the three components.

As a further improvement of the scheme, the potassium salt accounts for 90-97 percent of the molten salt mixture in percentage by mass, and the KNO3、KCl、K2SO4The mass ratio of (55-65): (15-25): (10-20).

In particular, potassium salt is used as the main component of the molten salt mixture to better ensure the full performance of ion exchange, and specific KNO is selected3、KCl、K2SO4The mass ratio of the three components is utilized, the synergistic effect of the three components is exerted, the obstruction of impurities to ion exchange can be further eliminated, eutectic is formed, and the melting temperature is reduced.

As a further improvement of the above aspect, the adsorbent comprises Al2O3

Specifically, Al2O3As adsorbent, the glaze surface shows selective adsorption to different cations in the molten salt mixture, Ca2+、Sr2+、Ba2+Collecting impurity ions on the surface of the glaze layer to inhibit ion exchange, and adding a certain amount of Al2O3Can adsorb impurity ions on the surface of the glaze layer.

Further, the adsorbent accounts for 0.2-3% of the molten salt mixture by mass percent, and too much or too little adsorbent is not beneficial to Al2O3Adsorption to impurity ions.

As a further improvement of the above, the activator comprises Sb2O3

Specifically, the activator is preferably Sb2O3Wherein the function of the molten salt mixture is mainly to eliminate the passivation of potassium salt in the ion exchange process, thereby improving the ion exchange rate. KNO3KNO is generated during the heating process2And O2Oxygen adhering to the glaze surface affects K in the molten salt mixture+With Na in the glaze layer+Exchange of (1), addition of Sb2O3Then, Sb2O3And O2Chemical reaction occurs to generate Sb2O5Thereby eliminating the effect of oxygen on ion exchange.

Further, the activator accounts for 0.5-5% of the molten salt mixture by mass percent, and the specific dosage of the activator is favorable for better increasing the ion exchange rate.

As a further improvement of the above scheme, the temperature of the surface treatment in the step S2 is 440-460 ℃.

In particular, when the glaze is treated at different temperatures, the ion exchange rate increases and then decreases as the temperature increases and the time increases, because: under the condition of unchanging time, when the exchange temperature is lower, the ion exchange activation energy is low, the barrier can not be crossed, the diffusion is not completely carried out in the exchange process, and enough surface pressure stress can not be formed on the surface of the glaze layer, so that the strength is not high; along with the increase of the exchange temperature, the ion exchange activation energy is increased, the exchange capacity in unit time is increased, the compression stress layer is thickened, and the strength is improved; with the continuous increase of the temperature, the glaze layer structure is relaxed, and potassium ions and sodium ions are rearranged or migrated to generate stress relaxation, so that the strength is reduced; the effect of exchange time on intensity can be divided into three phases: in the initial stage of exchange, the strength increases with the extension of the exchange time, which is the first stage in which the increase in the compressive stress due to ion exchange is the main factor; in the second stage, the exchange time is prolonged, the increase of the compressive stress generated by exchange and the reduction of the stress caused by stress relaxation reach balance, and the strength tends to be stable; in the third stage, stress relaxation will become a major factor, and the strength decreases with further time. The stress will disappear when the time is extended indefinitely. Therefore, the preferred treatment temperature is 440-.

Further, the time of the surface treatment in step S2 is 7 to 9 hours, and the ion exchange rate is optimized during the treatment time.

As a further improvement of the above, the melting reaction vessel of step S1 is an aluminum salt bath or a silver salt bath, and other metal materials are easily corroded by molten salt, and thus are not suitable for use as a salt bath. Meanwhile, the aluminum salt tank is preferable because the cost of the silver salt tank is high.

The invention also provides a technical scheme that the surface treatment method of the glazed tile is applied to glazed ceramics to improve the wear resistance of the glazed ceramics surface.

Compared with the prior art, the invention at least has the following technical effects or advantages:

the glazed tile is immersed in the low-temperature molten salt mixture, so that the alkali metal ions in the glaze layer and the alkali metal ions in the molten salt mixture are subjected to ion exchange due to mutual diffusion, and the surface of the glaze layer generates compressive stress, thereby enhancing the wear resistance of the glaze. Meanwhile, the adsorbent in the molten salt mixture can adsorb impurity ions in the glaze layer, and the activating agent is used for eliminating the passivation of potassium salt in the ion exchange process, so that the ion exchange rate is further improved, the synergistic effect of the potassium salt, the adsorbent and the activating agent is realized, and the wear resistance of the glazed tile is enhanced together.

