The following companies were present or represented:

We would also like to thank for their presence and collaboration offered during the study:

Mr.Tinazzi, Chemical Engineer of the Chemical Laboratory of the Chamber of Commerce who put at our disposal the scanning electron microscope mentioned several times during this work.

Mr.Beltramino of C.I.A.T. who thanks to his twenty-year experience in the field of chlorinated solvents has given us precious help in the understanding of problems related to the use of halogen derivatives.

At the beginning of meeting participants were given a warm welcome and thanked for their active participation.

All tests carried out to find out the cause of the defects occurred over the last two years made it clear that the problem could not be solved by our company alone, but that it required the co-operation of all manufacturers. Based on this consideration we decided to summon this meeting - indeed the issue turned out to be far more complex than it was originally thought.

Each participant received a dossier summing up the topics to be dealt with during the meeting (subsequently the dossier formed the basis to draw up this book which is not meant to be a technical manual, nor an exhaustive analysis of all possible issues. It is just intended to become a term of reference for the future, to remember the findings of this work and the way it was communicated to all participants).

the aim of this meeting is not just solving now a problem cropped up in the past and explain its causes. The objective is to lay the basis for a future technical co-operation to prevent the occurrence of new problems that could indiscriminately affect manufacturers of tips, ink and finished products and undermine the image of us all.

We did our best to summon all manufacturers of the items involved in the production process of a pen, since it is only through perfect collaboration that the problem can be totally eradicated.

Many of you , despite your interest in the matter, could not participate because of various reasons, but they will receive a full account of the meeting. The topics and issues examined are both of a toxicological and environmental nature.

Toxicological problems that brought to the elimination of certain products belonging to the production process of ball-point pens.

There are environmental problems too because difficulties in the disposal of manufacturing by-products let to an inappropriate use of the products themselves.

During the opening speech, the opportunity was taken to thank two persons whose work has been essential to advance our research study:

- Mr.Tinazzi (expert in the use of the scanning electron microscope put at our disposal by the Chemical Laboratory of the Chamber of Commerce);

- Mr.Beltramino (who, thanks to his twenty-years experience in the field of chlorinated solvents, was extremely helpful in explaining the problems related to their use).

We divided the meeting into three main topics for discussion:

Mr.Buzzetti started up illustrating the specific issue and the results of tests reported in the first part of this text.

Subsequently, Mr.Tinazzi explained test procedures and will show the first findings.

Finally Mr.Beltramino went into the issue of chlorinated solvents, their properties and the most appropriate way of using them to avoid risks of any kind.

The opening speech was closed expressing the hope that the meeting could be helpful to all of us, not just to collect information on what REINOL discovered, but to promote an exchange of the experiences gathered so far by the different manufacturers.

Mr.Tinazzi started of f with a description of the research methodology used between January 1992 and June 1993 and briefly showed the instruments applied: a scanning electron microscope JEOL 6400 with a resolution power of about 100 A at 35 Kv and magnification potential up to 300.000x.

The scanning electron microscope (SEM) displays three-D images with a remarkable depth of field. Its monitor does not record primary electrons which would affect the sample being studied and possibly cross it, but the secondary electrons emitted by the sample following the clash of primary electron beams. Moreover secondary electrons, in contrast with primary electrons, are not to be focused but just collected.

Another advantage of this instrument is its wide range of magnification power (you can start from a very low magnification like 10-15x) that provides a more detailed analysis leaving the depth of field unchanged (notice the sharpness of Picture n. 21).

Since each element has a specific emission spectrum, X-ray were used to analyse the various materials. The detection system used in the tests carried out at the Chemical Laboratory of the Chamber of Commerce in Turin consists of an EDS probe (X energy dispersion spectrophotometer TRACOR Z-MAX 30).

With the conventional X-rays detection instruments elements like Carbon, Nitrogen, Oxigen, Fluorine, Litium, cannot be detected. For this reason a NORVAR window has been used through which these elements can pass despite the low energy of their radiations.

This system is made of two plates with a thin silicon-lithium crystal in-between: when an X radiation hits the crystal, its ionises it and generates a current specific to that element.

In the final tests carried our by the Chemical Laboratory of the Chamber of Commerce, tried to verify whether the defects registered up to that moment could be traced back to a single cause, that is the acid corrosion of ball-point pen tips caused by the inappropriate use of chlorinated solvents during washing. Based on this a thorough examination of the following samples was carried out:

a) Defective refills. nickel-plated tips and competitors' ink (Annex D Sample 1)

The tip taken from a defective refill was lightly washed with butanol so as to extract ink without affecting inner parts.

The washed tip was subsequently observed at the electronic microscope with two well-defined landmarks:

- Ball seat (See Picture n. 25);

- Inner wall behind the capillary duct (see Picture n. 26).