The glazed tile surface treatment method has the advantages of strong controllability, simple operation and low equipment requirement, and cannot influence the glossiness and whiteness of the glaze.

Detailed Description

The present invention is described in detail below by way of examples to facilitate understanding of the present invention by those skilled in the art, and it is to be specifically noted that the examples are provided only for the purpose of further illustrating the present invention and are not to be construed as limiting the scope of the present invention.

Example 1

A surface treatment method of a glazed tile comprises the following steps:

s1, firstly, weighing and mixing raw materials of sylvite, an adsorbent and an activating agent, wherein the raw materials comprise the following components in percentage by weight: 95% of potassium salt, 1.5% of adsorbent and 3.5% of activating agent, wherein the potassium salt is KNO3、KCl、K2SO4Mixed salt of the three, and KNO3、KCl、K2SO4The mass ratio of (A) to (B) is 63: 22: 15, the adsorbent is Al2O3The activator is Sb2O3(ii) a Then, the raw materials are put into an aluminum salt tank to be uniformly mixed, and are heated to 450 ℃ for melting to obtain a molten salt mixture;

s2, immersing the glazed tile in the molten salt mixed solution for treatment, taking out, immersing at 450 ℃ for 8 hours, taking out, cooling to room temperature, and cleaning the surface to obtain the glazed tile with the treated surface.

Example 2 (lower treatment temperature relative to example 1)

A surface treatment method of a glazed tile comprises the following steps:

s1, firstly, weighing and mixing raw materials of sylvite, an adsorbent and an activating agent, wherein the raw materials comprise the following components in percentage by weight: 95% of potassium salt, 1.5% of adsorbent and 3.5% of activating agent, wherein the potassium salt is KNO3、KCl、K2SO4Mixed salt of the three, and KNO3、KCl、K2SO4The mass ratio of (A) to (B) is 63: 22: 15, the adsorbent is Al2O3The activator is Sb2O3(ii) a Then, the raw materials are put into an aluminum salt tank to be uniformly mixed, and are heated to 400 ℃ for melting to obtain a molten salt mixture;

s2, immersing the glazed tile in the molten salt mixed solution for treatment, taking out, immersing at 400 ℃ for 8 hours, taking out, cooling to room temperature, and cleaning the surface to obtain the glazed tile with the treated surface.

Example 3 (higher treatment temperature relative to example 1)

A surface treatment method of a glazed tile comprises the following steps:

s1, firstly, weighing and mixing raw materials of sylvite, an adsorbent and an activating agent, wherein the raw materials comprise the following components in percentage by weight: 95% of potassium salt, 1.5% of adsorbent and 3.5% of activating agent, wherein the potassium salt is KNO3、KCl、K2SO4Mixed salt of the three, and KNO3、KCl、K2SO4The mass ratio of (A) to (B) is 63: 22: 15, the adsorbent is Al2O3The activator is Sb2O3(ii) a Then, the raw materials are put into an aluminum salt tank to be uniformly mixed, and are heated to 400 ℃ for melting to obtain a molten salt mixture;

and S2, immersing the glazed tile in the molten salt mixed solution for treatment, taking out, immersing at 480 ℃ for 8 hours, taking out, cooling to room temperature, and cleaning the surface to obtain the glazed tile with the treated surface.

Example 4 (less treatment time compared to example 1)

A surface treatment method of a glazed tile comprises the following steps:

s1, firstly, weighing and mixing raw materials of sylvite, an adsorbent and an activating agent, wherein the raw materials comprise the following components in percentage by weight: 95% of potassium salt, 1.5% of adsorbent and 3.5% of activating agent, wherein the potassium salt is KNO3、KCl、K2SO4Mixed salt of the three, and KNO3、KCl、K2SO4The mass ratio of (A) to (B) is 63: 22: 15, the adsorbent is Al2O3The activator is Sb2O3(ii) a Then, the raw materials are put into an aluminum salt tank to be uniformly mixed, and are heated to 450 ℃ for melting to obtain a molten salt mixture;

s2, immersing the glazed tile in the molten salt mixed solution for treatment, taking out, immersing at 450 ℃ for 5 hours, taking out, cooling to room temperature, and cleaning the surface to obtain the glazed tile with the treated surface.

Example 5 (more treatment time than in example 1)

A surface treatment method of a glazed tile comprises the following steps:

s1, firstly, weighing the originalMixing potassium salt, an adsorbent and an activating agent, wherein the raw materials comprise the following components in percentage by weight: 95% of potassium salt, 1.5% of adsorbent and 3.5% of activating agent, wherein the potassium salt is KNO3、KCl、K2SO4Mixed salt of the three, and KNO3、KCl、K2SO4The mass ratio of (A) to (B) is 63: 22: 15, the adsorbent is Al2O3The activator is Sb2O3(ii) a Then, the raw materials are put into an aluminum salt tank to be uniformly mixed, and are heated to 450 ℃ for melting to obtain a molten salt mixture;

s2, immersing the glazed tile in the molten salt mixed solution for treatment, taking out, immersing at 450 ℃ for 10 hours, taking out, cooling to room temperature, and cleaning the surface to obtain the glazed tile with the treated surface.

Example 6 (use of other salt baths than example 1)

A surface treatment method of a glazed tile comprises the following steps:

s1, firstly, weighing and mixing raw materials of sylvite, an adsorbent and an activating agent, wherein the raw materials comprise the following components in percentage by weight: 95% of potassium salt, 1.5% of adsorbent and 3.5% of activating agent, wherein the potassium salt is KNO3、KCl、K2SO4Mixed salt of the three, and KNO3、KCl、K2SO4The mass ratio of (A) to (B) is 63: 22: 15, the adsorbent is Al2O3The activator is Sb2O3(ii) a Then, the raw materials are put into a copper salt tank to be uniformly mixed, and are heated to 450 ℃ for melting to obtain a molten salt mixture;

s2, immersing the glazed tile in the molten salt mixed solution for treatment, taking out, immersing at 450 ℃ for 8 hours, taking out, cooling to room temperature, and cleaning the surface to obtain the glazed tile with the treated surface.

Example 7 (use of a single potassium salt as opposed to example 1)

S1, firstly, weighing and mixing raw materials of sylvite, an adsorbent and an activating agent, wherein the raw materials comprise the following components in percentage by weight: 95% of potassium salt, 1.5% of adsorbent and 3.5% of activating agent, wherein the potassium salt is KNO3The adsorbent is Al2O3The activator is Sb2O3(ii) a Then, the raw materials are put into an aluminum salt tank to be uniformly mixed, and are heated to 450 ℃ for melting to obtain a molten salt mixture;

s2, immersing the glazed tile in the molten salt mixed solution for treatment, taking out, immersing at 450 ℃ for 8 hours, taking out, cooling to room temperature, and cleaning the surface to obtain the glazed tile with the treated surface.

Example 8 (two potassium salts used in comparative example 1)

S1, firstly, weighing and mixing raw materials of sylvite, an adsorbent and an activating agent, wherein the raw materials comprise the following components in percentage by weight: 95% of potassium salt, 1.5% of adsorbent and 3.5% of activating agent, wherein the potassium salt is KNO3KCl, the adsorbent is Al2O3The activator is Sb2O3(ii) a Then, the raw materials are put into an aluminum salt tank to be uniformly mixed, and are heated to 450 ℃ for melting to obtain a molten salt mixture;

s2, immersing the glazed tile in the molten salt mixed solution for treatment, taking out, immersing at 450 ℃ for 8 hours, taking out, cooling to room temperature, and cleaning the surface to obtain the glazed tile with the treated surface.

Example 9

A surface treatment method of a glazed tile comprises the following steps:

s1, firstly, weighing and mixing raw materials of sylvite, an adsorbent and an activating agent, wherein the raw materials comprise the following components in percentage by weight: 92% of potassium salt, 3% of adsorbent and 5% of activating agent, wherein the potassium salt is KNO3、KCl、K2SO4Mixed salt of the three, and KNO3、KCl、K2SO4The mass ratio of (A) to (B) is 63: 22: 15, the adsorbent is Al2O3The activator is Sb2O3(ii) a Then, the raw materials are put into an aluminum salt tank to be uniformly mixed, and are heated to 440 ℃ for melting to obtain a molten salt mixture;

s2, immersing the glazed tile in the molten salt mixed solution for treatment, taking out, immersing at 440 ℃ for 7 hours, taking out, cooling to room temperature, and cleaning the surface to obtain the glazed tile with the treated surface.