The analysis of Picture n. 25 reveals hollow formations and uneven profiles due to a starting corrosion process which becomes even more evident in the inner part of the tip where hollowness is much more visible and widespread (Picture n. 26).

b) Artificially polluted Reinol ink (see Annex D samples 2 and 3)

To conform the origin and chemical-physical constitution of this gelatinous mass, we artificially polluted our black ink 101/MG for ball-point pens with Zinc and Copper Chloride.

The ensuing mixture was analysed at the electronic microscope (Picture n. 27 and 28).

Especially in the case of contamination with Copper Chloride, the mass corresponds to the one already observed during previous observations of ink present in defective refills (Picture n. 5 and 30).

c) Defective refills: X-10 tips and Reinol ink (see Annex D sample 4).

We first examined the tip to check whether corrosion had already started or not.

The tip taken from a defective refill was lightly washed with butanol so as to extract the ink present without affecting inner walls.

The washed tip was subsequently observed at the electronic microscope with special attention to the part behind the capillary duct that in the previous examination had already yielded the most representative results (see Pictures n. 29).

Here again, the analysis of the walls reveals a clear on-going corrosion process, though less significant and widespread as against the tips of sample n. 1 (point a).

To obtain more accurate results, we also analysed the tip ink content already extracted at the washing stage.

The first microscopic observation showed that the ink mass was not homogeneous, but it had in it a gelatinous area which at a subsequent microscopic analysis (Picture n. 30) revealed the same physical structure detected in previous tests (see Picture n. 5).

We were able to set the constitution of this area thanks to the use of an EDS microprobe (Picture n. 31): the result points to the presence of copper and chlorine causing the gelling of ink.

The chlorine produced through an improper tip washing reacted with copper forming copper chloride. The latter reacts with ink carboxyl and generates carboxylates (metal soap). The final rheology is different from the original one and ink does not flow down smoothly in the duct.

To bear out this theoretical assumption the same analysis was carried out with ink of the same refill but taken from a different area, with no contact with the tip.

In this case the EDS test (see Picture n. 32) did not reveal the typical copper and chlorine peaks, meaning that the two elements are present only inside the tip and not in the original ink formulation.

d) Tips treated with hydrochloric acid (see Annex D sample 5).

To make sure that the root cause of all problems was really an acid etching of the tips produced during washing, we decided to reproduce the defect in the laboratory.

1 part of distilled water was mixed with 1 part of Methylene chloride previously extracted from the washing tank of a tip manufacturer.

The mixture thus obtained was shaken, and after the separation of the two solvents, water was used to dampen some good quality defect-free tips.

After 48 hours the tips of that lot were put directly under the electronic microscope to be observed.

Behind the capillary duct (Picture n. 33) you can already see the formation of saline efflorescence (whitish ramifications) which will react to the ink introduced into duct, leaving original sites empty and consequently forming hollow areas.

e) Non corroded X-10 tips (Annex D sample 6).

To obtain a further confirmation of this, a new test was performed with tips belonging to a lot of defect-free refills.

In this case there was no corrosion in the ball seat (Picture n.34), and even on the inner wall only rare corrosion sites are to be observed (Picture n.35).

- Corroded X-10 tips (see Annex D sample 7).

To confirm the presence or absence of oxidation in new tips, not yet filled with ink, the electronic microscope was used to observe new tips taken from lots with defective refills.

There are clear signs of corrosion and hollowness both in the ball seat (Picture n.36) and on the wall behind the capillary duct (Picture n.37). Please note the inappropriate machining of the ink feeding duct; it is obstructed and will not permit a normal ink flow.

There are already numerous crystalline formations of copper and zinc chlorides on the wall behind the inner duct, and if used to assemble refills they will react with ink.

Mr.Tinazzi closed his contribution showing to participants the above-mentioned pictures taken during recent tests.

Mr.Beltramino, who has a twenty-years experience in this specific sector, was invited to the meeting as expert in chlorinated solvents.

He opened his speech with a quick explanation of the main characteristics of chlorinated solvents and how they are industrially obtained.

After a short introduction, he quickly moved to the specific use of these solvents, emphasising the need of their appropriate use - "though stabilised chlorinated solvents are highly unstable".

It is very important to underline that chlorinated solvents, if correctly used and controlled, can yield exceptional results, if they are not properly used however, they can cause a lot of troubles.

The need was stressed to carry out regular checks of washing baths to prevent all the problems mentioned during this discussion.

To explain the remarkable strength of chlorinated solvents, reference was made to the borderline case of a plant manufacturing metal parts that had had serious corrosion problems because washing baths were very close to the production plant.

In that case it was enough to separate the washing department from the manufacturing one to sensitively limit the defect.