Example 10

A surface treatment method of a glazed tile comprises the following steps:

s1, firstly, weighing and mixing raw materials of sylvite, an adsorbent and an activating agent, wherein the raw materials comprise the following components in percentage by weight: 97% of potassium salt, 0.5% of adsorbent and 2.5% of activating agent, wherein the potassium salt is KNO3、KCl、K2SO4Mixed salt of the three, and KNO3、KCl、K2SO4The mass ratio of (A) to (B) is 63: 22: 15, the adsorbent is Al2O3The activator is Sb2O3(ii) a Then, the raw materials are put into an aluminum salt tank to be uniformly mixed, and are heated to 460 ℃ for melting to obtain a molten salt mixture;

s2, immersing the glazed tile in the molten salt mixed solution for treatment, taking out, immersing at 460 ℃ for 9 hours, taking out, cooling to room temperature, and cleaning the surface to obtain the glazed tile with the treated surface.

Comparative example 1 (No activator addition relative to example 1)

A surface treatment method of a glazed tile comprises the following steps:

s1, firstly, weighing and mixing raw materials of sylvite and an adsorbent, wherein the raw materials comprise the following components in percentage by weight: 98.5 percent of potassium salt and 1.5 percent of adsorbent, wherein the potassium salt is KNO3、KCl、K2SO4Mixed salt of the three, and KNO3、KCl、K2SO4The mass ratio of (A) to (B) is 63: 22: 15, the adsorbent is Al2O3The activator is Sb2O3(ii) a Then, the raw materials are put into an aluminum salt tank to be uniformly mixed, and are heated to 450 ℃ for melting to obtain a molten salt mixture;

s2, immersing the glazed tile in the molten salt mixed solution for treatment, taking out, immersing at 450 ℃ for 8 hours, taking out, cooling to room temperature, and cleaning the surface to obtain the glazed tile with the treated surface.

Comparative example 2 (No adsorbent added with respect to example 1)

A surface treatment method of a glazed tile comprises the following steps:

s1, firstly, weighing raw material sylvite and an activating agent, and mixing the raw material sylvite and the activating agentThe percentage is as follows: 96.5 percent of potassium salt and 3.5 percent of activating agent, wherein the potassium salt is KNO3、KCl、K2SO4Mixed salt of the three, and KNO3、KCl、K2SO4The mass ratio of (A) to (B) is 63: 22: 15, the adsorbent is Al2O3The activator is Sb2O3(ii) a Then, the raw materials are put into an aluminum salt tank to be uniformly mixed, and are heated to 450 ℃ for melting to obtain a molten salt mixture;

s2, immersing the glazed tile in the molten salt mixed solution for treatment, taking out, immersing at 450 ℃ for 8 hours, taking out, cooling to room temperature, and cleaning the surface to obtain the glazed tile with the treated surface.

Product wear resistance detection

The wear resistance test method comprises the following steps: adopt LM-8 abrasion tester, press from both sides glazed tile's glaze upwards under metal fixture, add grinding medium in the charge door from the anchor clamps top, cover the lid and prevent grinding medium loss, set up the preset revolution of sample. And after the preset revolution number is reached, taking down the sample, cleaning the sample, and drying the sample in a drying oven at 110 +/-5 ℃. And measuring the mass before and after the friction by a constant balance to quantitatively characterize the wear resistance of the surface of the ceramic glaze.

The surface-treated glazed tiles obtained in examples 1 to 10 and comparative examples 1 to 2 were respectively subjected to the relevant property tests, and the test results are shown in table 1 below.

TABLE 1 comparison table of abrasion resistance of glazed tile before and after treatment of each example and comparative example

Glazed tile Abrasion before surface treatment (%) Surface treatment after abrasion (%)
Example 1 -0.11±0.01 -0.04±0.01
Example 2 -0.11±0.01 -0.07±0.01
Example 3 -0.11±0.01 -0.08±0.01
Example 4 -0.11±0.01 -0.09±0.01
Example 5 -0.11±0.01 -0.07±0.01
Example 6 -0.11±0.01 -0.09±0.01
Example 7 -0.11±0.01 -0.08±0.01
Example 8 -0.11±0.01 -0.07±0.01
Example 9 -0.11±0.01 -0.06±0.01
Example 10 -0.11±0.01 -0.05±0.01
Comparative example 1 -0.11±0.01 -0.11±0.01
Comparative example 2 -0.11±0.01 -0.10±0.01

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are intended to be within the scope of the invention.

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