Mr.Beltramino moved then to illustrating the most well-known methods to control solvents and detect their acidity. Some of these methods have already been covered before.

The cleaning of the equipment is of paramount importance: the presence of brass powder in the bath may act as catalyst of the decomposition process and increase the acidity of the product.

The presence of oil in the washing bath proportionately increases the solvent boiling temperature. This require an increase in distillation temperature with a consequent greater risk of thermal decomposition.

When Mr.Beltramino ended his presentation, Mr.Rosso from R.P.R. (a company manufacturing tips for ball-point pens and refills of various kind), asked all participants to co-operate with Reinol in the future, so as to make it easier to perform tests and detect the cause of possible writing problems.

Mr.Rosso continued his speech asking Mr.Beltramino to explain the reason why such a serious defect has cropped up only very recently even though companies had been using the same working method fro twenty years.

Mr.Beltramino explained that the dismissal of the stabiliser known as 1,4-dioxan had, at least at first, increased the number of problems due to the corrosion of metal parts in every sector of the metal and steel industry.

In the past, the strong stabilisation power of 1,4-dioxan had counterbalanced the effects of inadequate washing.

At this point, Mr.Rosso reply asking for what reason the manufacturers of chlorinated solvents had not let the others know that this stabiliser had been replaced.

According to Mr.Beltramino, not only had these products been presented to all final users, but each manufacturer of chlorinated solvents tends now to emphasise the super-stability of hyper-stability of its solvents.

The owner of R.P.R. himself, who had been informed of the problem a few months before (he had taken part in the final stage of the tests together with Reinol), replaced the old solvent with another one, more suitable to that specific use and is still considering the use of special equipment to vacuum wash his tips (with this method the presence of steam is eliminated because the air re-entered in the machine is previously de-hydrated).

Thanks to a twenty-years experience in the field of washing machines using chlorinated solvents, Dr.Nicol could join to help the audience understand the issue better.

In his opinion, it is unthinkable that in certain companies the problems under study do not occur, since the use of chlorinated solvents is often inappropriate and the equipment, in most cases, unsuitable.

It is very important to update machines and equipments with necessary modifications, so as to limit as much as possible the thermal shock to which every solvent is subjected during heating stage.

He further recommended to avoid heating the solvent with heating elements that are the main cause of thermal decomposition.

to demonstrate this, he gave the example of washing machines for garments where the solvent was directly heated with heating elements. The latter became corroded and unusable in very short time. By contrast, heating carried out with steam coils, ensured a longer life of the equipment (even as long as ten years) manufactured in zinc-plated steel at the time.

Here again the pH control play a very important role.

Based on his personal experience, Dr.Nicol advised against the used of vacuum plants: results do not seem to live up to the expectations, especially with respect to separation at the aqueous stage.

This was also confirmed by Mr.Pagani of Universal. He also recommended to try and avoid the presence of water when working in total absence of thermal shocks.

The very interesting contribution by Mr.Dumusois stressed that Hauser too performed studies on the corrosion of roller tips.

The question was raised how can corrosion attack tips machined without using oil, unwashed and, what is more surprising, attack the un-machined part of the tip.

Mr.Buzzetti with the support of Mr.Rosso explained that over his latest visit to Boillat (manufacturer of brass bars), these problems had been touched upon. Apparently the manufacturers of brass themselves carry out the pickling of brass bars using chlorinated solvents (at the end of the extrusion process).

The reason why Mr.Dumusois observed corrosion in an un-machined part of the tip can be easily explained. In this case corrosion started at the brass bar manufacturing stage already.

At this point Mr.Santini raised a very interesting question: can the ink pH play an important role in corrosion?.

He pointed out that among German manufacturers there are two schools of thought in the formulation on ink fro ball-point pens: one prefers inks with an acid pH, the other a neutral or slightly alkaline pH.

Mr.Buzzetti replied that Reinol is familiar with both options and, in fact, it adopts both for the following reasons.

Many years ago tips were obtained from a brass tube by pressing. Brass used have a very high copper content, therefore inks with an acid pH were very good, whereas inks with a neutral or slightly alkaline pH had a limited shelf-life, a year approximately. In some cases neutral or alkaline inks yielded the best results, for instance when using tip manufactured in aluminium alloys.

Now both inks are being produced, but with corroded tips they raise the same problems.

Moreover the same defects have been registered in refills with ink formulated according to both theories.

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Picture n.

25 - 26 - 27 - 28 - 29 - 30 - 31 - 32 - 33 - 34 - 35 - 36 - 37

At the end of the meeting Reinol stated that a number of customers showed interest in the setting up of a centralised laboratory specialised in research and study of these issues and in products quality control.

To meet this need, Reinol suggested to utilise an already existing structure with highly qualified personnel specialised in this sector and made its own laboratory available.